TWI832965B - Adhesive, manufacturing method of intermediate laminate and intermediate laminate - Google Patents

Abstract

The adhesive of the present invention includes an adhesive polymer as a polymer of monomer components, a compound colored by an acid, and an acid generator. The glass transition temperature of the adhesive polymer is below 0°C. The shear storage modulus G' at 20°C to 50°C is 1.0×10 ⁴ Pa or more and 1.0×10 ⁶ Pa or less.

Description

Adhesive, manufacturing method of intermediate laminate and intermediate laminate

The present invention relates to an adhesive, a method for manufacturing an intermediate laminated body, and an intermediate laminated body. Specifically, it relates to an adhesive, a method for manufacturing an intermediate laminated body obtained by using an adhesive layer containing the adhesive, and the intermediate laminated body. The intermediate laminated body obtained by the manufacturing method of the laminated body.

In recent years, displays equipped with organic EL (Electroluminescence, electroluminescence) panels have been known. The organic EL panel has a highly reflective electrode layer, so it is easy to reflect external light or reflect the background.

Furthermore, it is known to provide a layer (light absorption layer) having a function of absorbing light on the reflective surface of the electrode layer in order to prevent reflection of external light or reflection of the background.

As such a light-absorbing layer, a light-absorbing layer containing a carbon black pigment and a dye has been proposed (for example, see Patent Document 1). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-203810

[Problem to be solved by the invention]

On the other hand, when the layer having the function of absorbing light is an adhesive layer, transparency may be required from the viewpoint of inspection, etc.

The present invention provides an adhesive that can be colored by irradiating active light at any time, a method for manufacturing an intermediate laminated body obtained by using an adhesive layer containing the adhesive, and a method for manufacturing the intermediate laminated body. The intermediate layered body. [Technical means to solve problems]

The present invention [1] is an adhesive which contains an adhesive polymer as a monomer component, a compound colored by an acid, and an acid generator, and the glass transition temperature of the adhesive polymer is 0°C or lower. , and the shear storage modulus G' at 20°C to 50°C is 1.0×10 ⁴ Pa or more and 1.0×10 ⁶ Pa or less.

The present invention [2] includes the adhesive agent according to the above [1], wherein the monomer component includes an acidic vinyl monomer having an anionic group.

The present invention [3] includes the adhesive as described in the above [1] or [2], wherein the above monomer component does not substantially contain a basic vinyl monomer having a lone electron pair.

The present invention [4] includes a method for manufacturing an intermediate laminated body, which includes the following steps: a preparation step, which is to prepare an adhesive layer containing the adhesive described in any one of the above [1] to [3]; and an irradiation step, It is to irradiate the above-mentioned adhesive layer with active rays to form a high-irradiation part where the irradiation amount of active rays is relatively high, and an unirradiated/low-irradiation part where the irradiation amount of active rays is relatively low or where no active rays are irradiated. , thereby making the visible light transmittance at the wavelength of 550 nm of the above-mentioned high-irradiation part smaller than the visible light transmittance at the wavelength of 550 nm of the above-mentioned non-irradiation/low-irradiation part; and the laminating step, which is to stick the other side of the above-mentioned adhesive layer Suitable for the adherend.

The present invention [5] includes the method for manufacturing an intermediate laminated body as described in the above [4], wherein the irradiation step is performed after the preparation step, and the laminating step is performed after the irradiation step.

The present invention [6] includes the method for manufacturing an intermediate laminated body according to the above [4], wherein the laminating step is performed after the preparation step, and the irradiation step is performed after the laminating step.

The present invention [7] includes the method for manufacturing an intermediate laminated body as described in the above [6], wherein in the irradiation step, the adhesive layer is irradiated with active light from the surface side of the adhesive layer.

The present invention [8] includes the method for manufacturing an intermediate laminated body as described in the above [6], wherein in the irradiation step, the adhesive layer is irradiated with active light from the surface side of the adherend.

The present invention [9] includes the method for manufacturing an intermediate laminated body as described in the above [8], wherein the average transmittance of active light of the adherend is 60% or more, and in the irradiation step, the adherend is After arranging a mask to block the active light on a part of the other side, the above-mentioned adhesive layer is irradiated with the active light.

The present invention [10] includes the method for manufacturing an intermediate laminated body as described in the above [8], characterized in that the adherend blocks active light, and in the laminating step, the adherend is disposed on the adhesive part of the other side of the layer.

The present invention [11] includes the method for manufacturing an intermediate laminated body according to any one of the above [4] to [10], wherein the non-irradiated/low-irradiated portion is an unirradiated portion that is not irradiated with active light, and the above-mentioned unirradiated portion The visible light transmittance of the irradiated part at a wavelength of 550 nm is over 80%.

The present invention [12] includes the method for manufacturing an intermediate laminated body according to any one of the above [4] to [9], wherein the non-irradiated/low-irradiated portion is a low-irradiated portion with a low irradiation amount of active light, and the irradiated portion The steps include: a first irradiation step, which is to irradiate the above-mentioned adhesive layer with active rays by arranging a first mask that blocks active rays, so as to form a first irradiation part irradiated with active rays on the above-mentioned adhesive layer, and a first irradiation part that is not irradiated to the part that has not yet been irradiated with active rays; and a second irradiation step, which involves irradiating the above-mentioned part of the adhesive layer that has not yet been irradiated with active rays by arranging a second mask that blocks the active rays at the above-mentioned first irradiation part. , so that the temporarily unirradiated part is formed as the second irradiated part; and any one of the first irradiated part and the second irradiated part is the high irradiated part, and the other is the low irradiated part.

The present invention [13] includes the method for manufacturing an intermediate laminated body according to any one of the above [4] to [9], wherein the non-irradiated/low-irradiated portion is a low-irradiated portion with a low irradiation amount of active light, and the irradiated portion The steps include: a third irradiation step, which is performed by irradiating the entire adhesive layer with active light, so that the entire adhesive layer is formed into a third irradiated portion that is irradiated with the active light; and a fourth irradiation step, which is performed by irradiating the entire adhesive layer with active light. Since a mask that blocks the active light is disposed in a part of the third irradiation part and the remaining part of the third irradiation part is irradiated with active ray, the remaining part of the third irradiation part is formed into a fourth irradiation part; and the above-mentioned The third irradiation part is the low irradiation part, and the fourth irradiation part is the high irradiation part.

The present invention [14] includes the method for manufacturing an intermediate laminated body as described in the above [12] or [13], wherein the visible light transmittance at a wavelength of 550 nm in the high irradiation part is less than 20%, and the wavelength of the low irradiation part is The visible light transmittance at 550 nm is above 20% and below 70%.

The present invention [15] includes an intermediate laminate having an adhesive layer containing the adhesive agent according to any one of [1] to [3] above, and an adherend arranged on the other side of the adhesive layer, and The above-mentioned adhesive layer has a high light transmittance portion with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion with a relatively small visible light transmittance at a wavelength of 550 nm.

The present invention [16] includes the intermediate laminate according to the above [15], wherein the low light transmittance portion has a pattern shape.

The present invention [17] includes the intermediate laminate according to the above [15] or [16], wherein the visible light transmittance at a wavelength of 550 nm in the high light transmittance portion is 80% or more.

The present invention [18] includes the intermediate laminate as described in the above [15] or [16], wherein the visible light transmittance at the wavelength of 550 nm in the low light transmittance part is less than 20%, and the visible light transmittance in the wavelength of 550 nm in the high light transmittance part is The visible light transmittance at nm is above 20% and below 70%. [Effects of the invention]

The adhesive of the present invention includes an adhesive polymer, a compound colored by an acid, and an acid generator.

The acid generator is a compound that generates acid by irradiation with active light or heating. The compound that is colored by acid is specifically a compound that changes from colorless (transparent) to colored by acid.

Therefore, the adhesive generates acid from the acid generator by irradiation with active light or heating, and the compound colored by the acid is colored by the acid, thereby changing from colorless (transparent) to colored.

In this way, according to this adhesive, it can be colored by irradiating active light at any time.

Furthermore, the glass transition temperature of the adhesive polymer in the present invention is 0°C or lower.

Therefore, the step followability is excellent.

Furthermore, the adhesive polymer in the present invention has a shear storage modulus G′ at 20°C to 50°C of 1.0×10 ⁴ Pa or more and 1.0×10 ⁶ Pa or less.

Therefore, the adhesion is excellent, and when the shear storage modulus G' is lower, the step followability is also excellent.

The manufacturing method of the intermediate laminated body of this invention includes the preparation step of preparing the adhesive layer containing the adhesive agent of this invention.

Therefore, the adhesive layer can be colored by irradiating the adhesive layer with active light.

Furthermore, the method for manufacturing the intermediate laminated body includes an irradiation step in which the adhesive layer forms a high-irradiation portion where the irradiation amount of active rays is relatively high, and the irradiation amount of active rays is relatively low or the active rays are not irradiated. The unirradiated/lowly irradiated part of the light makes the visible light transmittance at the wavelength of 550 nm in the highly irradiated part smaller than the visible light transmittance at the wavelength of 550 nm in the unirradiated/lowly irradiated part.

Therefore, it is possible to leave the colored portion in the adhesive layer transparently or to make the coloring amount smaller than the colored portion.

In the intermediate laminate of the present invention, the adhesive layer has a high light transmittance portion with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion with a relatively small visible light transmittance at a wavelength of 550 nm.

Therefore, the adhesive layer in the intermediate laminate has a function of absorbing light in the colored part, and has transparency outside the colored part or a function of absorbing light lower than that of the colored part.

1. Adhesive The adhesive of the present invention includes an adhesive polymer, a compound colored by an acid, and an acid generator.

The adhesive polymer is formulated to impart adhesiveness to the adhesive.

Examples of adhesive polymer monomer components (described below) include acrylic polymers, silicone polymers, urethane polymers, rubber polymers, etc., in terms of optical transparency From the viewpoint of control of adhesiveness, adhesion, and storage modulus, acrylic polymers are preferred.

Acrylic polymers are obtained by polymerization of monomer components containing alkyl (meth)acrylate as a main component.

Alkyl (meth)acrylate is an acrylate and/or methacrylate, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. Butyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, Amyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylate Isodecyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, isotri-dodecyl (meth)acrylate, myristyl (meth)acrylate Ester, isotetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, (meth) ) Steearyl acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosanyl (meth)acrylate and other linear or branched C1-20 alkyl (meth)acrylate, etc., preferably methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, more preferably Examples include methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate.

The alkyl (meth)acrylate can be used alone or in combination of two or more types.

As the (meth)acrylic acid alkyl ester, from the viewpoint of adjusting the glass transition temperature and the shear storage modulus G', a single one selected from the group consisting of C4-12 alkyl (meth)acrylic acid esters can be preferably used. Or the use of plural types, or the combined use of methyl methacrylate and C4-12 alkyl acrylate, more preferably, the combined use of methyl methacrylate and C4-12 alkyl acrylate.

When methyl methacrylate and C4-12 alkyl acrylate are used together as the (meth)acrylic acid alkyl ester, relative to 100 parts by mass of the total amount of methyl methacrylate and C4-12 alkyl acrylate, The blending ratio of methyl methacrylate is, for example, 5 parts by mass or more, and, for example, 20 parts by mass or less. The blending ratio of C4-12 alkyl acrylate is, for example, 80 parts by mass or more, and, for example, 95 parts by mass. the following.

The compounding ratio of the alkyl (meth)acrylate is, for example, 50 mass% or more, preferably 60 mass% or more, and, for example, 99 mass% or less, preferably 80 mass% or less, relative to the monomer component. .

Moreover, the monomer component preferably contains an acidic vinyl monomer having an anionic group.

If the monomer component contains an acidic vinyl monomer having an anionic group, the separation is accelerated by the strong acid generated from the acid generator (described below), the color tone becomes stronger, and the coloring stability described below is excellent.

Examples of the acidic vinyl monomer having an anionic group include carboxyl group-containing vinyl monomers, sulfo group-containing vinyl monomers, phosphate group-containing vinyl monomers, and the like.

Examples of the carboxyl group-containing vinyl monomer include: (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, carboxypentylcarboxypentyl(meth)acrylate, itaconic acid, maleic acid, rich Horse acid, crotonic acid, etc.

Examples of the carboxyl group-containing vinyl monomer include acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride.

Examples of the sulfovinyl-containing monomer include styrenesulfonic acid, allylsulfonic acid, and the like.

Examples of the phosphate group-containing vinyl monomer include 2-hydroxyethyl acrylphosphate.

The acidic vinyl monomer having an anionic group can be used alone or in combination of two or more types.

The compounding ratio of the acidic vinyl monomer having an anionic group is, for example, 3 parts by mass or more and, for example, 10 parts by mass or less based on 100 parts by mass of the alkyl (meth)acrylate, and relative to the monomer The component is, for example, 1% by mass or more, and may be 8% by mass or less.

Moreover, it is preferable that the monomer component does not substantially contain a basic vinyl monomer having a lone electron pair that can be copolymerized with alkyl (meth)acrylate.

Specifically, the blending ratio of the basic vinyl monomer having a lone electron pair is, for example, 3% by mass or less, preferably 1% by mass or less, and further preferably 0.5% by mass or less based on the monomer component. Especially preferably, it is 0 mass % or less. In other words, it is particularly preferred that the monomer component does not contain a basic vinyl monomer having a lone electron pair.

If the monomer component does not substantially contain a basic vinyl monomer having a lone electron pair, elution of each monomer component can be suppressed and the coloring stability described below can be improved.

The basic vinyl monomer having a lone electron pair is a heterocyclic-containing basic vinyl monomer having nitrogen in the heterocyclic ring. Examples thereof include: N-vinylpyrrolidone, methylvinylpyrrolidone, Vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyridine, vinyl pyrrole, vinyl imidazole, vinyl 㗁azole, vinyl pyridine, N-acrylamide, N-vinyl caprolactam, etc.

Furthermore, the monomer component preferably contains a functional group-containing vinyl monomer capable of being copolymerized with alkyl (meth)acrylate (the above-mentioned acidic vinyl monomer having an anionic group and a basic vinyl monomer having a lone electron pair). Except monomer).

Examples of the functional group-containing vinyl monomer include: hydroxyl group-containing vinyl monomer, cyano group-containing vinyl monomer, glycidyl group-containing vinyl monomer, aromatic vinyl monomer, vinyl ester monomer, vinyl ether Monomer etc.

Examples of the hydroxyl-containing vinyl monomer include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 4-hydroxybutyl ester, (meth)acrylic acid 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 4-(hydroxymethyl)acrylate ) cyclohexyl methyl ester, etc., preferably 2-hydroxyethyl (meth)acrylate, more preferably 2-hydroxyethyl acrylate.

Examples of the cyano group-containing vinyl monomer include (meth)acrylonitrile.

Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth)acrylate.

Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, o-methylstyrene, α-methylstyrene, and the like.

Examples of the vinyl ester monomer include ethyl acetate, vinyl propionate, and the like.

Examples of the vinyl ether monomer include methyl vinyl ether and the like.

The functional group-containing vinyl monomer can be used alone or in combination of two or more types. When formulating a cross-linking agent (described below), from the viewpoint of introducing a cross-linked structure into the polymer, a hydroxyl group-containing vinyl monomer is preferably used.

The blending ratio of the functional group-containing vinyl monomer is, for example, 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 15 parts by mass or more, based on 100 parts by mass of the alkyl (meth)acrylate. , for example, it is 20 parts by mass or less, and relative to the monomer component, it is, for example, 4 mass % or more, preferably 10 mass % or more, and, for example, 30 mass % or less, preferably 20 mass % or less.

Furthermore, the acrylic polymer is a polymer obtained by polymerizing the above-mentioned monomer components.

When polymerizing the monomer component, for example, alkyl (meth)acrylate, and optionally a basic vinyl monomer and a functional group-containing vinyl monomer are prepared to prepare the monomer component, for example, by solution polymerization, block Acrylic polymers are prepared by well-known polymerization methods such as polymerization and emulsion polymerization.

As a polymerization method, solution polymerization is preferably mentioned.

In solution polymerization, for example, a monomer component and a polymerization initiator are mixed with a solvent to prepare a monomer solution, and then the monomer solution is heated.

Examples of the solvent include organic solvents and the like.

Examples of organic solvents include aromatic hydrocarbon solvents such as toluene, benzene, and xylene; ether solvents such as diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; and ester solvents such as ethyl acetate. ; For example, amide-based solvents such as N,N-dimethylformamide; preferably, ester-based solvents can be used, and more preferably, ethyl acetate can be used.

The solvent can be used alone or in combination of two or more.

The blending ratio of the solvent is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, and, for example, 500 parts by mass or less, preferably 300 parts by mass or less based on 100 parts by mass of the monomer component.

Examples of the polymerization initiator include peroxide polymerization initiators, azo polymerization initiators, and the like.

Examples of the peroxide-based polymerization initiator include peroxycarbonate, peroxyketone, peroxyketal, hydroperoxide, dialkyl peroxide, diyl peroxide, peroxyester, etc. Organic peroxide.

Examples of the azo polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis( Azo compounds such as 2,4-dimethylvaleronitrile) and 2,2'-dimethyl azobisisobutyrate.

As the polymerization initiator, an azo-based polymerization initiator is preferably used, and 2,2'-azobisisobutyronitrile is more preferably used.

The polymerization initiator can be used alone or in combination of two or more types.

The blending ratio of the polymerization initiator is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, based on 100 parts by mass of the monomer component.

The heating temperature is, for example, 50°C or more and 80°C or less, and the heating time is, for example, 1 hour or more and 8 hours or less.

Thereby, the monomer component is polymerized, and the acrylic polymer solution containing an acrylic polymer is obtained.

The solid content concentration of the acrylic polymer solution is, for example, 20 mass% or more, and, for example, 80 mass% or less.

The weight average molecular weight of the acrylic polymer is, for example, 100,000 or more, preferably 300,000 or more, more preferably 500,000 or more, further preferably 650,000 or more, and, for example, 5,000,000 or less, preferably 3,000,000 or less, more preferably 2,000,000 or less. .

In addition, the weight average molecular weight mentioned above is a value calculated by measuring by GPC (gel permeation chromatography) and converting to polystyrene.

The glass transition temperature of the adhesive polymer is, for example, 0°C or lower, preferably -20°C or lower, and usually -70°C or higher.

If the glass transition temperature of the adhesive polymer is equal to or lower than the above upper limit, the step followability will be excellent.

Furthermore, the glass transition temperature is obtained by calculation according to the FOX formula.

Compounds colored by acid are compounds that change from colorless (transparent) to colored by acid. Examples include leuco pigments, such as p,p',p''-tri-dimethylaminotriphenylmethane, etc. Triarylmethane dyes, such as 4,4-bis-dimethylaminophenyl diphenylmethyl benzyl ether and other diphenylmethane dyes, such as 3-diethylamino-6-methyl-7-chlorofluorescence Preferred examples include fluorescent yellow matrix pigments such as yellow matrix, spiropyran pigments such as 3-methylspirodinaphthopyran, rose bengal pigments such as rose bengal-B-anilinolactamide, etc. Take leuco pigments.

The compound colored by acid can be used alone or in combination of two or more.

The compounding ratio of the acid-colored compound is, for example, 0.5 parts by mass or more, and, for example, 5 parts by mass or less, preferably 2 parts by mass or less, based on 100 parts by mass of the adhesive polymer.

Examples of the acid generator include photoacid generators, thermal acid generators, and the like.

Photoacid generators are compounds that generate acid by irradiation with light (active light).

Examples of active rays include ultraviolet rays, visible rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. From the viewpoint of diversity of equipment used and ease of operation, ultraviolet rays are preferably used.

In addition, ultraviolet rays refer to electromagnetic waves in the wavelength range of 1 nm or more and 400 nm or less.

Among such photoacid generators, examples of compounds that generate acid upon irradiation with ultraviolet rays (ultraviolet acid generators) include onium compounds and the like.

Examples of the onium compound include onium cations such as iodonium and sulfonium, and Cl ^- , Br ^- , I ^- , ZnCl ₃ - , HSO ₃ ^- , BF ₄ ^- , PF ₆ ^{- ,} AsF ₆ ^- , SbF ₆ ^- , and CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (C ₆ F ₅ ) ₄ B ^- , (C ₄ H ₉ ) ₄ B ^- and other anionic salts, etc.

Preferred examples of such onium compounds include salts containing strontium (onium cation) and (C ₆ F ₅ ) ₄ B ^- (anion).

In addition, as the ultraviolet acid generator, commercially available products can also be used, and examples thereof include CPI-310B (a salt containing sulfonium and (C ₆ F ₅ ) ₄ B ^- , manufactured by San-Apro).

The photoacid generator can be used alone or in combination of two or more types.

The thermal acid generator is a compound that generates acid by heating, and examples thereof include aryl sulfonium salts, aryl ionium salts, and the like.

The thermal acid generator can be used alone or in combination of two or more types.

As an acid generator, from the viewpoint of preventing coloration during film formation by heating or coloring treatment in a short time, selecting a photoacid generator can prevent coloration or avoid coloration during film formation by UV (ultraviolet, ultraviolet) polymerization. Select a thermal acid generator from the viewpoint of the effect of UV on the adherend (described below).

The compounding ratio of the acid generator is, for example, 1 part by mass or more based on 100 parts by mass of the adhesive polymer, and is, for example, 20 parts by mass or less, preferably 15 parts by mass or less.

Furthermore, the adhesive is prepared by preparing and mixing an adhesive polymer (a polymer solution when the adhesive polymer is prepared by solution polymerization), a compound colored by an acid, and an acid generator in the above ratios. Preparation (when using a polymer solution as an adhesive polymer, prepare a solution of the adhesive).

From the viewpoint of introducing a cross-linked structure into the adhesive polymer, it is preferable to blend the cross-linking agent into the adhesive.

Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, carbodiimide-based cross-linking agents, and metal chelates. Compounds are cross-linking agents, etc.

Examples of isocyanate-based crosslinking agents include aliphatic diisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; and lipids such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate. Cyclic diisocyanates; for example, aromatic diisocyanates such as 2,4-methylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.

Examples of the isocyanate-based crosslinking agent include derivatives of the above-mentioned isocyanates (for example, isocyanurate modified products, polyol modified products, etc.).

As the isocyanate-based crosslinking agent, commercially available products can also be used, and examples thereof include: Coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh), Coronate HL (hexamethylene diisocyanate) Trimethylolpropane adduct, manufactured by Tosoh), Coronate HX (isocyanurate body of hexamethylene diisocyanate, manufactured by Tosoh), Takenate D110N (trimethylolpropane of xylylene diisocyanate) Adducts, manufactured by Mitsui Chemicals), etc.

Preferable examples of the isocyanate-based crosslinking agent include the trimethylolpropane adduct of hexamethylene diisocyanate and the trimethylolpropane adduct of xylylenediisocyanate.

Examples of the epoxy cross-linking agent include diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and the like.

As the epoxy cross-linking agent, commercially available products can also be used, and examples include Tetrad C (manufactured by Mitsubishi Gas Chemical Co., Ltd.).

As the epoxy cross-linking agent, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane can be preferably exemplified.

As the cross-linking agent, an isocyanate-based cross-linking agent is preferably exemplified.

The cross-linking agent can be used alone or in combination of two or more types.

If a cross-linking agent is added to the adhesive, functional groups such as hydroxyl groups in the polymer react with the cross-linking agent to introduce a cross-linked structure into the polymer.

The compounding ratio of the cross-linking agent is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, and, for example, 10 parts by mass or less, relative to 100 parts by mass of the adhesive polymer. It is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less.

Furthermore, when a cross-linking agent is blended into the adhesive, a cross-linking catalyst may be blended in order to promote the cross-linking reaction.

Examples of the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, iron acetyl acetonate, butyl tin oxide, and dioctyl tin dilaurate.

The cross-linking catalyst can be used alone or in combination of two or more types.

The blending ratio of the cross-linking catalyst is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and, for example, 0.05 parts by mass or less based on 100 parts by mass of the adhesive polymer.

In addition, if necessary, the adhesive may contain, for example, a silane coupling agent, an adhesiveness imparting agent, a plasticizer, a softener, an anti-deterioration agent, a filler, a colorant, a surfactant, etc. within the scope that does not impair the effect of the present invention. Various additives such as antistatic agents, UV absorbers, antioxidants and other additives from the viewpoint of stabilization under fluorescent lamps or natural light.

Thereby, an adhesive (a solution of an adhesive when a polymer solution is used as the adhesive polymer) is obtained.

The shear storage modulus G' of the adhesive (solid component) at 20°C to 50°C is, for example, 1.0×10 ⁴ Pa or more, preferably 2.0×10 ⁴ Pa or more, more preferably 4.0×10 ⁴ Pa The above value is, for example, 1.0×10 ⁶ Pa or less, preferably 5.0×10 ⁵ Pa or less.

When the shear storage modulus G' is within the above range, the adhesion is excellent. When the shear storage modulus G' is lower, the step followability is also excellent.

Furthermore, the details of the above-mentioned shear storage modulus G' are described in the following examples, through the dynamic viscosity under the conditions of frequency 1 Hz, temperature rise rate 5°C/min, and temperature range -70°C ~ 250°C. Elastometric measurements were made.

Furthermore, the adhesive includes an adhesive polymer, a compound colored by an acid, and an acid generator.

Therefore, the adhesive generates acid from the acid generator by irradiation with light (active light) or heating, and the compound colored by the acid is colored by the acid, thereby changing from colorless (transparent) to colored. That is, the adhesive is colorless (transparent) before irradiation with light (active light) or heating.

In addition, colorless (transparent) means that the transmittance measured in the following examples is, for example, 60% or more, preferably 70% or more, more preferably 90% or more, and, for example, 100% or less.

In addition, colored means that the transmittance measured in the following examples is, for example, 0% or more, and for example, it means that it is less than 60%, and preferably it is 50% or less.

Furthermore, the shear storage modulus G' at 20°C to 50°C of the adhesive (adhesive layer 1 described below) after being irradiated with light (activated light) is, for example, 1.0×10 ⁴ Pa or more, which is smaller than It is preferably 2.0×10 ⁴ Pa or more, more preferably 4.0×10 ⁴ Pa or more, and, for example, it is 1.0×10 ⁶ Pa or less, preferably 5.0×10 ⁵ Pa or less.

That is, the shear storage modulus G' of this adhesive (adhesive layer 1 described below) does not change significantly before and after light (active light) irradiation, and the adhesive force does not change significantly either.

2.Adhesive layer The adhesive layer 1 is a pressure-sensitive adhesive layer used to adhere to the adherend 4 (described below). Moreover, the adhesive layer 1 has a film shape extending in the plane direction, and has a flat plane and a flat lower surface.

The adhesive layer 1 is formed of the above-mentioned adhesive.

Hereinafter, the method of manufacturing the adhesive layer 1 will be described with reference to FIG. 1 .

When forming the adhesive layer 1, first, as shown in FIG. 1A, a release film 2 is prepared.

Examples of the release film 2 include flexible plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films.

The thickness of the release film 2 is, for example, 3 μm or more, preferably 10 μm or more, and, for example, 200 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.

It is preferable that the release film 2 be subjected to a release treatment using a release agent such as a silicone-based, fluorine-based, long-chain alkyl-based, fatty amide-based release agent, or the like, or a release treatment using silica powder.

Then, as shown in FIG. 1B , the above-mentioned adhesive (adhesive solution) is coated on one side of the release film 2 , and the solvent is dried and removed if necessary.

Examples of coating methods for the adhesive include roll coating, contact roll coating, gravure coating, reverse coating, roller brushing, spray coating, dip roll coating, rod coating, knife coating, Air knife coating, curtain coating, die lip coating, die nozzle coating, etc.

As drying conditions, drying temperature is, for example, 50°C or higher, preferably 70°C or higher, more preferably 100°C or higher, and, for example, 200°C or lower, preferably 180°C or lower, more preferably 150°C or lower, drying time For example, it is 5 seconds or more, and preferably it is 10 seconds or more, and for example, it is 20 minutes or less, preferably 15 minutes or less, and more preferably 10 minutes or less.

Thereby, the adhesive layer 1 is arranged (formed) on one side of the release film 2 .

In addition, if necessary, another release film 2 may be disposed on one side of the adhesive layer 1 (see the dotted line in FIG. 1B ).

Furthermore, when the adhesive contains a cross-linking agent, it is preferable to perform cross-linking by aging while drying and removing it, or after drying the solvent (after layering the peeling film 2 on one area of the adhesive layer 1 if necessary). .

The aging conditions are appropriately set according to the type of cross-linking agent. The aging temperature is, for example, 20°C or more, and for example, it is 160°C or less, preferably 50°C or less. The aging time is 1 minute or more, preferably 12 hours or more. , more preferably 1 day or more, and, for example, 7 days or less.

3. Adhesive sheet From the viewpoint of operability, the adhesive layer 1 may also be prepared as the adhesive layer 1 of the adhesive sheet 3 .

Hereinafter, the method of manufacturing the adhesive sheet 3 will be described with reference to FIG. 2 .

The method of manufacturing the adhesive sheet 3 includes the following steps: preparing the base material 5 and arranging the adhesive layer 1 on one side of the base material 5 .

In the step of preparing the base material 5, as shown in FIG. 2A, the base material 5 is prepared.

The base material 5 is the lower layer of the adhesive sheet 3 . The base material 5 is a support layer (support material) that ensures the mechanical strength of the adhesive sheet 3 . Furthermore, the base material 5 has a film shape extending in the plane direction, and has a flat plane and a flat lower surface.

The base material 5 includes flexible plastic material.

Examples of such plastic materials include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; for example, polymethacrylate, etc. (Meth)acrylic resin (acrylic resin and/or methacrylic resin); such as polyethylene, polypropylene, cyclic olefin polymer (COP) and other polyolefin resins; such as polycarbonate resin; such as polyether ester resin Resin; such as polyarylate resin; such as melamine resin; such as polyamide resin; such as polyimide resin; such as cellulose resin; such as polystyrene resin; synthetic resin such as norphene resin, etc.

When the adhesive layer 1 is colored by irradiating active light (preferably ultraviolet rays) from the base material 5 side, it is preferable that the base material 5 has transparency to light. Specifically, the total light transmittance (JIS K 7375-2008) of the base material 5 is, for example, 80% or more, preferably 85% or more.

From the viewpoint of having both transparency to light and mechanical strength, as the plastic material, polyester resin is preferably used, and polyethylene terephthalate (PET) is more preferably used.

The thickness of the base material 5 is, for example, 4 μm or more, preferably 20 μm or more, more preferably 30 μm or more, further preferably 45 μm or more, and, for example, 500 μm or less, from the viewpoint of flexibility and operability. Specifically, it is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less.

In the step of disposing the adhesive layer 1, as shown in FIG. 2B, the adhesive layer 1 is disposed on one side of the base material 5.

The adhesive layer 1 is disposed on the entire surface of the base material 5 , and is the upper layer of the adhesive sheet 3 .

When arranging the adhesive layer 1 on one side of the base material 5, apply the adhesive (adhesive solution) on one side of the base material 5 in the same manner as above, and dry and remove the solvent if necessary.

In this way, the adhesive layer 1 is formed on one side of the base material 5 , and the adhesive sheet 3 including the base material 5 and the adhesive layer 1 arranged on one side of the base material 5 is obtained.

Moreover, as shown in FIG. 2C , the adhesive sheet 3 may also have a release film 2 laminated on one surface of the adhesive layer 1 if necessary.

In this case, the adhesive sheet 3 includes the base material 5, the adhesive layer 1, and the release film 2 in this order.

4. Intermediate laminated body As shown in FIG. 3 , the intermediate laminate 6 has a film shape (including a sheet shape) with a specific thickness, extends in a direction (surface direction) orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface. .

Specifically, the intermediate laminated body 6 includes an adhesive layer 1 and an adherend 4 arranged on the other side of the adhesive layer 1 .

In addition, if necessary, the release film 2 may be disposed on one side of the adhesive layer 1 (see the dotted line in Figure 3).

In this case, the intermediate laminated body 6 includes the release film 2 , the adhesive layer 1 arranged on the other side of the release film 2 , and the adherend 4 arranged on the other side of the adhesive layer 1 .

Details will be described below. The intermediate laminate 6 is obtained by attaching the above-mentioned adhesive layer 1 to the adherend 4 .

4-1.Adhesive layer As mentioned above, the adhesive layer 1 is formed of the above-mentioned adhesive.

Moreover, in the following description, the adhesive contains a photoacid generator as an acid generator.

In addition, the adhesive layer 1 has a high light transmittance portion 10 with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion 11 with a relatively small visible light transmittance at a wavelength of 550 nm.

Furthermore, as will be described in detail below, the visible light transmittance at a wavelength of 550 nm of the high light transmittance portion 10 and the low light transmittance portion 11 is determined by the manufacturing method of the intermediate laminate 6 described below.

4-2. Adhered body Examples of the adherend 4 include optical devices, electronic devices and their constituent parts.

Furthermore, in FIG. 3 , the adherend 4 has a flat plate shape, but the shape of the adherend 4 is not particularly limited, and various shapes can be selected according to the types of optical devices, electronic devices, and structural parts thereof.

In addition, as will be described in detail below, in the method of manufacturing the intermediate laminated body 6, when the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) from the surface side of the adherend 4 (see 2A below) Embodiment), the manufacturing method of the intermediate laminate 6 is determined depending on whether the adherend 4 transmits active light (preferably ultraviolet light) or blocks active light (preferably ultraviolet light).

Among such adherends 4 , the adherend 4 that transmits active light (hereinafter referred to as the first adherend 30 ) may preferably be the first adherend 30 that transmits ultraviolet rays.

Examples of the first adherend 30 that transmits ultraviolet rays include alkali-free glass, PET film, and the like.

The average transmittance of the active rays of the first adherend 30 that transmits the active rays is, for example, 60% or more, preferably 65% or more. In particular, the first adherend 30 that transmits the active rays transmits ultraviolet rays. In the case of the first adherend 30 , the average transmittance of the first adherend 30 that transmits ultraviolet rays at a wavelength of 300 nm or more and 400 nm or less is, for example, 60% or more, preferably 65% or more.

If the average transmittance is equal to or higher than the lower limit, active rays (preferably ultraviolet rays) pass through the first adherend 30 , and the adhesive layer 1 can be irradiated with active rays (preferably ultraviolet rays).

In addition, as the adherend 4 (hereinafter referred to as the second adherend 31) that blocks active rays (preferably ultraviolet rays) among such adherends 4, there may be mentioned a second adherend that absorbs active rays. 31. The second adherend 31 that reflects the active light (does not transmit the active light).

As the second adherend 31 that absorbs active rays, a preferred example is the second adherend 31 that absorbs ultraviolet rays.

Examples of the second adherend 31 that absorbs ultraviolet rays include a polyimide film, a glass plate coated with an ultraviolet absorber, and the like.

The average transmittance of active rays of the second adherend 31 that absorbs active rays is, for example, 15% or less, preferably 10% or less. In particular, the second adherend 31 that absorbs active rays is the second adherend that absorbs ultraviolet rays. In the case of the adherend 31, the average transmittance of the second adherend 31 that absorbs ultraviolet rays at a wavelength of 300 nm or more and 400 nm or less is, for example, 15% or less, preferably 10% or less.

If the average transmittance is equal to or higher than the lower limit, the second adherend 31 can absorb active light (preferably ultraviolet light).

As the second adherend 31 that reflects active light, a preferred example is the second adherend 31 that reflects ultraviolet rays.

Examples of the second adherend 31 that reflects ultraviolet rays include metal substrates such as copper plates.

4-3. Manufacturing method of intermediate laminate The manufacturing method of the intermediate laminate 6 includes the following steps: a preparation step, which prepares the above-mentioned adhesive layer 1; and an irradiation step, which irradiates the adhesive layer 1 with active light (preferably ultraviolet light) to form active light (preferably ultraviolet light) in the adhesive layer 1. The high irradiation part 20 where the irradiation amount of ultraviolet rays (preferably ultraviolet rays) is relatively high, and the irradiation amount of active rays (preferably ultraviolet rays) is relatively low, or the non-irradiation/low irradiation part where active rays (preferably ultraviolet rays) are not irradiated part 21, whereby the visible light transmittance at the wavelength of 550 nm of the high-irradiation part 20 is smaller than the visible light transmittance at the wavelength of 550 nm of the unirradiated/low-irradiation part 21; and a laminating step, which is to separate the other part of the adhesive layer 1 One side is attached to the adherend 4.

Since the manufacturing method of the intermediate laminate 6 includes the above preparation steps, the adhesive layer 1 can be colored by irradiating active light (preferably ultraviolet light) to the adhesive layer 1 .

Furthermore, since the manufacturing method of the intermediate laminated body 6 includes the above-mentioned irradiation step, the colored portions in the adhesive layer 1 (non-irradiated/low-irradiated portions 21) can remain transparent or the amount of coloring can be smaller than that of the colored portions.

Hereinafter, the manufacturing method of the intermediate laminated body 6 will be described based on the order of each step and the irradiation direction of active light (preferably ultraviolet light).

Specifically, as the order of each step, the irradiation step is performed after the preparation step, and the bonding step is performed after the irradiation step (hereinafter referred to as the first embodiment), or the bonding step is performed after the preparation step, and the bonding step is performed after the irradiation step. After the bonding step, the irradiation step is performed (hereinafter referred to as the second embodiment).

In addition, as the irradiation direction of active light (preferably ultraviolet light), in the second embodiment, the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) from the surface side of the adherend 4 (hereinafter referred to as 2A implementation form), or the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) from the surface side of the adhesive layer 1 (hereinafter referred to as the 2B embodiment).

Each embodiment is described in detail below.

Furthermore, in the manufacturing method of the intermediate laminated body 6 , whether the non-irradiated/low-irradiated portion 21 becomes the non-irradiated portion 22 or the low-irradiated portion 23 is determined according to the irradiation amount of active light (preferably ultraviolet rays), but as follows: In the description, the case where the unirradiated/low irradiated portion 21 is the unirradiated portion 22 will be described in detail.

In addition, the unirradiated portion 22 is a portion that is not irradiated with active light (preferably ultraviolet light). The visible light transmittance of the unirradiated portion 22 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

If the visible light transmittance is equal to or higher than the lower limit, the unirradiated portion 22 has transparency.

Moreover, in the following description, the case where the adhesive layer 1 with the release film 2 arrange|positioned on both sides of the adhesive layer 1 is used as the adhesive layer 1 is demonstrated.

4-3-1. First embodiment In the first embodiment, the irradiation step is performed after the preparation step, and the bonding step is performed after the irradiation step.

The first embodiment will be described with reference to FIG. 4 .

In the preparation step, as shown in FIG. 4A , an adhesive layer 1 is prepared on one side of the release film 2 , and then another release film 2 is prepared on one side of the adhesive layer 1 .

In the irradiation step, as shown in FIG. 4B , the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) to form a high-irradiation portion 20 in which the amount of active light (preferably ultraviolet light) is relatively high. and the unirradiated portion 22 that is not irradiated with active light (preferably ultraviolet rays).

Furthermore, in the following description, a case where a part of the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) will be described. Specifically, the adhesive layer 1 is divided into three parts in the surface direction, and one of the parts is divided into three parts. Both end portions 2 are irradiated with active light (preferably ultraviolet light), and a part of the adhesive layer 1 that is irradiated with active light (preferably ultraviolet light) is set as the high-irradiation part 20 (in other words, the adhesive layer 1 is divided in the surface direction There are three parts, and only the central part is the unirradiated part 22).

Specifically, in the irradiation step, in the adhesive layer 1, the highly irradiated portion 20 is irradiated with active rays (preferably ultraviolet rays) from the surface side of the release film 2, and the non-irradiated portion 22 is not irradiated with active rays (more specifically, ultraviolet rays). Preferably UV).

Specifically, the mask 7 that blocks active light (preferably ultraviolet light) is not disposed in the high-irradiation part 20 (specifically, the other side of the release film 2 disposed on the other side of the high-irradiation part 20). The irradiation part 22 (specifically, the other side of the release film 2 disposed on the other side of the non-irradiation part 22) is equipped with a mask 7 that blocks active light (preferably ultraviolet rays). The surface side of layer 1) is irradiated with active light (preferably ultraviolet light).

Thereby, only the highly irradiated part 20 is irradiated with active light (preferably ultraviolet rays).

Furthermore, in the adhesive layer 1 in the highly irradiated portion 20, an acid is generated from the photoacid generator, and the compound colored by the acid is colored (specifically, black) by the acid. As a result, the adhesive layer 1 in the highly irradiated portion 20 changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low). In this way, the visible light transmittance of the highly irradiated portion 20 at a wavelength of 550 nm is smaller than the visible light transmittance of the unirradiated portion 22 at a wavelength of 550 nm (specifically, the highly irradiated portion 20 becomes black compared to the unirradiated portion 22 ).

That is, the highly irradiated portion 20 having a relatively small visible light transmittance at a wavelength of 550 nm and the unirradiated portion 22 having a relatively large visible light transmittance at a wavelength of 550 nm are formed.

In this way, the highly irradiated portion 20 becomes the low light transmittance portion 11 , and the unirradiated portion 22 becomes the high light transmittance portion 10 .

In the bonding step, as shown in FIG. 4C , the other side of the adhesive layer 1 is attached to the adherend 4 .

Specifically, the release film 2 is peeled off from the other side of the adhesive layer 1 , and the adherend 4 is placed on the other side of the adhesive layer 1 .

Thereby, an intermediate laminated body 6 is obtained, which includes the release film 2 , the adhesive layer 1 arranged on the other side of the release film 2 , and the adherend 4 arranged on the other side of the adhesive layer 1 .

Furthermore, in the intermediate laminate 6, the adhesive layer 1 has a high light transmittance portion 10 with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion 11 with a relatively small visible light transmittance at a wavelength of 550 nm. .

Furthermore, in the intermediate laminate 6, the visible light transmittance at the wavelength of 550 nm of the low light transmittance portion 11 is, for example, less than 20%, preferably less than 10%, and, for example, more than 0.01%, and high light transmittance. The visible light transmittance of the high-efficiency part 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

If the visible light transmittance of the low light transmittance portion 11 does not reach the upper limit, the low light transmittance portion 11 can be reliably given the function of absorbing light.

Furthermore, if the visible light transmittance of the high light transmittance portion 10 is equal to or higher than the lower limit, the high light transmittance portion 10 has transparency.

According to the first embodiment, the effect of the above-mentioned manufacturing method of the intermediate laminated body 6 is exerted, and since the irradiation step is performed after the preparation step and the bonding step is performed after the irradiation step, the colored portion can be used to improve alignment accuracy.

In particular, if the adherend 4 is the second adherend 31 , the unirradiated portion 22 can be suppressed from being colored by external light (active light) from the surface side of the second adherend 31 .

4-3-2. 2A embodiment In the 2A embodiment, the bonding step is performed after the preparation step, and the irradiation step is performed after the bonding step.

Furthermore, in the 2A embodiment, in the irradiation step, the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) from the surface side of the adherend 4 .

In the 2A embodiment, the active light (preferably ultraviolet) is transmitted or blocked depending on the adherend 4 (specifically, the adherend 4 is the first adherend 30 Or the second adherend 31) determines the manufacturing method of the intermediate laminate 6.

In the following, the description will be divided into the case where the adherend 4 is the first adherend 30 and the case where the adherend 4 is the second adherend 31 .

Embodiment 2A when the adherend 4 is the first adherend 30 will be described with reference to FIG. 5 .

In the preparation step, as shown in FIG. 5A , the adhesive layer 1 is prepared in the same manner as in the above-described first embodiment.

In the bonding step, as shown in FIG. 5B , the other surface of the adhesive layer 1 is bonded to the first adherend 30 in the same manner as in the first embodiment.

In the irradiation step, as shown in FIG. 5C , the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) to form a high-irradiation portion 20 with a relatively high amount of active light (preferably ultraviolet light) in the adhesive layer 1 . and the unirradiated portion 22 that is not irradiated with active light (preferably ultraviolet rays).

Specifically, in the irradiation step, in the adhesive layer 1, the highly irradiated portion 20 is irradiated with active light (preferably ultraviolet light) from the first adherend 30 side, and the non-irradiated portion 22 is not irradiated with active rays ( Preferably ultraviolet).

Specifically, after arranging the mask 7 for blocking active rays (preferably ultraviolet rays) on a part of the other surface of the first adherend 30 , the adhesive layer 1 is irradiated with active rays (preferably ultraviolet rays).

More specifically, the high-irradiation part 20 (specifically, the other surface of the first adherend 30 disposed on the other surface of the high-irradiation part 20) is not provided with a mask that blocks active light (preferably ultraviolet light). 7. Arrange a mask 7 for blocking active light (preferably ultraviolet light) on the non-irradiated portion 22 (specifically, the other surface of the first adherend 30 disposed on the other surface of the non-irradiated portion 22). 1. The surface side of the adherend 30 is irradiated with active light (preferably ultraviolet light).

At this time, since the first adherend 30 transmits active rays (preferably ultraviolet rays), only the highly irradiated portion 20 can be irradiated with active rays (preferably ultraviolet rays).

Thereby, the highly irradiated part 20 (low light transmittance part 11) and the unirradiated part 22 (high light transmittance part 10) can be formed similarly to the said 1st Embodiment.

By the above, as shown in FIG. 5D , an intermediate laminated body 6 is obtained, which includes a release film 2 , an adhesive layer 1 arranged on the other side of the release film 2 , and an adherend 4 arranged on the other side of the adhesive layer 1 ( 1st adherend 30).

Furthermore, in the intermediate laminate 6, the adhesive layer 1 has a high light transmittance portion 10 with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion 11 with a relatively small visible light transmittance at a wavelength of 550 nm. .

Furthermore, in the intermediate laminate 6, the visible light transmittance at the wavelength of 550 nm of the low light transmittance portion 11 is, for example, less than 20%, preferably less than 10%, and, for example, more than 0.01%, and high light transmittance. The visible light transmittance of the high-efficiency part 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

If the visible light transmittance of the low light transmittance portion 11 does not reach the upper limit, the low light transmittance portion 11 can be reliably given the function of absorbing light.

Furthermore, if the visible light transmittance of the high light transmittance portion 10 is equal to or higher than the lower limit, the high light transmittance portion 10 has transparency.

According to the 2A embodiment (the case where the adherend 4 is the first adherend 30), the effect of the above-mentioned manufacturing method of the intermediate laminated body 6 is exerted, and since the laminating step is performed after the preparation step, and after the laminating step The irradiation step is implemented, so foreign matter or air bubbles can be confirmed during the bonding step.

Furthermore, according to the 2A embodiment (the case where the adherend 4 is the first adherend 30), in the irradiation step, the adhesive layer 1 is irradiated with activity from the surface side of the adherend 4 (the first adherend 30). Light (preferably ultraviolet light) is used, so the positioning accuracy of the part to be colored is improved.

Furthermore, according to the 2A embodiment (the case where the adherend 4 is the first adherend 30 ), since the first adherend 4 is used, it can be applied from the surface side of the adherend 4 (the first adherend 30 ). The adhesive layer 1 is reliably irradiated with active light (preferably ultraviolet light).

Next, the 2B embodiment in the case where the adherend 4 is the second adherend 31 will be described with reference to FIG. 6 .

In the preparation step, as shown in FIG. 6A , the adhesive layer 1 is prepared in the same manner as in the above-described first embodiment.

In the bonding step, as shown in FIG. 6B , the second adherend 31 is disposed on a part of the other surface of the adhesive layer 1 .

Specifically, the release film 2 is peeled off from the other side of the adhesive layer 1 , and the second adherend 31 is disposed on a part of the other side of the adhesive layer 1 .

Furthermore, in the following description, a case will be described in which, as shown in FIG. 6B , the adhesive layer 1 is divided into three parts in the surface direction, and the second adherend is arranged at the central part 1 of the parts. 31.

In the irradiation step, as shown in FIG. 6C , the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) to form a high-irradiation portion 20 in which the amount of active light (preferably ultraviolet light) is relatively high. and the unirradiated portion 22 that is not irradiated with active light (preferably ultraviolet rays).

Specifically, in the irradiation step, in the adhesive layer 1, the highly irradiated part 20 is irradiated with active light (preferably ultraviolet light) from the surface side of the second adherend 31, and the unirradiated part 22 is not irradiated with active light. Light (preferably ultraviolet light).

Specifically, unlike the above-mentioned first embodiment and the second embodiment (where the adherend 4 is the first adherend 30), the mask 7 for blocking active light (preferably ultraviolet light) is directly Active light (preferably ultraviolet light) is irradiated from the surface side of the second adherend 31 .

At this time, since the second adherend 31 blocks the active light (preferably ultraviolet), the second adherend 31 can replace the mask 7 that blocks the active light (preferably ultraviolet), thereby preventing the configuration of the active light (preferably ultraviolet). The unirradiated portion 22 of the second adherend 31 is irradiated with active rays (preferably ultraviolet rays). On the other hand, only the highly irradiated portion 20 where the second adherend 31 is not arranged can be irradiated with active rays (preferably ultraviolet rays). ).

Thereby, the highly irradiated part 20 (low light transmittance part 11) and the unirradiated part 22 (high light transmittance part 10) can be formed similarly to the said 1st Embodiment.

By the above, as shown in FIG. 6D, an intermediate laminated body 6 is obtained, which includes a release film 2, an adhesive layer 1 arranged on the other side of the release film 2, and an adherend 4 arranged on the other side of the adhesive layer 1 ( The second adherend 31).

Furthermore, in the intermediate laminate 6, the adhesive layer 1 has a high light transmittance portion 10 with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion 11 with a relatively small visible light transmittance at a wavelength of 550 nm. .

Furthermore, in the intermediate laminate 6, the visible light transmittance at the wavelength of 550 nm of the low light transmittance portion 11 is, for example, less than 20%, preferably less than 10%, and, for example, more than 0.01%, and high light transmittance. The visible light transmittance of the high-efficiency part 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

If the visible light transmittance of the low light transmittance portion 11 does not reach the upper limit, the low light transmittance portion 11 can be reliably given the function of absorbing light.

Furthermore, if the visible light transmittance of the high light transmittance portion 10 is equal to or higher than the lower limit, the high light transmittance portion 10 has transparency.

According to the 2A embodiment (the case where the adherend 4 is the second adherend 31), the effect of the above-mentioned manufacturing method of the intermediate laminated body 6 is exerted, and since the laminating step is performed after the preparation step, and after the laminating step The irradiation step is implemented, so foreign matter or air bubbles can be confirmed during the bonding step.

Furthermore, according to the 2A embodiment (the case where the adherend 4 is the second adherend 31), in the irradiation step, the adhesive layer 1 is irradiated with activity from the surface side of the adherend 4 (the second adherend 31). Light (preferably ultraviolet light) is used, so the positioning accuracy of the part to be colored is improved.

Furthermore, according to the 2A embodiment (the case where the adherend 4 is the second adherend 31), it is possible to reliably prevent the portion where the second adherend 4 is arranged (the non-irradiated portion 22) from being irradiated with active light (relative to the second adherend 31). Preferably UV).

4-3-3. 2B implementation form In the 2B embodiment, the bonding step is performed after the preparation step, and the irradiation step is performed after the bonding step.

Furthermore, in the 2B embodiment, in the irradiation step, the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) from the adhesive layer 1 side.

Embodiment 2B will be described with reference to FIG. 7 .

In the preparation step, as shown in FIG. 7A , the adhesive layer 1 is prepared in the same manner as in the above-described first embodiment.

In the bonding step, as shown in FIG. 7B , the other surface of the adhesive layer 1 is bonded to the adherend 4 in the same manner as in the first embodiment.

In the irradiation step, as shown in FIG. 7C , the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) to form a high-irradiation portion 20 in which the amount of active light (preferably ultraviolet light) is relatively high. and the unirradiated portion 22 that is not irradiated with active light (preferably ultraviolet rays).

Specifically, in the irradiation step, in the adhesive layer 1, active light (preferably ultraviolet light) is irradiated from the surface side of the release film 2 (the surface side of the adhesive layer 1) for the highly irradiated portion 20, and for the non-irradiated portion 22. Do not irradiate active light (preferably ultraviolet light).

Specifically, the mask 7 for blocking active light (preferably ultraviolet light) is not disposed in the highly irradiated part 20 (specifically, one side of the release film 2 disposed on one side of the high irradiated part 20). 22 (specifically, one side of the peeling film 2 disposed on the side of the unirradiated portion 22) is provided with a mask 7 that blocks active light (preferably ultraviolet rays), from the surface side of the peeling film 2 (the surface of the adhesive layer 1 Side) is irradiated with active light (preferably ultraviolet light).

Thereby, only the highly irradiated portion 20 can be irradiated with active light (preferably ultraviolet rays), and the highly irradiated portion 20 (low light transmittance portion 11) and the unirradiated portion 22 (high light transmittance portion 11) can be formed in the same manner as in the first embodiment. Transmittance section 10).

Thereafter, as shown in FIG. 7D , an intermediate laminated body 6 is obtained, which includes the release film 2 , the adhesive layer 1 arranged on the other side of the release film 2 , and the adherend 4 arranged on the other side of the adhesive layer 1 .

Furthermore, in the intermediate laminate 6, the adhesive layer 1 has a high light transmittance portion 10 with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion 11 with a relatively small visible light transmittance at a wavelength of 550 nm. .

Furthermore, in the intermediate laminate 6, the visible light transmittance at the wavelength of 550 nm of the low light transmittance portion 11 is, for example, less than 20%, preferably less than 10%, and, for example, more than 0.01%, and high light transmittance. The visible light transmittance of the high-efficiency part 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

If the visible light transmittance of the low light transmittance portion 11 does not reach the upper limit, the low light transmittance portion 11 can be reliably given the function of absorbing light.

Furthermore, if the visible light transmittance of the high light transmittance portion 10 is equal to or higher than the lower limit, the high light transmittance portion 10 has transparency.

According to the 2B embodiment, the effect of the above-mentioned manufacturing method of the intermediate laminated body 6 is exerted, and since the laminating step is performed after the preparation step, and the irradiation step is performed after the laminating step, foreign matter or air bubbles can be eliminated during the laminating step. to confirm.

Furthermore, according to the 2B embodiment, since the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) from the surface side of the adhesive layer 1 in the irradiation step, the adhesive layer 1 can be reliably irradiated with active light (preferably ultraviolet light). ).

In particular, if the adherend 4 is the second adherend 31 , the unirradiated portion 22 can be suppressed from being colored by external light (active light) from the surface side of the second adherend 31 .

4-3-4. Variations In the above description, the case where the non-irradiation/low irradiation part 21 is the non-irradiation part 22 has been described. In the following description, the non-irradiation/low irradiation part 21 may also be the low irradiation part 23.

When the non-irradiated/low-irradiated part 21 is the low-irradiated part 23, the irradiation step includes: a first irradiation step, which is performed by arranging a first mask 8 that blocks active light (preferably ultraviolet light) and then adheres to it. The layer 1 is irradiated with active rays (preferably ultraviolet rays), and a first irradiation part 40 that is irradiated with active rays (preferably ultraviolet rays) is formed in the adhesive layer 1, and a first irradiation part 40 that is not irradiated with active rays (preferably ultraviolet rays) is formed. The irradiation part 41; and the second irradiation step, which is to irradiate the temporarily unirradiated part 41 of the adhesive layer 1 by disposing the second mask 9 that blocks active light (preferably ultraviolet light) in the first irradiation part 40 Active light (preferably ultraviolet light) is used, so that the temporarily unirradiated part 41 becomes the second irradiated part 42.

Furthermore, details will be described below. Since the irradiation amount of active light (preferably ultraviolet light) in the first irradiation step is different from the irradiation amount of active light (preferably ultraviolet light) in the second irradiation step, the Either one of the first irradiation part 40 and the second irradiation part 42 becomes the high irradiation part 20 , and the other one becomes the low irradiation part 23 .

In the following description, a case where the non-irradiated/low-irradiated portion 21 becomes the low-irradiated portion 23 in the first embodiment (hereinafter referred to as a first modification of the first embodiment) will be described with reference to FIG. 8 .

In the preparation step, as shown in FIG. 8A , the adhesive layer 1 is prepared in the same manner as in the above-described first embodiment.

In the irradiation step, the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) to form a high-irradiation portion 20 with a relatively high amount of active light (preferably ultraviolet light) in the adhesive layer 1, and an active light (preferably ultraviolet light) It is the low irradiation part 23 where the irradiation amount of ultraviolet rays is relatively low.

Specifically, in the first irradiation step among the irradiation steps, the first irradiation part 40 and the not yet irradiated part 41 are formed, and in the second irradiation step among the irradiation steps, the not yet irradiation part 41 becomes the second irradiation part. 42.

In the first irradiation step, as shown in FIG. 8B , the first irradiation part 40 is irradiated with active light (preferably ultraviolet light) from the surface side of the release film 2 (the surface side of the adhesive layer 1 ), and the part that has not been irradiated yet is 41. Do not irradiate active light (preferably ultraviolet light).

Furthermore, in the following description, the adhesive layer 1 is divided into three parts in the surface direction, and the two end portions 2 are set as the first irradiation parts 40 (in other words, the adhesive layer 1 is divided in the surface direction. There are three parts, and only the central part among them is the unirradiated part 41) for description.

More specifically, the first irradiation part 40 (specifically, the other side of the release film 2 disposed on the other side of the first irradiation part 40) is not provided with a first shield that blocks active rays (preferably ultraviolet rays). The cover 8 is a first cover 8 that blocks active light (preferably ultraviolet light), which is disposed on the not-yet-irradiated portion 41 (specifically, the other side of the release film 2 disposed on the other side of the not-yet-irradiated portion 41). Active light (preferably ultraviolet light) is irradiated from the surface side of the release film 2 (the surface side of the adhesive layer 1).

Thereby, only the first irradiation part 40 can be irradiated with active light (preferably ultraviolet rays).

Furthermore, in the adhesive layer 1 in the first irradiation part 40, the acid is generated from the photoacid generator, and the compound colored by the acid is colored (specifically, black) by the acid. As a result, the adhesive layer 1 in the first irradiation part 40 changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low).

Next, in the second irradiation step, the portion 41 that has not yet been irradiated becomes the second irradiation portion 42 .

Specifically, as shown in FIG. 8C , in the second irradiation step, the unirradiated portion 41 is irradiated from the surface side of the adhesive layer 1 with active light (preferably ultraviolet light) of a different amount from that in the first irradiation step. On the other hand, the first irradiation part 40 is not irradiated with active light (preferably ultraviolet rays).

More specifically, the second shield that blocks active light (preferably ultraviolet light) is not disposed in the not yet irradiated portion 41 (specifically, the other side of the release film 2 disposed on the other side of the not yet irradiated portion 41 ). The cover 9 is provided with a second mask 9 that blocks active rays (preferably ultraviolet rays) on the first irradiation part 40 (specifically, the other side of the release film 2 disposed on the other side of the first irradiation part 40). The surface side of the self-adhesive layer 1 is irradiated with active light (preferably ultraviolet light).

Thereby, only the temporarily unirradiated part 41 can be irradiated with active light (preferably ultraviolet light), and the temporarily unirradiated part 41 becomes the second irradiated part 42 .

Furthermore, in the adhesive layer 1 in the second irradiation portion 42, the acid is generated from the photoacid generator, and the compound colored by the acid is colored (specifically, black) by the acid. As a result, the adhesive layer 1 in the second irradiation part 42 changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low).

Thereby, the first irradiation part 40 and the second irradiation part 42 are formed in the adhesive layer 1 .

Furthermore, as mentioned above, in the second irradiation step, active light (preferably ultraviolet rays) with a different light amount from that in the first irradiation step is irradiated.

That is, the first irradiation part 40 and the second irradiation part 42 have different irradiation amounts of active light rays (preferably ultraviolet rays).

Therefore, any one of the first irradiation part 40 and the second irradiation part 42 becomes the high irradiation part 20 in which the irradiation amount of active light (preferably ultraviolet light) is relatively high (in other words, the visible light transmittance at the wavelength of 550 nm is The relatively low low light transmittance part 11), and the other becomes the low irradiation part 23 with a relatively low irradiation amount of active light (preferably ultraviolet light) (in other words, the visible light transmittance at a wavelength of 550 nm is relatively high High light transmittance part 10).

In addition, in FIG. 8 , the description will be made assuming that the first irradiation part 40 is the high irradiation part 20 (low light transmittance part 11 ), and the second irradiation part 42 is the low irradiation part 21 (high light transmittance part 10 ). .

Specifically, the visible light transmittance of the high-irradiation part 20 at the wavelength of 550 nm is, for example, less than 20%, preferably less than 10%, and, for example, 0.01% or more, and the low-irradiation part 23 at the wavelength of 550 nm. The visible light transmittance is, for example, 20% or more, preferably 40% or more, and, for example, 70% or less.

Moreover, in the bonding step, as shown in FIG. 8D , the other surface of the adhesive layer 1 is bonded to the adherend 4 in the same manner as in the first embodiment.

Thereby, an intermediate laminated body 6 is obtained, which includes the release film 2 , the adhesive layer 1 arranged on the other side of the release film 2 , and the adherend 4 arranged on the other side of the adhesive layer 1 .

Furthermore, in the intermediate laminate 6, the adhesive layer 1 has a high light transmittance portion 10 with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion 11 with a relatively small visible light transmittance at a wavelength of 550 nm. .

Furthermore, in the intermediate laminate 6, the visible light transmittance at the wavelength of 550 nm of the low light transmittance portion 11 is, for example, less than 20%, preferably less than 10%, and, for example, more than 0.01%, and high light transmittance. The visible light transmittance at the wavelength of 550 nm of the high-efficiency part 10 is, for example, 20% or more, preferably 40% or more, and, for example, 70% or less.

If the visible light transmittance of the low light transmittance portion 11 is within the above range, and the visible light transmittance of the high light transmittance portion 10 is within the above range, the relationship between the light transmittance portion 11 and the high light transmittance portion 10 can be reliably changed. hue.

According to the first modification of the first embodiment, the effect of the above-mentioned manufacturing method of the intermediate laminated body 6 is exerted, and the high irradiation part 20 (low light transmittance part 11) and The low irradiation part 23 (high light transmittance part 10) makes it possible to manufacture the intermediate laminate 6 including the adhesive layer 1 having areas with different color tones.

In particular, if the adherend 4 is the second adherend 31 , the low-irradiation portion 23 can be suppressed from being colored by external light (active light) from the surface side of the second adherend 31 .

In addition, when the non-irradiated/low-irradiated part 21 is the low-irradiated part 23, the irradiation step includes: a third irradiation step, which is performed by irradiating the entire adhesive layer 1 with active light (preferably ultraviolet light). The entire adhesive layer 1 is formed into the third irradiation part 43 that is irradiated with active light (preferably ultraviolet light); and the fourth irradiation step is performed by arranging a part 45 of the third irradiation part 43 to block the active light (preferably ultraviolet ray). After the mask 7 is used, the remaining portion 46 of the third irradiation portion 43 is irradiated with active light (preferably ultraviolet rays), so that the remaining portion 46 of the third irradiation portion 43 becomes the fourth irradiation portion 44 .

In the following description, a case where the non-irradiated/low-irradiated portion 21 becomes the low-irradiated portion 23 in the 1A embodiment will be described with reference to FIG. 9 (hereinafter referred to as a second variation of the 1A embodiment).

In the preparation step, as shown in FIG. 9A , the adhesive sheet 1 is prepared in the same manner as in the above-described 1A embodiment.

In the irradiation step, the adhesive layer 1 is irradiated with active light (preferably ultraviolet light) to form a high-irradiation portion 20 with a relatively high amount of active light (preferably ultraviolet light) in the adhesive layer 1, and an active light (preferably ultraviolet light) It is the low irradiation part 23 where the irradiation amount of ultraviolet rays is relatively low.

Specifically, in the third irradiation step among the irradiation steps, the third irradiation portion 43 is formed, and in the fourth irradiation step among the irradiation steps, the remaining portion 46 (to be described below) of the third irradiation portion 43 becomes the fourth Irradiation section 44.

In the third irradiation step, as shown in FIG. 9B , the entire adhesive layer 1 is irradiated with active light (preferably ultraviolet light) from the surface side of the release film 2 (the surface side of the adhesive layer 1 ).

Thereby, the entire adhesive layer 1 is formed into the third irradiation portion 43 .

Moreover, in the adhesive layer 1 (third irradiation part 43), the acid is generated from the photoacid generator, and the compound colored by the acid is colored (specifically, black) by the acid. As a result, the entire adhesive layer 1 (the third irradiated portion 43) changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low).

Then, in the fourth irradiation step, as shown in FIG. 9C , by arranging a mask 7 that blocks active light (preferably ultraviolet light) in part 45 of the third irradiation part 43, the remaining part of the third irradiation part is 46 irradiates active light (preferably ultraviolet light), so that the remaining portion 46 of the third irradiation portion 43 becomes the fourth irradiation portion 44.

Furthermore, in the following description, the adhesive sheet 1 is divided into three parts in the surface direction, and the two end parts 2 are set as the remaining parts 46 of the third irradiation part 43 (in other words, the adhesive sheet 1 is 1 is divided into three parts in the plane direction, and only the central part 1 is a part 45) of the third irradiation part 43 for explanation.

Specifically, in the fourth irradiation step, active light (preferably ultraviolet light) is irradiated from the surface side of the adhesive layer 1 to the remaining portion 46 of the third irradiation portion 43 . The remaining parts are not irradiated with active light (preferably ultraviolet light).

More specifically, no active ray-blocking (relative to The mask 7, preferably ultraviolet), is disposed on a part 45 of the third irradiation part 43 (specifically, the other side of the release film 2 disposed on the other side of the part 45 of the third irradiation part 43) to block active light ( The mask 7, preferably ultraviolet light, irradiates active light (preferably ultraviolet light) from the surface side of the adhesive layer 1.

Thereby, only the remaining portion 46 of the third irradiation portion 43 can be irradiated with active light (preferably ultraviolet light), and the remaining portion 46 of the third irradiation portion 43 becomes the fourth irradiation portion 44 .

Furthermore, in the adhesive layer 1 in the fourth irradiation part 44, the acid is generated from the photoacid generator, and the compound colored by the acid is colored (specifically, black) by the acid. As a result, the adhesive layer 1 in the fourth irradiation part 44 changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low).

Thereby, the visible light transmittance at the wavelength of 550 nm of the fourth irradiation part 44 becomes lower than that of the third irradiation part 43 .

That is, the third irradiation part 43 becomes the low irradiation part 23 in which the irradiation amount of active light (preferably ultraviolet light) is relatively low (in other words, the third irradiation part 43 is the high light transmittance part 10 in which the visible light transmittance at the wavelength of 550 nm is relatively high), The fourth irradiation part 44 becomes the high irradiation part 20 in which the irradiation amount of active light (preferably ultraviolet light) is relatively high (in other words, the low light transmittance part 11 in which the visible light transmittance at the wavelength of 550 nm is relatively low).

Specifically, the visible light transmittance of the high-irradiation part 20 at the wavelength of 550 nm is, for example, less than 20%, preferably less than 10%, and, for example, 0.01% or more, and the low-irradiation part 23 at the wavelength of 550 nm. The visible light transmittance is, for example, 20% or more, preferably 40% or more, and, for example, 70% or less.

Furthermore, in the bonding step, as shown in FIG. 9D , the other surface of the adhesive sheet 1 (the other surface of the adhesive layer 1 ) is bonded to the adherend 4 in the same manner as in the above-described 1A embodiment.

Thereby, an intermediate laminated body 6 is obtained, which includes the release film 2 , the adhesive layer 1 arranged on the other side of the release film 2 , and the adherend 4 arranged on the other side of the adhesive layer 1 .

Furthermore, in the intermediate laminate 6, the adhesive layer 1 has a high light transmittance portion 10 with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion 11 with a relatively small visible light transmittance at a wavelength of 550 nm. .

Furthermore, in the intermediate laminate 6, the visible light transmittance at the wavelength of 550 nm of the low light transmittance portion 11 is, for example, less than 20%, preferably less than 10%, and, for example, more than 0.01%, and high light transmittance. The visible light transmittance at the wavelength of 550 nm of the high-efficiency part 10 is, for example, 20% or more, preferably 40% or more, and, for example, 70% or less.

If the visible light transmittance of the low light transmittance portion 11 is within the above range, and the visible light transmittance of the high light transmittance portion 10 is within the above range, the relationship between the light transmittance portion 11 and the high light transmittance portion 10 can be reliably changed. hue.

According to the second modification example of the 1A embodiment, the effect of the above-mentioned manufacturing method of the intermediate laminated body 6 is exerted, and the high irradiation part 20 (low light transmittance part 11) and The low irradiation part 23 (high light transmittance part 10) makes it possible to manufacture the intermediate laminate 6 including the adhesive layer 1 having areas with different color tones.

In particular, if the adherend 4 is the second adherend 31 , the low-irradiation portion 23 can be suppressed from being colored by external light (active light) from the surface side of the second adherend 31 .

In the above description, the case where the non-irradiated/low-irradiated portion 21 is set as the low-irradiated portion 23 in the 1A embodiment has been explained. In the 1B embodiment and the 2A embodiment (using the first adherend) case) and the 2B embodiment, the non-irradiated/low-irradiated portion 21 may be set to the low-irradiated portion 23 based on the same procedure as the irradiation step in the first variation or the second variation of the above-mentioned 1A embodiment.

In addition, by using a plurality of masks 7 that block active light (preferably ultraviolet rays), it is possible to obtain the intermediate laminate 6 in which the low light transmittance portion 11 of the adhesive layer 1 has a pattern shape.

Specifically, in the irradiation step of the first embodiment, as shown in FIG. 9A , a plurality of masks 7 for blocking active light (preferably ultraviolet light) are arranged on the other side of the release film 2 (specifically, Arrange 4 at intervals).

Furthermore, by carrying out the preparation step, the irradiation step and the laminating step in the same manner as in the above-described first embodiment, the intermediate laminate 6 in which the low light transmittance portion 11 in the adhesive layer 1 has a pattern shape can be obtained as shown in FIG. 9B .

In the intermediate laminate 6, if the low light transmittance portion 11 has a pattern shape, the pattern shape can be freely designed.

In the above description, the case where the acid generator is a photoacid generator is explained. When the acid generator is a thermal acid generator, in the above description, the adhesive layer 1 is heated in the irradiation step instead of heating it. The step of irradiating the adhesive layer 1 with light (irradiation step). Thereby, the acid generator (thermal acid generator) in the self-adhesive layer 1 generates an acid, and the compound colored by the acid is colored by the acid, whereby the adhesive layer 1 changes from colorless (transparent) to colored. [Example]

Examples and comparative examples will be disclosed below to explain the present invention more specifically. In addition, the present invention is not limited at all by the Examples and Comparative Examples. In addition, specific numerical values such as blending ratios (content ratios), physical property values, and parameters used in the following description may be replaced by corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Embodiments". The corresponding recorded upper limit value (a value defined as "below" or "under") or a lower limit value (a value defined as "above" or "exceeds").

In addition, "parts" and "%" are based on mass unless otherwise mentioned.

1. Details of components Each component used in each Example and each Comparative Example is described below. 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate BA: butyl acrylate NVP: N-vinylpyrrolidone HEA: 2-hydroxyethyl acrylate AA: Takenate acrylate D110N: xylylene diisocyanate 75% ethyl acetate solution of trimethylolpropane adduct, manufactured by Mitsui Chemicals Coronate HX: Isocyanurate body of hexamethylene diisocyanate, manufactured by Tosoh Tetrad C: Trade name: 1,3-bis (N,N-diglycidylaminomethyl)cyclohexane (epoxy cross-linking agent), Mitsubishi Gas Chemical Co., Ltd. BLACK ND1: Leuco dye, Yamada Chemical Co., Ltd. CPI-310B: Contains sulfide and (C ₆ F ₅ ) ₄ B ^- salt, photoacid generator, manufactured by San-Apro Solvent Black 29: dye

2. Preparation of adhesive polymer Synthesis example 1 63 parts by mass of 2-ethylhexyl acrylate (2EHA) and 15 parts by mass of N-vinylpyrrolidone (NVP) as monomer components were put into a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling pipe, and a nitrogen introduction pipe. , 9 parts by mass of methyl methacrylate (MMA), 13 parts by mass of 2-hydroxyethyl acrylate (HEA), 0.2 parts by mass of azobisisobutyronitrile as a polymerization initiator, 233 parts by mass of ethyl acetate as a solvent portion, add nitrogen, and perform nitrogen replacement for about 1 hour while stirring. Thereafter, the mixture was heated to 60° C. and reacted for 7 hours to obtain a solution of an adhesive polymer with a weight average molecular weight (Mw) of 1,200,000.

In addition, the glass transition temperature of the adhesive polymer calculated by the FOX formula is -34°C.

Synthesis Example 2 to Synthesis Example 3 A solution of an adhesive polymer was produced in the same manner as in Synthesis Example 1, except that the formulation of the monomer components was changed according to Table 1.

3. Preparation of adhesive and adhesive layer Example 1 To the solution of the adhesive polymer in Synthesis Example 1, 1.1 parts by mass of Takenate D-110N (xylylenedimethyldiethylene) as a cross-linking agent was added to 100 parts by mass of the adhesive polymer in the solution of the adhesive polymer. 75% ethyl acetate solution of trimethylolpropane adduct of isocyanate, manufactured by Mitsui Chemicals), 1 part by mass per 100 parts by mass of the adhesive polymer in the solution is colored by acid The compound BLACK ND1 (leuco dye) and CP-310B (photoacid generator) as an acid generator are 2 parts by mass per 100 parts by mass of the adhesive polymer in the solution, uniformly Mix to prepare adhesive.

Then, use a grooved roller to coat the adhesive of Example 1 on one side of the polyethylene terephthalate film with a thickness of 50 μm that has been released from the mold in such a way that the thickness after drying becomes 25 μm, and then heat at 130°C. Dry for 1 minute to remove the solvent. This forms an adhesive layer. Then, the release-treated surface of the release film (polyethylene terephthalate film with a thickness of 25 μm and a surface treated with polysiloxane release treatment) was bonded to the adhesive side. Thereafter, aging treatment was performed for 4 days in an environment of 25°C to allow cross-linking reaction. This creates an adhesive layer of 25 μm.

Example 2 Two pieces of the 25 μm adhesive layer obtained in Example 1 were laminated to obtain a 50 μm adhesive layer.

Example 3 Three pieces of the 25 μm adhesive layer obtained in Example 1 were laminated to obtain a 75 μm adhesive layer.

Example 4 Four pieces of the 25 μm adhesive layer obtained in Example 1 were laminated to obtain a 100 μm adhesive layer.

Example 5 The formulation was changed according to Table 2, except that the adhesive sheet (25 μm adhesive layer) was produced in the same manner as in Example 1.

Example 6 Two pieces of the 25 μm adhesive layer obtained in Example 5 were laminated to obtain a 50 μm adhesive layer.

Example 7 Three pieces of the 25 μm adhesive layer obtained in Example 5 were laminated to obtain a 75 μm adhesive layer.

Example 8 Four pieces of the 25 μm adhesive layer obtained in Example 5 were laminated to obtain a 100 μm adhesive layer.

Example 9 The formulation was changed according to Table 2, except that the adhesive sheet (25 μm adhesive layer) was produced in the same manner as in Example 1.

Comparative Example 1 to Comparative Example 3 The formulation was changed according to Table 2, except that the adhesive sheet (25 μm adhesive layer) was produced in the same manner as in Example 1.

Furthermore, in Comparative Example 3, Solvent Black 29 was used as the dye.

4.Evaluation (Cut storage modulus and tan δ) For the adhesive layers of Examples 1, 5, and 9, 60 pieces of the adhesive layers were prepared, and the adhesive layers were laminated to prepare a sample for measuring the shear storage modulus of 1.5 mm. The "Advanced Rheometric Expansion System (ARES)" manufactured by Rheometric Scientific was used to measure the shear storage modulus and tan δ of the sample for shear storage modulus measurement under the following conditions. The results are shown in Table 2.

(Measurement conditions) Deformation mode: Torsion Measurement frequency: 1 Hz Heating rate: 5℃/min Measurement temperature: -70℃～250℃ Shape: Parallel plate 8.0 mm

(transmittance) The adhesive layer of each example and each comparative example was attached to a glass substrate, and the transmittance at 550 nm before and after irradiating LED (Light Emitting Diode, light-emitting diode) (365 nm, 8000 mJ/□) was measured.

Furthermore, only the data measured on the glass substrate were used as the baseline.

The results are shown in Table 2.

(Reflectivity) The adhesive layer of each example and each comparative example was attached to an adherend made of aluminum foil attached to an acrylic plate, and the reflectance at 550 nm before and after irradiation with LED (365 nm, 8000 mJ/□) was measured.

Furthermore, the data measured only on the adherend in which the aluminum foil was attached to an acrylic plate was set as the baseline.

The results are shown in Table 2.

(coloring stability) The adhesive layer of each example and each comparative example was irradiated with light of 8000 mJ/□ and left at 85°C for 3 days. The transmittance before and after being left for 3 days was measured by the same procedure as the above-mentioned transmittance measurement method.

In addition, the adhesive sheet of each example and each comparative example was irradiated with light of 8000 mJ/□, left for 3 days at 85°C and a relative humidity of 85%, and measured by the same procedure as the above transmittance measurement method. Transmittance before and after.

The results are shown in Table 2.

(transparent stability) The adhesive layer of each example and each comparative example was placed at 23°C and a relative humidity of 50% for 3 days, and the transmittance before and after being placed for 3 days was measured by the same procedure as the above-mentioned transmittance measurement method.

The results are shown in Table 2. [Table 1] Table 1 Synthesis example No. Synthesis example 1 Synthesis example 2 Synthesis example 3 Monomer composition Alkyl (meth)acrylates 2EHA 63 95 - MMA 9 - - BA - - 95 Basic vinyl monomer with lone electron pair NVP 15 - - Functional vinyl monomer HEA 13 5 - Acidic vinyl monomer with anionic group AA - - 5 weight average molecular weight 1200000 440000 600000 Glass transition temperature (℃) Calculated according to FOX formula -34 -68 -50 [Table 2] Table 2 Example/Comparative Example No. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative example 1 Comparative example 2 Comparative example 3 Adhesive adhesive polymer Adhesive polymer of synthesis example 1 100 100 100 100 - - - - - 100 100 100 Adhesive polymer of synthesis example 2 - - - - 100 100 100 100 - - - - Adhesive polymer of synthesis example 3 - - - - - - - - 100 - - - Cross-linking agent Takenate D110N 1.1 1.1 1.1 1.1 - - - - - 1.1 1.1 1.1 Coronate HX - - - - 4 4 4 4 - - - - Tetrad C - - - - - - - - 0.075 - - - Compounds colored by acids BLACK ND1 (leuco dye) 1 1 1 1 1 1 1 1 1 - 1 - acid generator CPI-310B 2 2 2 2 2 2 2 2 2 2 - - Solvent Black 29 - - - - - - - - - - - 1 adhesive layer Thickness(μm) 25 50 75 100 25 50 75 100 25 25 25 25 Evaluation Shear storage modulus (Pa) 20℃ 3.75×10 ⁵ - - - 9.55×10 ⁴ - - - 2.43×10 ⁵ - - - Shear storage modulus (Pa) 50℃ 1.32×10 ⁵ - - - 1.06×10 ⁵ - - - 8.93×10 ⁴ - - - tanδ 20℃ 8.73× ^10-1 - - - 2.82× ^10-2 - - - 7.44× ^10-1 - - - tanδ 50℃ 3.54× ^10-1 - - - 9.51× ^10-3 - - - 3.76× ^10-1 - - - Transmittance (%) before light exposure 100 100 100 100 100 100 100 100 98 100 100 30.1 After light exposure 36.2 12.6 4.1 1.5 40.1 18.2 6.3 2.3 28.2 100 100 31.4 Reflectivity(%) before light exposure 91.0 - - - 90.1 - - - 89.5 90.3 90.5 14.5 After light exposure 13.0 - - - 15.8 - - - 10.1 90.4 90.2 15.0 Coloring stability (85℃, placed for 3 days) Initial state (before placement) 36.2 - - - 40.1 - - - 28.2 - - - After placing 63.1 - - - 72.4 - - - 33.1 - - - Changes before and after placement 26.9 - - - 32.3 - - - 4.9 - - - Coloring stability (85℃, relative humidity 85%, left for 3 days) Initial state (before placement) 36.2 - - - 40.1 - - - 28.2 - - - After placing 100 - - - 98.5 - - - 44.4 - - - Changes before and after placement 63.8 - - - 58.4 - - - 16.2 - - - Transparency stability (23℃, relative humidity 50%, left for 3 days) Initial state (before placement) 100 - - - 100 - - - 98.0 - - - After placing 72.2 - - - 72.0 - - - 56.0 - - - Changes before and after placement 27.8 - - - 28.0 - - - 44.0 - - -

In addition, the above-mentioned invention is provided as an exemplary embodiment of the present invention, but it is only an example and cannot be interpreted in a restrictive manner. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Industrial availability]

The adhesive, the manufacturing method of the intermediate laminate and the intermediate laminate of the present invention can be preferably used in optical devices, electronic devices and their constituent parts.

1: Adhesive layer 2: Peel off film 3: Adhesive sheet 4: Adhered body 5:Substrate 6: Intermediate laminated body 7: Mask 8: 1st mask 9: 2nd mask 10: High light transmittance part 11: Low light transmittance part 20: High irradiation part 21: Unirradiated/low irradiated part 22: Unirradiated part 23: Low irradiation part 30: The first adherend 31: The second adherend 40: 1st irradiation part 41: Part not irradiated yet 42: 2nd irradiation part 43: 3rd irradiation part 44: 4th irradiation part 45: part 46:The rest

FIG. 1 is a schematic diagram showing an embodiment of a method for manufacturing an adhesive layer. FIG. 1A shows the steps of preparing a release film, and FIG. 1B shows the steps of arranging an adhesive layer on one side of the release film. Figure 2 is a schematic diagram showing an embodiment of a method for manufacturing an adhesive sheet. Figure 2A shows the steps of preparing the base material. Figure 2B shows the step of arranging the adhesive layer on one side of the base material. Figure 2C shows the step of arranging the adhesive layer on one side. Steps to peel off the film. FIG. 3 is a schematic diagram showing an embodiment of the intermediate laminated body of the present invention. FIG. 4 is a schematic view showing the first embodiment of the method for manufacturing an intermediate laminated body of the present invention. FIG. 4A shows the preparation steps for preparing an adhesive layer. FIG. 4B shows the surface side of the self-release film (the surface side of the adhesive layer) to the adhesive layer. The step of irradiating the layer with active light, Figure 4C shows the step of joining the adhesive layer to the adherend. FIG. 5 is a schematic diagram showing the 2A embodiment of the method for manufacturing an intermediate laminated body of the present invention (when the adherend is the first adherend). FIG. 5A shows the preparation steps for preparing the adhesive layer, and FIG. 5B shows the adhesive layer. The step of laminating the layer to the first adherend is shown in Figure 5C. The step of irradiating the adhesive layer with active light from the surface side of the first adherend is shown. Figure 5D shows the 2A embodiment (the adherend is the first adherend). Intermediate laminate produced in the case of adherends). FIG. 6 is a schematic view showing the 2A embodiment of the method for manufacturing an intermediate laminated body of the present invention (when the adherend is the second adherend). FIG. 6A shows the preparatory steps for preparing the adhesive layer, and FIG. 6B shows the step of preparing the adhesive layer. The step of bonding the layer to the second adherend is shown in Figure 6C. The step of irradiating the adhesive layer with active light from the surface side of the second adherend is shown. Figure 6D shows the 2A embodiment (the adherend is the second adherend). Intermediate laminate produced in the case of adherends). FIG. 7 is a schematic diagram showing the 2B embodiment of the method for manufacturing an intermediate laminated body of the present invention. FIG. 7A shows the preparatory steps for preparing the adhesive layer. FIG. 7B shows the joining steps for joining the adhesive layer to the adherend. 7C shows the step of irradiating the adhesive layer with active light from the surface side of the peeling film (the surface side of the adhesive layer), and FIG. 7D shows the intermediate laminate produced in Embodiment 2B. 8 is a schematic diagram showing a first modification example of the first A embodiment of the method for manufacturing an intermediate laminated body of the present invention. FIG. 8A shows a preparatory step for preparing an adhesive layer, and FIG. 8B shows the first irradiation by irradiating an active light ray. Part, and the first irradiation step of the unirradiated part. Figure 8C shows the second irradiation step of forming the unirradiated part into the second irradiated part by irradiating the unirradiated part with active light. Figure 8D shows the adhesive layer. The step of attaching to the adherend. FIG. 9 is a schematic diagram showing a second modification example of the first A embodiment of the method for manufacturing an intermediate laminated body of the present invention. FIG. 9A shows the preparation steps for preparing an adhesive sheet, and FIG. 9B shows the overall activation by irradiation of the adhesive layer. The third irradiation step is to form the entire adhesive layer into a third irradiation part by irradiating light. FIG. 9C shows that the remaining part of the third irradiation part is irradiated by arranging a mask that blocks the active light in a part of the third irradiation part. In the fourth irradiation step, the remaining parts of the third irradiation part are formed into the fourth irradiation part by using active light. Figure 9D shows the lamination step of laminating the adhesive sheet to the adherend. Figure 10 is a schematic diagram showing a method of manufacturing an intermediate laminate in which the low light transmittance portion of the adhesive layer has a pattern shape. Figure 10A shows the irradiation step of arranging a plurality of masks for blocking active light. Figure 10B shows the method of manufacturing the intermediate laminate in the adhesive layer. The low light transmittance part has a pattern-shaped intermediate laminate.

1: Adhesive layer

2: Peel off film

Claims (18)

An adhesive characterized in that it contains an adhesive polymer as a polymer as a monomer component, a compound colored by an acid, and an acid generator, and the glass transition temperature of the adhesive polymer is 0°C or lower and 20°C. The shear storage modulus G' at ~50°C is 1.0×10 ⁴ Pa or more and 1.0×10 ⁶ Pa or less. The adhesive of claim 1, wherein the monomer component includes an acidic vinyl monomer with anionic groups. The adhesive according to claim 1 or 2, wherein the above-mentioned monomer component does not substantially contain an alkaline vinyl monomer with a lone electron pair. A method for manufacturing an intermediate laminated body, characterized in that it includes the following steps: a preparation step, which is to prepare an adhesive layer containing the adhesive according to claim 1; The irradiation step is to irradiate the above-mentioned adhesive layer with active rays to form a high-irradiation part where the irradiation amount of active rays is relatively high, and an unirradiated part where the irradiation amount of active rays is relatively low or where no active rays are irradiated. The low-irradiation part, whereby the visible light transmittance at the wavelength of 550 nm in the above-mentioned high-irradiation part is smaller than the visible light transmittance at the wavelength of 550 nm in the above-mentioned unirradiated/low-irradiation part; and The bonding step involves bonding the other side of the above-mentioned adhesive layer to the adherend. The method for manufacturing an intermediate laminated body according to claim 4, wherein the irradiation step is performed after the preparation step, and The above-mentioned bonding step is performed after the above-mentioned irradiation step. The manufacturing method of the intermediate laminated body of claim 4, wherein the above-mentioned laminating step is performed after the above-mentioned preparation step, and The above-mentioned irradiation step is performed after the above-mentioned bonding step. The method for manufacturing an intermediate laminated body according to claim 6, wherein in the irradiation step, the adhesive layer is irradiated with active light from the surface side of the adhesive layer. The method for manufacturing an intermediate laminated body according to claim 6, wherein in the irradiation step, the adhesive layer is irradiated with active light from the surface side of the adherend. The method for manufacturing an intermediate laminated body according to claim 8, wherein the average transmittance of active light rays of the adherend is above 60%, and In the above-mentioned irradiation step, after arranging a mask for blocking active rays on a part of the other surface on the side of the adherend, the above-mentioned adhesive layer is irradiated with active rays. The manufacturing method of the intermediate laminate according to claim 8, wherein the adherend blocks active light, and In the above-mentioned laminating step, the above-mentioned adherend is arranged on a part of the other side of the above-mentioned adhesive layer. The method for manufacturing an intermediate laminated body according to any one of claims 4 to 10, wherein the unirradiated/low-irradiated portion is an unirradiated portion that is not irradiated with active light, and The visible light transmittance of the above-mentioned unirradiated part at a wavelength of 550 nm is more than 80%. The method for manufacturing an intermediate laminated body according to any one of claims 4 to 9, wherein the non-irradiated/low-irradiated portion is a low-irradiated portion with a low irradiation amount of active light, The above-mentioned irradiation step includes: a first irradiation step, which is to irradiate the above-mentioned adhesive layer with active rays by arranging a first mask that blocks active rays, thereby forming a first irradiation part irradiated with active rays on the above-mentioned adhesive layer, and The unexposed portion that is not exposed to active light; and The second irradiation step is to irradiate the temporarily unirradiated part of the above-mentioned adhesive layer with active light after arranging a second mask that blocks active light in the first irradiation part, so that the temporarily unirradiated part is formed into 2nd irradiation part; and Either one of the first irradiation part and the second irradiation part is the high irradiation part, and the other one is the low irradiation part. The method for manufacturing an intermediate laminated body according to any one of claims 4 to 9, wherein the non-irradiated/low-irradiated portion is a low-irradiated portion with a low irradiation amount of active light, The above-mentioned irradiation step includes: a third irradiation step, in which the entirety of the above-mentioned adhesive layer is irradiated with active light, so that the entirety of the above-mentioned adhesive layer is formed into a third irradiation part that is irradiated with active light; and The fourth irradiation step is to form the remaining part of the third irradiation part by arranging a mask that blocks active rays in a part of the third irradiation part and then irradiating the remaining parts of the third irradiation part with active rays. is part 4 of the irradiation; and The above-mentioned third irradiation part is the above-mentioned low irradiation part, The above-mentioned fourth irradiation part is the above-mentioned high irradiation part. The manufacturing method of the intermediate laminate according to claim 12, wherein the visible light transmittance at the wavelength of 550 nm in the highly irradiated portion does not reach 20%, and The visible light transmittance at the wavelength of 550 nm in the above-mentioned low-irradiation part is between 20% and below 70%. An intermediate laminate characterized by having an adhesive layer containing the adhesive according to claim 1, and an adherend arranged on the other side of the adhesive layer, and The above-mentioned adhesive layer has a high light transmittance portion with a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion with a relatively small visible light transmittance at a wavelength of 550 nm. The intermediate laminate according to claim 15, wherein the low light transmittance portion has a pattern shape. The intermediate laminate of claim 15 or 16, wherein the visible light transmittance of the high light transmittance portion at a wavelength of 550 nm is more than 80%. The intermediate laminate of claim 15 or 16, wherein the visible light transmittance of the low light transmittance portion at a wavelength of 550 nm does not reach 20%, and The visible light transmittance at the wavelength of 550 nm in the above-mentioned high light transmittance part is 20% or more and 70% or less.