KR102419776B1 - Adhesive, manufacturing method of intermediate laminate and intermediate laminate - Google Patents

Abstract

An adhesive contains the adhesive polymer which is a polymer of a monomer component, the compound colored with an acid, and an acid generator. The glass transition temperature of the tacky polymer is 0° C. or less. 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 a pressure-sensitive adhesive, a method for producing an intermediate laminate, and an intermediate laminate, and more particularly, to a method for producing an intermediate laminate obtained by using a pressure-sensitive adhesive and an adhesive layer made of the pressure-sensitive adhesive, and production of the intermediate laminate It relates to an intermediate laminate obtained by the method.

In recent years, a display equipped with an organic EL panel is known. Since the organic EL panel has an electrode layer with high reflectivity, reflection of external light, reflection of the background, and the like are likely to occur.

And in order to prevent reflection of external light or a background, it is known to provide the layer (light absorption layer) which has a function which absorbs light on the reflective surface of an electrode layer.

As such a light absorption layer, a light absorption layer containing a carbon black pigment and dye has been proposed (for example, refer to Patent Document 1).

Japanese Patent Laid-Open No. 2017-203810

On the other hand, when the layer having a function of absorbing light is an adhesive layer, transparency is sometimes required from the viewpoint of inspection and the like.

The present invention relates to a method for producing an intermediate laminate obtained by using a pressure-sensitive adhesive capable of being colored by irradiating actinic light at an arbitrary timing, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive, and an intermediate laminate obtained by the method for producing the intermediate laminate It is about providing a body.

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

This invention [2] contains the adhesive as described in said [1] in which the said monomer component contains the acidic vinyl monomer which has an anionic group.

The present invention [3] contains the pressure-sensitive adhesive according to [1] or [2], wherein the monomer component does not substantially contain a basic vinyl monomer having a lone pair of electrons.

The present invention [4] is a preparatory step for preparing an adhesive layer comprising the pressure-sensitive adhesive according to any one of [1] to [3], irradiating actinic light to the pressure-sensitive adhesive layer, and to the pressure-sensitive adhesive layer, The visible light transmittance at a wavelength of 550 nm of the highly irradiated portion by forming a highly irradiated portion with a high irradiation amount of A method for producing an intermediate laminate, comprising: an irradiation step of making the non-irradiated/low-irradiated portion smaller than the visible light transmittance at a wavelength of 550 nm, and a bonding step of adhering the other side of the adhesive layer to an adherend contains

This invention [5] includes the manufacturing method of the intermediate laminated body as described in said [4] which implements the said irradiation process after the said preparation process, and implements the said sticking process after the said irradiation process.

This invention [6] includes the manufacturing method of the intermediate laminated body as described in said [4] which implements the said sticking process after the said preparation process, and implements the said irradiation process after the said sticking process.

This invention [7] includes the manufacturing method of the intermediate|middle laminated body as described in said [6] which irradiates actinic light to the said adhesive layer from the surface side of the said adhesive layer in the said irradiation process.

This invention [8] includes the manufacturing method of the intermediate|middle laminated body as described in said [6] which irradiates actinic light to the said adhesive layer from the surface side of the said to-be-adhered body in the said irradiation process.

In the present invention [9], in the adherend, the average transmittance of actinic light is 60% or more, and in the irradiation step, after disposing a mask for blocking actinic light on a part of the other surface on the side of the adherend, The manufacturing method of the intermediate|middle laminated body as described in said [8] of irradiating actinic light to the said adhesive layer is included.

In the present invention [10], the intermediate according to the above [8], wherein the adherend blocks actinic light, and the adherend is disposed on a part of the other side of the adhesive layer in the sticking step A method for manufacturing a laminate is included.

In the present invention [11], the above [4] to [11], wherein the non-irradiated/low irradiated portion is a non-irradiated portion not irradiated with actinic light, and the non-irradiated portion has a visible light transmittance at a wavelength of 550 nm of 80% or more. The method for producing the intermediate laminate according to any one of [10] is included.

In the present invention [12], the non-irradiated/low-irradiated portion is a low-irradiation portion with a low irradiation amount of actinic light, and the irradiation step is performed on the adhesive layer after disposing a first mask that blocks the actinic light A first irradiation step of forming, in the adhesive layer, a first irradiated portion irradiated with actinic light and a temporary non-irradiated portion not irradiated with actinic light by irradiating the adhesive layer with the first irradiation; After arranging a second mask that blocks actinic light in the portion, second irradiation using the provisionally irradiated portion as a second irradiation portion by irradiating the provisionally irradiated portion with actinic light on the portion of the adhesive layer The intermediate lamination according to any one of [4] to [9], comprising a step, wherein either one of the first irradiated portion and the second irradiated portion is the high irradiated portion, and the other is the low irradiated portion. It includes a method for manufacturing a sieve.

In the present invention [13], the non-irradiated/low-irradiated portion is a low-irradiation portion with a low irradiation amount of actinic light, and in the irradiation step, all of the adhesive layer is irradiated with actinic light, whereby the adhesive layer is 3rd irradiation process which makes all of it the 3rd irradiation part irradiated with actinic light, and after arrange|positioning the mask which block|blocks actinic light in a part of said 3rd irradiation part, actinic light in the remainder of the said 3rd irradiation part a fourth irradiation step of making the remainder of the third irradiated portion into a fourth irradiated portion by irradiating The method for producing the intermediate laminate according to any one of [4] to [9], which is a highly irradiated portion, is included.

In the present invention [14], the high-irradiation portion has a visible light transmittance at a wavelength of 550 nm of less than 20%, and the low-irradiation portion has a visible light transmittance at a wavelength of 550 nm of 20% or more and 70% or less. ] or the method for producing the intermediate laminate as described in [13].

The present invention [15] includes an adhesive layer made of the adhesive according to any one of [1] to [3] and an adherend disposed on the other side of the adhesive layer, wherein the adhesive layer has a relative wavelength of 550 nm. An intermediate laminate comprising a high light transmittance portion having a large visible light transmittance and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm.

The present invention [16] includes the intermediate laminate according to [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 high light transmittance portion has a visible light transmittance at a wavelength of 550 nm of 80% or more.

In the present invention [18], the low light transmittance portion has a visible light transmittance at a wavelength of 550 nm is less than 20%, and the high light transmittance portion has a visible light transmittance at a wavelength of 550 nm of 20% or more and 70% or less. ] or the intermediate laminate according to [16].

The pressure-sensitive adhesive of the present invention contains a pressure-sensitive adhesive polymer, a compound colored with an acid, and an acid generator.

An acid generator is a compound which generate|occur|produces an acid by actinic light irradiation or heating, and the compound colored by an acid is specifically, a compound which changes from colorless (transparent) to colored by an acid.

Therefore, this pressure-sensitive adhesive changes from colorless (transparent) to colored by generating an acid from an acid generator by irradiation with actinic light or heating, and the compound colored by the acid is colored by the acid. .

Then, according to this adhesive, it can be made to color by irradiating actinic light at arbitrary timings.

Moreover, the glass transition temperature of the adhesive polymer in this invention is 0 degreeC or less.

Therefore, it is excellent in step|step difference followability|trackability.

Moreover, the shear storage modulus G' in 20 degreeC - 50 degreeC of the adhesive polymer in this invention is 1.0 x 10 ⁴ Pa or more and 1.0 x 10 ⁶ Pa or less.

Therefore, it is excellent in adhesiveness, and when shear storage elastic modulus G' is lower, it is also excellent in level|step difference followability|trackability.

The manufacturing method of the intermediate|middle laminated body of this invention is equipped with the preparatory process of preparing the adhesive layer which consists of the adhesive of this invention.

Therefore, the adhesion layer can be colored by irradiating actinic light to this adhesion layer.

Moreover, in the manufacturing method of this intermediate|middle laminated body, the highly irradiated part with a relatively high irradiation amount of actinic light, and a non-irradiated/low-irradiation part where the irradiation amount of actinic light is relatively low, or actinic light is not irradiated to an adhesive layer. An irradiation step of making the visible light transmittance at a wavelength of 550 nm of the highly irradiated portion smaller than the visible light transmittance of the non-irradiated/low irradiated portion at a wavelength of 550 nm is provided by forming a.

Therefore, it is made to remain|survive as it is transparent, except for the colored part in an adhesion layer, or can reduce the coloring amount rather than a colored part.

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

Therefore, the adhesive layer in an intermediate|middle laminated body has a function to absorb light in a colored part, and has transparency or has a function to absorb light lower than a colored part in other than a colored part.

1 is a schematic view showing an embodiment of a method for manufacturing an adhesive layer, in which FIG. 1A shows a step of preparing a release film, and FIG. 1B is a step of disposing an adhesive layer on one side of the release film indicates
[Fig. 2] Fig. 2 is a schematic view showing an embodiment of a method for manufacturing an adhesive sheet, in which Fig. 2A shows a process for preparing a substrate, and Fig. 2B shows a process for arranging an adhesive layer on one side of the substrate , Fig. 2C shows a step of disposing a release film on one side of the pressure-sensitive adhesive layer.
[Fig. 3] Fig. 3 is a schematic view showing one embodiment of the intermediate laminate of the present invention.
[Fig. 4] Fig. 4 is a schematic view showing a first embodiment of a method for manufacturing an intermediate laminate of the present invention, Fig. 4A showing a preparatory process for preparing an adhesive layer, and Fig. 4B showing a surface side of the release film (adhesive layer) The irradiation step of irradiating the adhesive layer with actinic light from the surface side) is shown, and Fig. 4C shows the sticking step of sticking the adhesive layer to the adherend.
[Fig. 5] Fig. 5 is a schematic diagram showing a second embodiment (when an adherend is a first adherend) of the method for manufacturing an intermediate laminate of the present invention, Fig. 5A shows a preparatory process for preparing an adhesive layer, Fig. 5B shows a sticking step of adhering the adhesive layer to the first adherend, Fig. 5C shows an irradiation step of irradiating the adhesive layer with actinic light from the surface side of the first adherend, and Fig. 5D shows the second A embodiment (adhering) In the case where the sieve is the first adherend), the intermediate laminate produced is shown.
[Fig. 6] Fig. 6 is a schematic view showing a second embodiment (when an adherend is a second adherend) of the method for manufacturing an intermediate laminate of the present invention, Fig. 6A shows a preparatory step for preparing an adhesive layer, Fig. 6B shows a bonding step of adhering the pressure-sensitive adhesive layer to the second adherend; The intermediate laminate produced in the case of the sieve as the second adherend) is shown.
[Fig. 7] Fig. 7 is a schematic view showing a second embodiment of the method for manufacturing an intermediate laminate of the present invention, in which Fig. 7A shows a preparatory process for preparing an adhesive layer, and Fig. 7B is a method for adhering the adhesive layer to an adherend. shows the sticking step, Fig. 7C shows the irradiation step of irradiating the pressure-sensitive adhesive layer with actinic light from the surface side of the release film (the surface side of the pressure-sensitive adhesive layer), and Fig. 7D shows the intermediate laminate produced in the second B embodiment. indicates.
[Fig. 8] Fig. 8 is a schematic view showing a first modification of Embodiment 1A of the method for manufacturing an intermediate laminate of the present invention, wherein Fig. 8A shows a preparation step for preparing an adhesive layer, and Fig. 8B shows actinic light A first irradiation step of forming a first irradiated portion and a provisionally irradiated portion by irradiating is shown. Fig. 8C shows the provisionally irradiated portion as a second irradiated portion by irradiating an actinic light to the provisionally irradiated portion The second irradiation step is shown, and Fig. 8D shows a sticking step of adhering the pressure-sensitive adhesive layer to the adherend.
[Fig. 9] Fig. 9 is a schematic view showing a second modification of the first embodiment 1A of the method for manufacturing an intermediate laminate of the present invention, wherein Fig. 9A shows a preparation step for preparing an adhesive sheet, and Fig. 9B shows the pressure-sensitive adhesive layer A third irradiation step is shown in which all of the adhesive layer serves as a third irradiated portion by irradiating the entire area with actinic light, and Fig. 9C is after arranging a mask for blocking actinic light on a part of the third irradiated portion , shows a fourth irradiation step in which the remainder of the third irradiated portion is irradiated with actinic light to the remaining portion of the third irradiated portion as a fourth irradiated portion, and FIG. represents the process.
[Fig. 10] Fig. 10 is a schematic view showing a method for manufacturing an intermediate laminate in which a low light transmittance portion in an adhesive layer has a pattern shape, Fig. 10A shows an irradiation process of arranging a plurality of masks for blocking actinic light, Fig. 10B shows the intermediate|middle laminated body in which the low light transmittance part in an adhesive layer has a pattern shape.

1. Adhesive

The pressure-sensitive adhesive of the present invention contains a pressure-sensitive adhesive polymer, a compound colored with an acid, and an acid generator.

An adhesive polymer is mix|blended in order to provide adhesiveness to an adhesive.

The adhesive polymer is a polymer of a monomer component (described later), for example, an acrylic polymer, a silicone polymer, a urethane polymer, a rubber polymer, etc., from the viewpoint of optical transparency, adhesiveness, and control of storage modulus , preferably an acrylic polymer.

The acrylic polymer is obtained by polymerization of a monomer component containing (meth)acrylic acid alkyl ester as a main component.

(meth)acrylic acid alkyl ester is acrylic acid ester and / or methacrylic acid ester, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid propyl, (meth) acrylic acid butyl, (meth) Acrylic acid isopropyl, (meth)acrylic acid butyl, (meth)acrylic acid isobutyl, (meth)acrylic acid s-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid pentyl, (meth)acrylic acid isopentyl, (meth)acrylic acid Neopentyl, (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid nonyl, (meth)acrylic acid isono Neyl, (meth)acrylic acid decyl, (meth)acrylic acid isodecyl, (meth)acrylic acid undecyl, (meth)acrylic acid dodecyl, (meth)acrylic acid isotridodecyl, (meth)acrylic acid tetradecyl, (meth)acrylic acid iso Tetradecyl, (meth)acrylic acid pentadecyl, (meth)acrylic acid cetyl, (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl, (meth)acrylic acid isooctadecyl, (meth)acrylic acid nonadecyl, (meth)acrylic acid eico linear or branched (meth)acrylic acid C1-20 alkyl esters such as yarn, preferably (meth)acrylic acid methyl, (meth)acrylic acid butyl, (meth)acrylic acid 2-ethylhexyl, more preferably Examples include methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate.

(meth)acrylic acid alkyl ester can be used individually or in combination of 2 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', it is preferably used alone or in plurality selected from (meth)acrylic acid C4-12 alkyl esters, or methyl methacrylate and acrylic acid A combined use of a C4-12 alkyl ester, more preferably a combination of methyl methacrylate and a C4-12 acrylic acid alkyl ester is used.

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

The blending ratio of the (meth)acrylic acid alkyl ester is, for example, 50 mass % or more, preferably 60 mass % or more, with respect to the monomer component, and for example, 99 mass % or less, preferably 80 mass % or less. % or less.

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

When a monomer component contains the acidic vinyl monomer which has an anionic group, separation is accelerated|stimulated by the strong acid generated from an acid generator (described later), a color becomes strong, and it is excellent in the coloring stability mentioned later.

As an acidic vinyl monomer which has an anionic group, a carboxyl group containing vinyl monomer, a sulfo group containing vinyl monomer, a phosphoric acid group containing vinyl monomer, etc. are mentioned, for example.

Examples of the carboxyl group-containing vinyl monomer include (meth)acrylic acid, (meth)acrylic acid 2-carboxyethyl, carboxypentyl (meth)acrylic acid carboxypentyl, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Moreover, as a carboxyl group containing vinyl monomer, acid anhydride group containing monomers, such as maleic anhydride and itaconic anhydride, are mentioned, for example.

Examples of the sulfo group-containing vinyl monomer include styrene sulfonic acid and allyl sulfonic acid.

As a phosphoric acid group containing vinyl monomer, 2-hydroxyethyl acryloyl phosphate etc. are mentioned, for example.

The acidic vinyl monomer which has an anionic group can be used individually or in combination of 2 or more types.

The blending 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, with respect to 100 parts by mass of the (meth)acrylic acid alkyl ester, the monomer component It is, for example, 1 mass % or more with respect to, and is 8 mass % or less, for example.

Further, the monomer component preferably does not substantially contain a basic vinyl monomer having a lone pair of electrons copolymerizable with the (meth)acrylic acid alkyl ester.

Specifically, the blending ratio of the basic vinyl monomer having a lone pair of electrons is, for example, 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, with respect to the monomer component, particularly preferably is 0 mass % or less. In other words, particularly preferably, the monomer component does not contain a basic vinyl monomer having a lone pair of electrons.

When a monomer component does not contain the basic vinyl monomer which has a lone electron pair substantially, elution of each monomer component can be suppressed and the coloring stability mentioned later can be improved.

The basic vinyl monomer having a lone pair of electrons is a basic vinyl monomer containing a heterocycle having nitrogen in the heterocyclic ring, for example, N-vinylpyrrolidone, methyl vinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine. , vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-acryloylmorpholine, N-vinylcaprolactam, and the like.

In addition, the monomer component preferably contains a functional group-containing vinyl monomer copolymerizable with (meth)acrylic acid alkyl ester (excluding the above acidic vinyl monomer having an anionic group and basic vinyl monomer having a lone pair of electrons).

Examples of the functional group-containing vinyl monomer include a hydroxyl group-containing vinyl monomer, a cyano group-containing vinyl monomer, a glycidyl group-containing vinyl monomer, an aromatic vinyl monomer, a vinyl ester monomer, and a vinyl ether monomer.

As the hydroxyl group-containing vinyl monomer, for example, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 4-hydroxybutyl, (meth)acrylic acid 6-hydroxy Hexyl, (meth)acrylic acid 8-hydroxyoctyl, (meth)acrylic acid 10-hydroxydecyl, (meth)acrylic acid 12-hydroxylauryl, (meth)acrylic acid 4-(hydroxymethyl)cyclohexyl)methyl, etc. These are mentioned, Preferably 2-hydroxyethyl (meth)acrylic acid is mentioned, More preferably, 2-hydroxyethyl acrylate is mentioned.

As a cyano group containing vinyl monomer, (meth)acrylonitrile etc. are mentioned, for example.

As a glycidyl group containing vinyl monomer, (meth)acrylic-acid glycidyl etc. are mentioned, for example.

As an aromatic vinyl monomer, styrene, p-methyl styrene, o-methyl styrene, (alpha)-methyl styrene etc. are mentioned, for example.

As a vinyl ester monomer, vinyl acetate, vinyl propionate, etc. are mentioned, for example.

As a vinyl ether monomer, methyl vinyl ether etc. are mentioned, for example.

The functional group-containing vinyl monomer may be used alone or in combination of two or more. When a crosslinking agent (described later) is blended, a hydroxyl group-containing vinyl monomer is preferably used from the viewpoint of introducing a crosslinked structure to the polymer.

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, with respect to 100 parts by mass of the (meth)acrylic acid alkyl ester, For example, it is 20 mass parts or less, and with respect to a monomer component, for example, 4 mass % or more, Preferably it is 10 mass % or more, For example, 30 mass % or less, Preferably 20 mass % or less. mass% or less.

And the acrylic polymer is a polymer formed by superposing|polymerizing the above-mentioned monomer component.

In order to polymerize the monomer component, for example, (meth)acrylic acid alkyl ester and, if necessary, a basic vinyl monomer and a functional group-containing vinyl monomer are blended to prepare a monomer component, and this is, for example, solution polymerization, bulk (塊狀) It prepares by well-known polymerization methods, such as polymerization and emulsion polymerization.

As a polymerization method, Preferably solution polymerization is mentioned.

In solution polymerization, a monomer component and a polymerization initiator are mix|blended with a solvent, for example, a monomer solution is prepared, and a monomer solution is heated after that.

As a solvent, an organic solvent etc. are mentioned, for example.

Examples of the organic solvent 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, For example, ester solvents, such as ethyl acetate, For example, amide solvents, such as N,N- dimethylformamide, are mentioned, Preferably an ester solvent is mentioned, More preferably, ethyl acetate is mentioned.

A solvent can be used individually or can use 2 or more types together.

The mixing 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 with respect to 100 parts by mass of the monomer component. to be.

As a polymerization initiator, a peroxide type polymerization initiator, an azo type polymerization initiator, etc. are mentioned, for example.

Examples of the peroxide-based polymerization initiator include organic peroxides such as peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxyester.

As the azo polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2, Azo compounds, such as 4-dimethylvaleronitrile) and 2,2'- azobisisobutyrate dimethyl, are mentioned.

As a polymerization initiator, Preferably it is an azo type polymerization initiator, More preferably, 2,2'- azobisisobutyronitrile is mentioned.

A polymerization initiator can be used individually or can use 2 or more types together.

The mixing 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 with respect to 100 parts by mass of the monomer component. is below.

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, a monomer component is superposed|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 is, for example, 80 mass% or less.

The weight average molecular weight of the acrylic polymer is, for example, 100000 or more, preferably 300000 or more, more preferably 500000 or more, still more preferably 650000 or more, and for example, 5000000 or less, preferably 300000 or less. , More preferably, it is 2000000 or less.

In addition, said weight average molecular weight is the value computed by polystyrene conversion by measuring by GPC (gel permeation chromatography).

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

When the glass transition temperature of the pressure-sensitive adhesive polymer is equal to or less than the upper limit, the level difference followability is excellent.

In addition, the glass transition temperature is obtained by calculation by the formula of FOX.

A compound colored by an acid is a compound that changes from colorless (transparent) to colored by an acid, for example, a leuco-based dye, for example, p,p',p"-tris-dimethylaminotriphenyl Triarylmethane-based dyes such as methane, for example, diphenylmethane-based dyes such as 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, for example 3-diethylamino-6-methyl Fluorane-based dyes such as -7-chlorofluoran, for example, spiropyran-based dyes such as 3-methylspirodynaphthopyran, for example, rhodamine-based dyes such as rhodamine-B-anilinolactam etc. are mentioned, Preferably a leuco-type pigment|dye is mentioned.

The compound colored by an acid can be used individually or can use 2 or more types together.

The compounding ratio of the compound colored with the acid 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 with respect to 100 parts by mass of the adhesive polymer.

As an acid generator, a photo-acid generator, a thermal acid generator, etc. are mentioned, for example.

A photo-acid generator is a compound which generate|occur|produces an acid by irradiation of light (actinic light).

Examples of the actinic light include ultraviolet rays, visible light, infrared rays, X-rays, α-rays, β-rays, and γ-rays, and preferably, ultraviolet rays from the viewpoint of diversity of equipment used and ease of handling.

In addition, an ultraviolet-ray means the electromagnetic wave in the wavelength range of 1 nm or more and 400 nm or less.

Among such photo-acid generators, as a compound (ultraviolet-ray acid generator) which generate|occur|produces an acid by irradiation of an ultraviolet-ray, an onium compound etc. are mentioned, for example.

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

As such an onium compound, Preferably, the salt which consists of sulfonium (onium cation) and (C ₆ F ₅ ) ₄ B ^- (anion) is mentioned.

Moreover, as an ultraviolet acid generator, a commercial item can also be used, For example, CPI-310B (salt which consists of sulfonium and (C ₆ F ₅ ) ₄ B ^- , the acid Apro company make) etc. are mentioned.

A photo-acid generator can be used individually or can use 2 or more types together.

A thermal acid generator is a compound which generate|occur|produces an acid by heating, For example, an arylsulfonium salt, an aryliodonium salt, etc. are mentioned.

A thermal acid generator can be used individually or can use 2 or more types together.

As the acid generator, a photo-acid generator is selected from the viewpoint of color prevention at the time of heating film forming, color treatment in a short time, etc. From the viewpoint of avoidance and the like, a thermal acid generator is selected.

The blending ratio of the acid generator is, for example, 1 part by mass or more, and for example, 20 parts by mass or less, preferably 15 parts by mass or less with respect to 100 parts by mass of the adhesive polymer.

Then, the pressure-sensitive adhesive is prepared by blending the pressure-sensitive adhesive polymer (a polymer solution when the pressure-sensitive adhesive polymer is prepared by solution polymerization), a compound colored with an acid, and an acid generator in the above ratio and mixing them. (When a polymer solution is used as an adhesive polymer, it is prepared as a solution of an adhesive).

A crosslinking agent is preferably mix|blended with an adhesive from a viewpoint of introduce|transducing a crosslinked structure into an adhesive polymer.

As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an oxazoline type crosslinking agent, an aziridine type crosslinking agent, a carbodiimide type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned, for example.

As an isocyanate type crosslinking agent, For example, aliphatic diisocyanate, such as butylene diisocyanate and hexamethylene diisocyanate, For example, cyclopentylene diisocyanate, cyclo Alicyclic diisocyanate, such as hexylene diisocyanate and isophorone diisocyanate, for example, 2,4-tolylene diisocyanate, 4,4'- diphenylmethane Aromatic diisocyanate, such as diisocyanate and xylylene diisocyanate, is mentioned.

Moreover, as an isocyanate type crosslinking agent, the derivative of said isocyanate (For example, isocyanurate modified body, polyol modified product, etc.) is also mentioned.

As an isocyanate type crosslinking agent, a commercial item can also be used, For example, Coronate L (trimethylol propane adduct body of tolylene diisocyanate, a dosing agent), Coronate HL (hexamethylene diamond) Trimethylolpropane adduct of isocyanate, dosing agent), Coronate HX (isocyanurate of hexamethylene diisocyanate, dosing agent), Takenate D110N (xylylene diisocyanate) The trimethylol propane adduct body of nate, the Mitsui Chemicals make) etc. are mentioned.

As an isocyanate type crosslinking agent, Preferably the trimethylol propane adduct body of hexamethylene diisocyanate and the trimethylol propane adduct body of xylylene diisocyanate are mentioned.

Examples of the epoxy-based crosslinking agent include diglycidylaniline and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.

As an epoxy-type crosslinking agent, a commercial item can also be used, For example, Tetrad C (made by Mitsubishi Gas Chemicals), etc. are mentioned.

As an epoxy-type crosslinking agent, Preferably 1, 3-bis (N, N- diglycidyl aminomethyl) cyclohexane is mentioned.

As a crosslinking agent, Preferably, an isocyanate type crosslinking agent is mentioned.

A crosslinking agent can be used individually or can use 2 or more types together.

When a crosslinking agent is blended with an adhesive, a functional group such as a hydroxyl group in the polymer reacts with the crosslinking agent to introduce a crosslinked structure into the polymer.

The mixing ratio of the crosslinking 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 more with respect to 100 parts by mass of the adhesive polymer. Hereinafter, Preferably it is 5 mass parts or less, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

Moreover, when mix|blending a crosslinking agent with an adhesive, in order to accelerate|stimulate a crosslinking reaction, you may mix|blend a crosslinking catalyst.

Examples of the crosslinking catalyst include metal-based crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, nashem ferric, butyltin oxide, and dioctyltin dilaurate.

A crosslinking catalyst can be used individually or can use 2 or more types together.

The mixing ratio of the crosslinking 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 with respect to 100 parts by mass of the adhesive polymer.

Further, the pressure-sensitive adhesive includes, if necessary, for example, a silane coupling agent, a tackifier, a plasticizer, a softener, an anti-degradation agent, a filler, a colorant, a surfactant, an antistatic agent, from the viewpoint of stabilization under fluorescent light or under natural light, ultraviolet rays Various additives, such as additives, such as a water absorbing agent and antioxidant, can be contained in the range which does not impair the effect of this invention.

Thereby, an adhesive (in the case of using a polymer solution as an adhesive polymer, the solution of an adhesive) is obtained.

The shear storage modulus G' of this pressure-sensitive adhesive (solid content) 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 or more. above, and for example, 1.0×10 ⁶ Pa or less, preferably 5.0×10 ⁵ Pa or less.

When said shear storage elastic modulus G' is in the said range, it is excellent in adhesiveness, and when shear storage elastic modulus G' is lower, it is also excellent also in step|step difference followability.

On the other hand, the shear storage modulus G' is described in detail in the Examples to be described later, but it is used for dynamic viscoelasticity measurement under the conditions of a frequency of 1 Hz, a temperature increase rate of 5° C./min, and a temperature range of -70° C. to 250° C. is measured by

And this adhesive contains an adhesive polymer, the compound colored with an acid, and an acid generator.

Therefore, this pressure-sensitive adhesive generates an acid from an acid generator by irradiation with light (actinic light) or heating, and the acid causes the compound to be colored by the acid to be colored from colorless (transparent) to colored. change to That is, before light (actinic light) irradiation or before heating, an adhesive is colorless (transparent).

In addition, colorless (transparent) means that the transmittance measured in Examples to be described later is, for example, 60% or more, preferably 70% or more, more preferably 90% or more, and, for example, 100% or more. % or less.

In addition, the color means that the transmittance|permeability measured in the Example mentioned later is, for example, 0 % or more, and is less than 60 %, for example, Preferably it is 50 % or less.

On the other hand, the shear storage modulus G' at 20°C to 50°C of the pressure-sensitive adhesive (adhesive layer 1 to be described later) after coloring (after irradiation with light (actinic light)) is, for example, 1.0×10 ⁴ Pa or more, preferably Preferably, it is 2.0×10 ⁴ Pa or more, more preferably 4.0×10 ⁴ Pa or more, and for example, 1.0×10 ⁶ Pa or less, preferably 5.0×10 ⁵ Pa or less.

That is, in this pressure-sensitive adhesive (adhesive layer 1 to be described later), the shear storage modulus G' does not significantly change before and after light (actinic light) irradiation, and the adhesive force does not change greatly either.

2. Adhesive layer

The pressure-sensitive adhesive layer 1 is a pressure-sensitive adhesive layer for adhering to the adherend 4 (described later). Further, 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 said adhesive.

Hereinafter, the method of manufacturing the adhesive layer 1 is demonstrated with reference to FIG.

In order to form the adhesion layer 1, first, as shown to FIG. 1A, the peeling film 2 is prepared.

As the release film 2, flexible plastic films, such as polyethylene, a polypropylene, a polyethylene terephthalate, a polyester film, are mentioned, for example.

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, more preferably 50 µm or less.

The release film 2 is preferably subjected to a release treatment with a release agent such as a silicone-based, fluorine-based, long-chain alkyl, or fatty acid amide-based release agent, or a release treatment with silica powder.

Next, as shown in FIG. 1B, the said adhesive (a solution of an adhesive) is apply|coated to one side of the peeling film 2, and a solvent is dried and removed as needed.

As a coating method of an adhesive, For example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die coating coating etc. are mentioned.

As the drying conditions, the 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 it is 150 degrees C or less, and drying time is, for example, 5 second or more, Preferably it is 10 second or more, For example, it is 20 minutes or less, Preferably, it is 15 minutes or less, More preferably, 10 minutes or less. less than a minute

Thereby, the adhesion layer 1 is arrange|positioned (formed) on one side of the peeling film 2.

Moreover, you may arrange|position the other peeling film 2 on one side of the adhesive layer 1 as needed (refer FIG. 1B dotted line).

On the other hand, when the pressure-sensitive adhesive contains a crosslinking agent, simultaneously with the drying removal or after drying the solvent (if necessary, after laminating the release film 2 on one side of the pressure-sensitive adhesive layer 1 ), preferably advances crosslinking by aging.

Aging conditions are appropriately set according to the type of crosslinking agent, and the aging temperature is, for example, 20 ° C. or higher, and for example, 160 ° C. or lower, preferably 50 ° C. or lower, and the aging time is, 1 minute or longer, preferably 12 hours or longer, more preferably 1 day or longer, and for example, 7 days or shorter.

3. Adhesive sheet

The adhesive layer 1 can also be prepared as the adhesive layer 1 of the adhesive sheet 3 from a viewpoint of handleability.

Hereinafter, the method of manufacturing the adhesive sheet 3 is demonstrated with reference to FIG.

The method of manufacturing the adhesive sheet 3 is equipped with the process of preparing the base material 5, and the process of arrange|positioning the adhesive layer 1 on one side of the base material 5.

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

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

The substrate 5 is made of a flexible plastic material.

As such a plastic material, for example, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, for example, (meth)acrylic resins such as polymethacrylate (acrylic resins) and/or methacrylic resin), such as polyethylene, polypropylene, polyolefin resin such as cycloolefin polymer (COP), such as polycarbonate resin, such as polyethersulfone resin, for example, polyarylate resins such as melamine resins such as polyamide resins such as polyimide resins such as cellulose resins such as polystyrene resins such as norbornene resins. A synthetic resin etc. are mentioned.

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

As a plastic material from a viewpoint of making transparency with respect to light and mechanical strength compatible, Preferably a polyester resin, More preferably, polyethylene terephthalate (PET) is mentioned.

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, still more preferably 45 µm or more, and further, for example, 500 µm or less, flexibility and handling properties. From a viewpoint, it is preferably 300 µm or less, more preferably 200 µm or less, still more preferably 100 µm or less.

In the process of arranging the adhesion layer 1, as shown in FIG. 2B, the adhesion layer 1 is arrange|positioned on one side of the base material 5.

The adhesive layer 1 is arrange|positioned on the whole surface of one side of the base material 5, The adhesive layer 1 is the upper layer of the adhesive sheet 3 .

In order to arrange the adhesive layer 1 on one side of the substrate 5, the above adhesive (solution of the adhesive) is applied to one side of the substrate 5 in the same manner as above, and, if necessary, the solvent is dried. Remove.

Thereby, the adhesive layer 1 is formed on one side of the base material 5, and the adhesive sheet 3 provided with the base material 5 and the adhesive layer 1 arrange|positioned on one side of the base material 5. is obtained

In addition, as shown to FIG. 2C, the adhesive sheet 3 may laminate|stack the peeling film 2 on one side of the adhesive layer 1 as needed.

In such a case, the adhesive sheet 3 is equipped with the base material 5, the adhesive layer 1, and the peeling film 2 in order.

4. Intermediate Laminate

As shown in Fig. 3, the intermediate laminate 6 has a film shape (including a sheet shape) having a predetermined thickness, extends in a direction (plane direction) orthogonal to the thickness direction, and has a flat upper surface and a flat have a bottom

Specifically, the intermediate laminate 6 includes an adhesive layer 1 and an adherend 4 disposed on the other surface of the adhesive layer 1 .

Moreover, the peeling film 2 can also be arrange|positioned on one side of the adhesive layer 1 as needed (refer FIG. 3 dotted line).

In such a case, the intermediate laminate 6 comprises a release film 2, an adhesive layer 1 disposed on the other side of the release film 2, and an adherend disposed on the other side of the adhesive layer 1 ( 4) is provided.

Although mentioned later in detail, the intermediate|middle laminated body 6 is obtained by sticking the above-mentioned adhesive layer 1 to the to-be-adhered body 4 .

4-1. adhesive layer

As described above, the pressure-sensitive adhesive layer 1 is formed of the above-described pressure-sensitive adhesive.

In addition, in the following description, an adhesive contains a photo-acid generator as an acid generator.

Further, the adhesive layer 1 includes a high light transmittance portion 10 having a relatively large visible light transmittance at a wavelength of 550 nm and a low light transmittance portion 11 having a relatively small visible light transmittance at a wavelength of 550 nm.

On the other hand, although described later in detail, the visible light transmittance of the high light transmittance portion 10 and the low light transmittance portion 11 at a wavelength of 550 nm is determined by a method for manufacturing the intermediate laminate 6 described later.

4-2. adherend

As the to-be-adhered body 4, an optical device, an electronic device, its component, etc. are mentioned, for example.

On the other hand, 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 are available depending on the types of optical devices, electronic devices, and structural parts thereof. this is chosen

In addition, although detailed later, in the manufacturing method of the intermediate|middle laminated body 6, when irradiating actinic light (preferably ultraviolet) to the adhesive layer 1 from the surface side of the to-be-adhered body 4 (described later) In the second embodiment of the present invention, the adherend 4 transmits an actinic light (preferably, ultraviolet light) or blocks the actinic light (preferably ultraviolet light), depending on whether the intermediate laminate 6) The manufacturing method is determined.

Among such adherends 4, as the adherend 4 that transmits the actinic light (hereinafter referred to as the first adherend 30), the first adherend 30 that transmits the ultraviolet rays is preferably used. can be heard

As the 1st to-be-adhered body 30 which permeate|transmits an ultraviolet-ray, alkali-free glass, a PET film, etc. are mentioned, for example.

The average transmittance of the actinic light of the first adherend 30 that transmits the actinic light is, for example, 60% or more, preferably 65% or more, and in particular, the first adherend 30 that transmits the actinic light ) is the first adherend 30 that transmits ultraviolet rays, 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.

When the above average transmittance is equal to or greater than the lower limit, the actinic light (preferably, ultraviolet light) passes through the first adherend 30 and the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet light). can

In addition, among such adherends 4, as the adherend 4 that blocks actinic light (preferably, ultraviolet rays) (hereinafter referred to as the second adherend 31), an agent that absorbs actinic light is used. 2 to-be-adhered body 31, and the 2nd to-be-adhered body 31 which reflects actinic light (it does not transmit actinic light) are mentioned.

As the second adherend 31 that absorbs actinic light, preferably, the second adherend 31 that absorbs ultraviolet rays is used.

As the 2nd to-be-adhered body 31 which absorbs an ultraviolet-ray, a polyimide film, the glass plate etc. to which the ultraviolet absorber was apply|coated are mentioned, for example.

The average transmittance of the actinic light of the second adherend 31 that absorbs the actinic light is, for example, 15% or less, preferably 10% or less, and in particular, the second adherend 31 which absorbs the actinic light ) is the second adherend 31 that absorbs ultraviolet rays, 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.

When the average transmittance is equal to or greater than the lower limit, the second adherend 31 can absorb actinic light (preferably, ultraviolet light).

The second adherend 31 that reflects the actinic light preferably includes a second adherend 31 that reflects the ultraviolet light.

As the 2nd to-be-adhered body 31 which reflects an ultraviolet-ray, metal substrates, such as a copper plate, etc. are mentioned, for example.

4-3. Method for producing an intermediate laminate

In the manufacturing method of the intermediate laminate 6, the preparatory step of preparing the adhesive layer 1 described above, the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet rays), the adhesive layer 1 is The highly irradiated portion 20 with a relatively high irradiation amount of actinic light (preferably, ultraviolet light), and a relatively low irradiation amount of actinic light (preferably ultraviolet light) or actinic light (preferably ultraviolet light) By forming the non-irradiated/low irradiated portion 21 that is not irradiated, the visible light transmittance at a wavelength of 550 nm of the highly irradiated portion 20 is higher than the visible light transmittance of the non-irradiated/low irradiated portion 21 at a wavelength of 550 nm. An irradiation process of making it small, and a sticking process of sticking the other surface of the adhesion layer 1 to the to-be-adhered body 4 are provided.

Since the manufacturing method of this intermediate|middle laminated body 6 is equipped with the above-mentioned preparatory process, by irradiating actinic light (preferably ultraviolet) to this adhesive layer 1, the adhesive layer 1 will be colored. can

In addition, since the manufacturing method of this intermediate|middle laminated body 6 is equipped with the said irradiation process, except the colored part (non-irradiated/low-irradiation part 21) in the adhesion layer 1, it is transparent as it is. It can be made to remain|survive, or the amount of coloring can be made less than a colored part.

Hereinafter, the manufacturing method of the intermediate|middle laminated body 6 is divided into the order of each process, and every irradiation direction of actinic light (preferably, an ultraviolet-ray), and is demonstrated.

In detail, as the order of each process, an irradiation process is implemented after a preparation process, an adhesion process is implemented after an irradiation process (it is set as 1st Embodiment hereafter), or a sticking process is implemented after a preparation process. And, after the sticking process, an irradiation process is implemented (it is set as 2nd Embodiment hereafter).

Further, as the irradiation direction of actinic light (preferably ultraviolet), in the second embodiment, the adhesive layer 1 is irradiated with actinic light (preferably ultraviolet) from the surface side of the adherend 4, or (Hereinafter, it is set as 2nd A Embodiment.) Alternatively, actinic light (preferably ultraviolet) is irradiated to the adhesive layer 1 from the surface side of the adhesive layer 1 (it is set as 2nd B embodiment hereafter). do.

Hereinafter, each embodiment is described in detail.

On the other hand, in the manufacturing method of this intermediate laminated body 6, the non-irradiated/low-irradiated part 21 will become the non-irradiated part 22 depending on the irradiation amount of actinic light (preferably, an ultraviolet-ray), or Whether or not it will be the low-irradiation part 23 is determined, but in the following description, the case where the non-irradiated/low-irradiated part 21 is the non-irradiated part 22 will be described in detail.

In addition, the non-irradiated portion 22 is a portion not irradiated with actinic light (preferably, ultraviolet rays), and the visible light transmittance of the non-irradiated portion 22 at a wavelength of 550 nm is, for example, 80% or more; Preferably it is 90% or more.

When the visible light transmittance is equal to or greater than the lower limit, the non-irradiated portion 22 has transparency.

In addition, in the following description, as the adhesive layer 1, the case where the adhesive layer 1 in which the peeling film 2 was arrange|positioned on both surfaces of the adhesive layer 1 is demonstrated.

4-3-1. first embodiment

In 1st Embodiment, an irradiation process is implemented after a preparation process, and a sticking process is implemented after an irradiation process.

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

In a preparatory process, as shown to FIG. 4A, the adhesive layer 1 is prepared on one side of the peeling film 2, After that, on one side of the adhesive layer 1, another peeling film 2 is applied. place it

In the irradiation step, as shown in FIG. 4B , the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet rays), and the adhesive layer 1 is relatively irradiated with actinic rays (preferably, ultraviolet rays). The highly irradiated portion 20 and the non-irradiated portion 22 not irradiated with active rays (preferably, ultraviolet rays) are formed.

On the other hand, in the following description, when irradiating actinic light (preferably, ultraviolet rays) to a part of the adhesive layer 1, specifically, the adhesive layer 1 is divided into three in the plane direction, and the Two places are irradiated with actinic light (preferably, ultraviolet rays), and a part of the adhesive layer 1 for irradiating actinic rays (preferably, ultraviolet rays) is placed on the highly irradiated portion 20 (in other words, the adhesive layer ( Among those obtained by dividing 1) into three in the plane direction, only one portion of the central portion is defined as the non-irradiated portion 22).

Specifically, in the irradiation step, in the adhesion layer 1, the highly irradiated portion 20 is irradiated with actinic light (preferably ultraviolet) from the surface side of the release film 2, and the non-irradiated portion ( 22) is not irradiated with actinic rays (preferably, ultraviolet rays).

Specifically, the highly irradiated portion 20 (specifically, the other side of the release film 2 disposed on the other side of the highly irradiated portion 20) has a mask ( 7) without arranging, to the non-irradiated portion 22 (specifically, the other side of the release film 2 disposed on the other side of the non-irradiated portion 22) to block actinic light (preferably, ultraviolet rays) The mask 7 to be used is disposed, and actinic light (preferably ultraviolet) is irradiated from the surface side of the release film 2 (the surface side of the adhesive layer 1).

Thereby, only the highly irradiated part 20 is irradiated with actinic light (preferably, an ultraviolet-ray).

And in the adhesion layer 1 in the highly irradiated part 20, an acid generate|occur|produces from a photo-acid generator, and the compound colored with an acid is colored (specifically, black) by the acid. As a result, the adhesion 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). Then, the visible light transmittance at a wavelength of 550 nm of the highly irradiated portion 20 becomes smaller than the visible light transmittance at a wavelength of 550 nm of the non-irradiated portion 22 (specifically, the highly irradiated portion 20 is a non-irradiated portion (22) is darker than that).

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

Then, the highly irradiated portion 20 becomes the low light transmittance portion 11 , and the non-irradiated portion 22 becomes the high light transmittance portion 10 .

In the sticking step, as shown in FIG. 4C , the other surface of the adhesion layer 1 is affixed to the adherend 4 .

Specifically, the release film 2 is peeled off from the other surface of the adhesion layer 1 , and the adherend 4 is disposed on the other surface of the adhesion layer 1 .

Thereby, the intermediate laminated body 6 provided with the release film 2, the adhesive layer 1 arrange|positioned on the other surface of the release film 2, and the to-be-adhered body 4 arrange|positioned on the other surface of the adhesion layer 1). ) is obtained.

Further, in the intermediate laminate 6, the adhesive layer 1 comprises a high light transmittance portion 10 having a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm ( 11) is provided.

And, in this intermediate laminate 6, the visible light transmittance of the low light transmittance portion 11 at a wavelength of 550 nm is, for example, less than 20%, preferably 10% or less, and further, for example, It is 0.01% or more, and the visible light transmittance of the high light transmittance portion 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

When the visible light transmittance of the low light transmittance portion 11 is less than the upper limit, the function of absorbing light can be reliably provided to the low light transmittance portion 11 .

In addition, when the above-described visible light transmittance of the high light transmittance portion 10 is equal to or more than the above lower limit, the high light transmittance portion 10 has transparency.

According to 1st Embodiment, while showing the effect of the manufacturing method of said intermediate|middle laminated body 6, since an irradiation process is implemented after a preparatory process, and a sticking process is performed after an irradiation process, a colored location is aligned. It can be used to improve the precision of

In particular, if the adherend 4 is the second adherend 31, it is possible to suppress the coloration of the non-irradiated portion 22 by external light (actinic light) from the surface side of the second adherend 31. can

4-3-2. 2A embodiment

In 2nd A embodiment, a sticking process is implemented after a preparatory process, and an irradiation process is implemented after a sticking process.

Moreover, in 2nd A, in the irradiation process, actinic light (preferably, ultraviolet-ray) is irradiated to the adhesion layer 1 from the surface side of the to-be-adhered body 4 .

In the second A embodiment, depending on whether the adherend 4 transmits actinic light (preferably, ultraviolet) or blocks the actinic light (preferably, ultraviolet) (specifically, the adherend 4 ) is the first adherend 30 or the second adherend 31), the manufacturing method of the intermediate laminate 6 is determined.

Hereinafter, the case where the adherend 4 is the first adherend 30 and the case where the adherend 4 is the second adherend 31 will be described.

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

In a preparatory process, as shown to FIG. 5A, the adhesion layer 1 is prepared similarly to above-mentioned 1st Embodiment.

In the sticking step, as shown in FIG. 5B , the other side of the adhesion layer 1 is affixed to the first adherend 30 , similarly to the first embodiment described above.

In the irradiation step, as shown in FIG. 5C , the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet rays), and the adhesive layer 1 is relatively irradiated with actinic rays (preferably, ultraviolet rays). The highly irradiated portion 20 and the non-irradiated portion 22 not irradiated with active rays (preferably, ultraviolet rays) are formed.

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

In detail, after disposing a mask 7 that blocks actinic light (preferably, ultraviolet light) on a part of the other side of the first adherend 30, actinic light (preferably UV light) is disposed on the adhesive layer 1 . , UV) is irradiated.

More specifically, in the highly irradiated portion 20 (specifically, the other surface of the first adherend 30 disposed on the other surface of the highly irradiated portion 20), actinic light (preferably, ultraviolet rays) is blocked. Without disposing the mask 7 to be used, actinic light rays (preferably , ultraviolet rays) is disposed, and actinic rays (preferably ultraviolet rays) are irradiated from the surface side of the first adherend 30 .

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

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

As described above, as shown in Fig. 5D, the release film 2, the adhesive layer 1 disposed on the other side of the release film 2, and the adherend 4 disposed on the other side of the adhesive layer 1) The intermediate laminate 6 provided with (1st to-be-adhered body 30) is obtained.

Further, in the intermediate laminate 6, the adhesive layer 1 comprises a high light transmittance portion 10 having a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm ( 11) is provided.

And, in this intermediate laminate 6, the visible light transmittance of the low light transmittance portion 11 at a wavelength of 550 nm is, for example, less than 20%, preferably 10% or less, and further, for example, It is 0.01% or more, and the visible light transmittance of the high light transmittance portion 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

When the visible light transmittance of the low light transmittance portion 11 is less than the upper limit, the function of absorbing light can be reliably provided to the low light transmittance portion 11 .

In addition, when the above-described visible light transmittance of the high light transmittance portion 10 is equal to or more than the above lower limit, the high light transmittance portion 10 has transparency.

According to the 2nd A embodiment (when the to-be-adhered body 4 is the 1st to-be-adhered body 30), while showing the effect of the manufacturing method of the said intermediate|middle laminated body 6, a sticking process is implemented after a preparatory process. And since an irradiation process is implemented after a sticking process, a foreign material and a bubble can be confirmed at the time of a sticking process.

Further, according to the second embodiment (when the adherend 4 is the first adherend 30), in the irradiation step, from the surface side of the adherend 4 (first adherend 30), In order to irradiate the adhesive layer 1 with actinic light (preferably, ultraviolet-ray), the precision of alignment of the location to be colored improves.

Further, according to the second embodiment (when the adherend 4 is the first adherend 30), since the first adherend 4 is used, the adherend 4 (the first adherend ( 30)), the adhesive layer 1 can be reliably irradiated with actinic light (preferably, ultraviolet rays).

Next, with reference to FIG. 6, 2nd Embodiment in the case where the to-be-adhered body 4 is the 2nd to-be-adhered body 31 is demonstrated.

In a preparatory process, as shown to FIG. 6A, the adhesion layer 1 is prepared similarly to above-mentioned 1st Embodiment.

In the sticking 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 .

In addition, in the following description, as shown in FIG. 6B, the case where the 2nd to-be-adhered body 31 is arrange|positioned at the center part of what divided the adhesive layer 1 into 3 in the plane direction is demonstrated. do.

In the irradiation step, as shown in FIG. 6C , the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet rays), and the adhesive layer 1 is relatively irradiated with actinic rays (preferably ultraviolet rays). The highly irradiated portion 20 and the non-irradiated portion 22 not irradiated with active rays (preferably, ultraviolet rays) are formed.

Specifically, in the irradiation step, in the adhesion layer 1 , the highly irradiated portion 20 is irradiated with actinic rays (preferably ultraviolet rays) from the surface side of the second adherend 31, and non-irradiated. The portion 22 is not irradiated with actinic rays (preferably, ultraviolet rays).

In detail, unlike the above-described first and second embodiments (when the adherend 4 is the first adherend 30), the mask 7 for blocking actinic light (preferably, ultraviolet rays) ) is not used, and actinic light (preferably, ultraviolet rays) is irradiated from the surface side of the second adherend 31 as it is.

At this time, since the second adherend 31 blocks actinic rays (preferably, ultraviolet rays), the second adherend 31 uses a mask 7 that blocks actinic rays (preferably, ultraviolet rays). can be replaced, and the non-irradiated portion 22 on which the second adherend 31 is disposed can be prevented from being irradiated with actinic rays (preferably, ultraviolet rays), while the second adherend 31 can be prevented from being irradiated. Only the highly irradiated portion 20 on which is not disposed can be irradiated with actinic rays (preferably, ultraviolet rays).

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

As described above, as shown in FIG. 6D , the release film 2 , the adhesive layer 1 disposed on the other side of the release film 2 , and the adherend 4 disposed on the other side of the adhesive layer 1 ) The intermediate laminate 6 provided with (2nd to-be-adhered body 31) is obtained.

Further, in the intermediate laminate 6, the adhesive layer 1 comprises a high light transmittance portion 10 having a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm ( 11) is provided.

And, in this intermediate laminate 6, the visible light transmittance of the low light transmittance portion 11 at a wavelength of 550 nm is, for example, less than 20%, preferably 10% or less, and further, for example, It is 0.01% or more, and the visible light transmittance of the high light transmittance portion 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

When the visible light transmittance of the low light transmittance portion 11 is less than the upper limit, the function of absorbing light can be reliably provided to the low light transmittance portion 11 .

In addition, when the above-described visible light transmittance of the high light transmittance portion 10 is equal to or more than the above lower limit, the high light transmittance portion 10 has transparency.

According to the 2nd embodiment (when the to-be-adhered body 4 is the 2nd to-be-adhered body 31), while showing the effect of the manufacturing method of the said intermediate|middle laminated body 6, a sticking process is implemented after a preparatory process. And since an irradiation process is implemented after a sticking process, a foreign material and a bubble can be confirmed at the time of a sticking process.

Further, according to the second embodiment (when the adherend 4 is the second adherend 31), in the irradiation step, from the surface side of the adherend 4 (the second adherend 31), In order to irradiate the adhesive layer 1 with actinic light (preferably, ultraviolet-ray), the precision of alignment of the location to be colored improves.

Further, according to the second embodiment (when the adherend 4 is the second adherend 31), the portion on which the second adherend 4 is disposed (the non-irradiated portion 22) is reliably activated It can block from light rays (preferably, ultraviolet rays).

4-3-3. 2B embodiment

In 2nd B Embodiment, a sticking process is implemented after a preparatory process, and an irradiation process is implemented after a sticking process.

Moreover, in 2nd B Embodiment, in an irradiation process, actinic light (preferably, an ultraviolet-ray) is irradiated to the adhesion layer 1 from the adhesion layer 1 side.

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

In a preparatory process, as shown to FIG. 7A, the adhesion layer 1 is prepared similarly to above-mentioned 1st Embodiment.

In the sticking step, as shown in FIG. 7B , the other side of the adhesion layer 1 is affixed to the adherend 4 similarly to the first embodiment described above.

In the irradiation step, as shown in FIG. 7C , the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet rays), and the adhesive layer 1 is relatively irradiated with actinic rays (preferably ultraviolet rays). The highly irradiated portion 20 and the non-irradiated portion 22 not irradiated with active rays (preferably, ultraviolet rays) are formed.

Specifically, in the irradiation step, in the adhesion layer 1, the highly irradiated portion 20 is directed to the surface side of the release film 2 (the surface side of the pressure-sensitive adhesive layer 1) from the active light beam (preferably, ultraviolet), and the non-irradiated portion 22 is not irradiated with actinic light (preferably, ultraviolet rays).

Specifically, in the highly irradiated portion 20 (specifically, one side of the release film 2 disposed on one side of the highly irradiated portion 20), the active light (preferably, ultraviolet rays) is blocked. Without disposing the mask 7, actinic light (preferably, A mask 7 that blocks ultraviolet rays) is disposed, and actinic light rays (preferably ultraviolet rays) are irradiated from the surface side of the release film 2 (the surface side of the adhesive layer 1).

Thereby, only the highly irradiated portion 20 can be irradiated with actinic light (preferably, ultraviolet rays), and, similarly to the first embodiment described above, the highly irradiated portion 20 (low light transmittance portion 11), A non-irradiated portion 22 (high light transmittance portion 10) may be formed.

Thereafter, as shown in Fig. 7D, the release film 2, the adhesive layer 1 disposed on the other side of the release film 2, and the adherend 4 disposed on the other side of the adhesive layer 1 were separated. The intermediate laminate 6 provided is obtained.

Further, in the intermediate laminate 6, the adhesive layer 1 comprises a high light transmittance portion 10 having a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm ( 11) is provided.

And, in this intermediate laminate 6, the visible light transmittance of the low light transmittance portion 11 at a wavelength of 550 nm is, for example, less than 20%, preferably 10% or less, and further, for example, It is 0.01% or more, and the visible light transmittance of the high light transmittance portion 10 at a wavelength of 550 nm is, for example, 80% or more, preferably 90% or more.

When the visible light transmittance of the low light transmittance portion 11 is less than the upper limit, the function of absorbing light can be reliably provided to the low light transmittance portion 11 .

In addition, when the above-described visible light transmittance of the high light transmittance portion 10 is equal to or more than the above lower limit, the high light transmittance portion 10 has transparency.

According to 2nd B Embodiment, while showing the effect of the manufacturing method of the said intermediate|middle laminated body 6, after a preparatory process, since a sticking process is implemented and an irradiation process is implemented after a sticking process, at the time of a sticking process , foreign matter or air bubbles can be checked.

Moreover, according to 2B Embodiment, in the irradiation process, in order to irradiate actinic light (preferably, ultraviolet-ray) to the adhesive layer 1 from the surface side of the adhesive layer 1, since the adhesive layer 1 is The actinic light (preferably, ultraviolet-ray) can be irradiated reliably.

In particular, if the adherend 4 is the second adherend 31, it is possible to suppress the coloration of the non-irradiated portion 22 by external light (actinic light) from the surface side of the second adherend 31. can

4-3-4. variation

In the above description, the case where the non-irradiated/low irradiated portion 21 is the non-irradiated portion 22 has been described, but in the following description, the non-irradiated/low irradiated portion 21 is the low irradiated portion 23 ) may be

When the non-irradiated/low-irradiated portion 21 is the low-irradiated portion 23 , the irradiation step is performed after disposing the first mask 8 that blocks actinic rays (preferably, ultraviolet rays), and then the adhesive layer (1) by irradiating actinic rays (preferably, ultraviolet rays) to the adhesive layer 1, the first irradiated portion 40 irradiated with actinic rays (preferably ultraviolet rays), and actinic rays ( Preferably, a first irradiation step of forming the provisionally irradiated portion 41 not irradiated with ultraviolet rays), and a second mask that blocks active rays (preferably ultraviolet rays) on the first irradiated portion 40 . After arranging (9), the provisionally irradiated portion 41 is converted into a second irradiated portion by irradiating the provisionally irradiated portion 41 in the adhesive layer 1 with actinic light (preferably, ultraviolet rays). The 2nd irradiation process referred to as (42) is provided.

And although mentioned later in detail, since the irradiation amount of actinic light (preferably, ultraviolet-ray) in a 1st irradiation process differs from the irradiation amount of actinic-ray (preferably, an ultraviolet-ray) in a 2nd irradiation process, , one of the first irradiated portion 40 and the second irradiated portion 42 becomes the high irradiated portion 20 , and the other becomes the low irradiated portion 23 .

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

In a preparatory process, as shown to FIG. 8A, the adhesion layer 1 is prepared similarly to above-mentioned 1st Embodiment.

In the irradiation step, the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet rays), and the adhesive layer 1 is subjected to a relatively high irradiation amount of actinic light (preferably ultraviolet) to the highly irradiated portion 20 ) and a relatively low irradiation amount 23 of actinic rays (preferably, ultraviolet rays) are formed.

Specifically, in the first irradiation step in the irradiation step, the first irradiation portion 40 and the provisionally irradiated portion 41 are formed, and in the second irradiation step in the irradiation step, the provisionally irradiated portion ( 41 ) as the second irradiation portion 42 .

In the first irradiation step, as shown in FIG. 8B , in the first irradiation part 40 , actinic light (preferably, ultraviolet rays) from the surface side of the release film 2 (the surface side of the adhesive layer 1) is irradiated, and the provisionally irradiated portion 41 is not irradiated with actinic rays (preferably, ultraviolet rays).

On the other hand, in the following description, the first irradiation part 40 (in other words, the adhesive layer 1 is divided into three parts in the plane direction) Among them, only one part of the central portion is used as the provisional irradiation part 41), and description will be made.

More specifically, the first irradiated portion 40 (specifically, the other side of the release film 2 disposed on the other side of the first irradiated portion 40) blocks actinic light (preferably, ultraviolet rays) Without disposing the first mask 8 to be used, actinic light (preferably , ultraviolet rays) is disposed, and actinic rays (preferably ultraviolet rays) are irradiated from the surface side of the release film 2 (the surface side of the adhesive layer 1).

Thereby, only the 1st irradiation part 40 can be irradiated with actinic light (preferably, an ultraviolet-ray).

And in the adhesion layer 1 in the 1st irradiation part 40, an acid generate|occur|produces from a photo-acid generator, and the compound colored with an acid is colored (specifically, black) by the acid. As a result, the adhesive layer 1 in the first irradiated portion 40 changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low).

Next, in a 2nd irradiation process, let the provisional irradiation part 41 be the 2nd irradiation part 42. As shown in FIG.

Specifically, as shown in Fig. 8C, in the second irradiation step, in the provisionally irradiated portion 41, from the surface side of the adhesive layer 1, actinic light of a different amount from the first irradiation step (preferably, While irradiating ultraviolet rays), the first irradiated portion 40 is not irradiated with actinic rays (preferably ultraviolet rays).

More specifically, in the provisionally irradiated portion 41 (specifically, the other side of the release film 2 disposed on the other side of the provisionally irradiated portion 41), an agent that blocks active light (preferably, ultraviolet rays) 2 Without disposing the mask 9, the first irradiated portion 40 (specifically, the other side of the release film 2 disposed on the other side of the first irradiated portion 40) is directed to the actinic light (preferably , ultraviolet rays) is disposed, and actinic rays (preferably ultraviolet rays) are irradiated from the surface side of the adhesive layer 1 .

As a result, only the provisionally irradiated portion 41 can be irradiated with actinic light (preferably, ultraviolet rays), and the provisionally irradiated portion 41 becomes the second irradiated portion 42 .

And in the adhesion layer 1 in the 2nd irradiation part 42, an acid generate|occur|produces from a photo-acid generator, and the compound colored with an acid is colored (specifically, black) by the acid. As a result, the adhesive layer 1 in the second irradiated portion 42 changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low).

Thereby, the 1st irradiation part 40 and the 2nd irradiation part 42 are formed in the adhesive layer 1 .

And as mentioned above, in a 2nd irradiation process, the actinic light (preferably ultraviolet) of the amount of light different from the 1st irradiation process is irradiated.

That is, the irradiation amounts of the actinic rays (preferably, ultraviolet rays) of the first irradiated portion 40 and the second irradiated portion 42 are different from each other.

Therefore, either one of the first irradiated portion 40 and the second irradiated portion 42 has a relatively high irradiation amount of actinic light (preferably, ultraviolet rays) high irradiation portion 20 (in other words, a relatively wavelength It becomes a low light transmittance portion 11 having a low visible light transmittance at 550 nm, and the other is a low irradiation portion 23 with a relatively low irradiation amount of actinic light (preferably, ultraviolet light) (in other words, relatively at a wavelength of 550 nm of high light transmittance portion 10) with high visible light transmittance.

On the other hand, in Fig. 8, the first irradiated portion 40 is the high irradiated portion 20 (low light transmittance portion 11), and the second irradiated portion 42 is the low irradiated portion 21 (high light transmittance portion 10). )) and will be described.

Specifically, the visible light transmittance at a wavelength of 550 nm of the highly irradiated portion 20 is, for example, less than 20%, preferably 10% or less, and further, for example, 0.01% or more, and low irradiation The visible light transmittance of the portion 23 at a wavelength of 550 nm is, for example, 20% or more, preferably 40% or more, and is, for example, 70% or less.

And in the sticking process, as shown in FIG. 8D, the other surface of the adhesion layer 1 is stuck to the to-be-adhered body 4 similarly to above-mentioned 1st Embodiment.

Thereby, the intermediate laminated body 6 provided with the release film 2, the adhesive layer 1 arrange|positioned on the other surface of the release film 2, and the to-be-adhered body 4 arrange|positioned on the other surface of the adhesion layer 1). ) is obtained.

Further, in the intermediate laminate 6, the adhesive layer 1 comprises a high light transmittance portion 10 having a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm ( 11) is provided.

And, in this intermediate laminate 6, the visible light transmittance of the low light transmittance portion 11 at a wavelength of 550 nm is, for example, less than 20%, preferably 10% or less, and further, for example, 0.01 % or more, and the visible light transmittance at a wavelength of 550 nm of the high light transmittance portion 10 is, for example, 20% or more, preferably 40% or more, and for example, 70% or less.

When the above-described visible light transmittance of the low light transmittance portion 11 is within the above range, and the above-described visible light transmittance of the high light transmittance portion 10 is within the above range, the light transmittance portion 11 and the high light transmittance portion 10 You can definitely change the color.

According to the 1st modification of 1st Embodiment, while showing the effect of the manufacturing method of the said intermediate|middle laminated body 6, the highly irradiated part 20 (low light) by a 1st irradiation process and a 2nd irradiation process. Since the transmittance portion 11) and the low irradiated portion 23 (high light transmittance portion 10) are formed, the intermediate laminate 6 including the adhesive layer 1 having regions having different colors can be manufactured. have.

In particular, if the adherend 4 is the second adherend 31, it is possible to suppress the coloration of the low-irradiated portion 23 by external light (actinic light) from the surface side of the second adherend 31. can

In addition, when the non-irradiated/low-irradiated portion 21 is the low-irradiated portion 23, the irradiation step is performed by irradiating all of the adhesive layer 1 with actinic rays (preferably, ultraviolet rays), A third irradiation step in which all of the adhesive layer 1 is a third irradiation portion 43 irradiated with actinic light (preferably, ultraviolet rays), and a part 45 of the third irradiation portion 43, After disposing the mask 7 for blocking actinic light (preferably, ultraviolet rays), the remaining portion 46 of the third irradiated portion is irradiated with actinic light (preferably ultraviolet) by irradiating the third irradiated portion The 4th irradiation process which makes the remainder 46 of (43) into the 4th irradiation part 44 is provided.

In the following description, in Embodiment 1A, the case where the non-irradiation/low irradiation portion 21 is the low-irradiation portion 23 (hereinafter, referred to as a second modification of Embodiment 1A) is illustrated. It will be described with reference to 9.

In a preparation process, as shown to FIG. 9A, the adhesive sheet 1 is prepared similarly to 1st A embodiment mentioned above.

In the irradiation step, the adhesive layer 1 is irradiated with actinic light (preferably, ultraviolet rays), and the adhesive layer 1 is subjected to a relatively high irradiation amount of actinic light (preferably ultraviolet) to the highly irradiated portion 20 ) and a relatively low irradiation amount 23 of actinic rays (preferably, ultraviolet rays) are formed.

Specifically, in the third irradiation process in the irradiation process, the third irradiation part 43 is formed, and in the fourth irradiation process in the irradiation process, the remainder 46 of the third irradiation part 43 is performed. ) (described later) is referred to as the fourth irradiation portion 44 .

In the 3rd irradiation process, as shown in FIG. 9B, actinic light (preferably ultraviolet rays) from the surface side of the peeling film 2 (the surface side of the adhesive layer 1) to all of the adhesion layer 1 investigate

Thereby, the whole of the adhesive layer 1 becomes the 3rd irradiation part 43. As shown in FIG.

Moreover, in the adhesion layer 1 (3rd irradiation part 43), an acid generate|occur|produces from a photo-acid generator, and the compound colored with an acid is colored (specifically, black) by the acid. As a result, all of the 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).

Next, in the fourth irradiation step, as shown in FIG. 9C , after disposing a mask 7 that blocks actinic light (preferably, ultraviolet rays) in a part 45 of the third irradiation part 43, By irradiating actinic light (preferably, ultraviolet rays) to the remainder 46 of the third irradiation portion, the remainder 46 of the third irradiation portion 43 is set as the fourth irradiation portion 44 .

On the other hand, in the following description, the remainder 46 of the third irradiated portion 43 (in other words, the pressure-sensitive adhesive sheet 1 is face-up at two ends of the adhesive sheet 1 divided into three in the plane direction). Only one of the central portions among those divided into three directions will be described as a part (45) of the third irradiated portion (43).

Specifically, in the fourth irradiation step, the remaining portion 46 of the third irradiation portion 43 is irradiated with actinic light (preferably ultraviolet) from the surface side of the adhesive layer 1, while the third irradiation The remainder of the portion 43 is not irradiated with actinic rays (preferably, ultraviolet rays).

More specifically, the remaining portion 46 of the third irradiated portion 43 (specifically, the other side of the release film 2 disposed on the other side of the remaining portion 46 of the third irradiated portion 43) has an active Without disposing the mask 7 for blocking light rays (preferably ultraviolet rays), part 45 of the third irradiated part 43 (specifically, part 45 of the third irradiated part 43 ) On the other side of the release film 2 disposed on the other side), a mask 7 that blocks actinic light (preferably, ultraviolet light) is disposed, and actinic light (preferably, UV rays).

Thereby, only the remaining part 46 of the 3rd irradiation part 43 can be irradiated with actinic light (preferably, an ultraviolet-ray), and the remainder 46 of the 3rd irradiation part 43 is a 4th irradiation part. (44) becomes.

And in the adhesion layer 1 in the 4th irradiation part 44, an acid generate|occur|produces from a photo-acid generator, and the compound colored with an acid is colored (specifically, black) by the acid. As a result, the adhesive layer 1 in the fourth irradiated portion 44 changes from colorless (transparent) to colored (visible light transmittance at a wavelength of 550 nm becomes low).

As a result, the fourth irradiated portion 44 has a lower visible light transmittance at a wavelength of 550 nm than the third irradiated portion 43 .

That is, the third irradiated portion 43 is a low irradiated portion 23 with a relatively low irradiation amount of actinic light (preferably, ultraviolet rays) (in other words, a high light transmittance portion with relatively high visible light transmittance at a wavelength of 550 nm ( 10)), and the fourth irradiated portion 44 has a relatively high irradiated portion 20 (in other words, a relatively low visible light transmittance at a wavelength of 550 nm) with a relatively high irradiation amount of actinic light (preferably, ultraviolet ray). low light transmittance portion 11).

Specifically, the visible light transmittance at a wavelength of 550 nm of the highly irradiated portion 20 is, for example, less than 20%, preferably 10% or less, and further, for example, 0.01% or more, and low irradiation The visible light transmittance of the portion 23 at a wavelength of 550 nm is, for example, 20% or more, preferably 40% or more, and is, for example, 70% or less.

And in the sticking process, as shown in FIG. 9D, the other side of the adhesive sheet 1 (the other side of the adhesive layer 1) is stuck to the to-be-adhered body 4 similarly to above-mentioned 1A Embodiment.

Thereby, the intermediate laminated body 6 provided with the release film 2, the adhesive layer 1 arrange|positioned on the other surface of the release film 2, and the to-be-adhered body 4 arrange|positioned on the other surface of the adhesion layer 1). ) is obtained.

Further, in the intermediate laminate 6, the adhesive layer 1 comprises a high light transmittance portion 10 having a relatively large visible light transmittance at a wavelength of 550 nm, and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm ( 11) is provided.

And, in this intermediate laminate 6, the visible light transmittance of the low light transmittance portion 11 at a wavelength of 550 nm is, for example, less than 20%, preferably 10% or less, and further, for example, 0.01 % or more, and the visible light transmittance at a wavelength of 550 nm of the high light transmittance portion 10 is, for example, 20% or more, preferably 40% or more, and for example, 70% or less.

When the above-described visible light transmittance of the low light transmittance portion 11 is within the above range, and the above-described visible light transmittance of the high light transmittance portion 10 is within the above range, the light transmittance portion 11 and the high light transmittance portion 10 You can definitely change the color.

According to the 2nd modification of 1A Embodiment, while showing the effect of the manufacturing method of the above-mentioned intermediate|middle laminated body 6, by a 3rd irradiation process and a 4th irradiation process, the highly irradiated part 20 (low light) Since the transmittance portion 11) and the low irradiated portion 23 (high light transmittance portion 10) are formed, the intermediate laminate 6 including the adhesive layer 1 having regions having different colors can be manufactured. have.

In particular, if the adherend 4 is the second adherend 31, it is possible to suppress the coloration of the low-irradiated portion 23 by external light (actinic light) from the surface side of the second adherend 31. can

In the above description, in the first A embodiment, the case where the non-irradiated/low irradiated portion 21 is the low irradiated portion 23 has been described. However, the 1B embodiment and the 2A embodiment (the first adherend Also in the case of use) and the second embodiment 2B, the non-irradiated/low-irradiation portion 21 is formed based on the same procedure as the irradiation process in the first modification or the second modification of the above-described embodiment 1A. It can be set as the low-irradiation part 23.

In addition, by using a plurality of masks 7 that block actinic light (preferably, ultraviolet rays), an intermediate laminate 6 in which the low light transmittance portion 11 in the adhesive layer 1 has a pattern shape is obtained. may be

Specifically, in the irradiation step of the first embodiment, as shown in FIG. 9A , a mask 7 that blocks a plurality of actinic rays (preferably ultraviolet rays) is disposed on the other surface of the release film 2 . (In detail, spaced apart from each other and placed 4).

And as shown in FIG. 9B by implementing a preparatory process, an irradiation process, and a sticking process similarly to said 1st Embodiment, the low-light transmittance part 11 in the adhesion layer 1 has a pattern shape intermediate|middle A laminate 6 can be obtained.

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, although the case where an acid generator is a photo-acid generator was demonstrated, when an acid generator is a thermal acid generator, in the said description, it is an irradiation process WHEREIN: The process of irradiating light to the adhesion layer 1 (irradiation) step) instead, the pressure-sensitive adhesive layer 1 is heated. Thereby, an acid is generated from the acid generator (thermal acid generator) in the adhesive layer 1, and the acid causes the compound to be colored by the acid to be colored, so that the adhesive layer 1 is colorless ( from transparent) to colored.

Example

Examples and comparative examples are shown below, and the present invention will be described more specifically. In addition, this invention is not limited at all to an Example and a comparative example. In addition, specific numerical values, such as a compounding ratio (content ratio), physical property value, parameter, etc. used in the following description are described in the above "Specific contents for carrying out the invention", and the corresponding compounding ratio (contains) ratio), physical properties, parameters, etc., may be substituted with the upper limit (the numerical value defined as “less than” or “less than”) or the lower limit (the numerical value defined as “more than” or “exceed”) of the description.

In addition, unless otherwise indicated, "part" and "%" are based on mass.

1. Details of ingredients

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: acrylic acid

Takenate D110N: 75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals

Coronate HX: isocyanurate form of hexamethylene diisocyanate, dosing agent

Tetrad C: Trade name: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (epoxy crosslinking agent), manufactured by Mitsubishi Gas Chemicals

BLACK ND1: leuco dye, made by Yamada Chemical Industries, Ltd.

CPI-310B: salt consisting of sulfonium and (C ₆ F ₅ ) ₄ B ^- , photoacid generator, acid aproze

Solvent Black29: Dye

2. Preparation of adhesive polymer

Synthesis Example 1

In a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling tube and a nitrogen gas introduction tube, as a monomer component, 63 parts by mass of 2-ethylhexyl acrylate (2EHA), 15 parts by mass of N-vinylpyrrolidone (NVP), and methacrylic 9 parts by mass of methyl acid (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, and nitrogen gas was flowed, and nitrogen was substituted for about 1 hour while stirring. Then, it heated at 60 degreeC, made it react for 7 hours, and obtained the solution of the adhesive polymer whose weight average molecular weight (Mw) is 120000.

In addition, the glass transition temperature of the adhesive polymer calculated by the formula of FOX was -34 degreeC.

Synthesis Example 2 to Synthesis Example 3

According to Table 1, except having changed the mixing|blending prescription of a monomer component, it carried out similarly to Synthesis Example 1, and prepared a solution of an adhesive polymer.

3. Preparation of adhesive and adhesive layer

Example 1

To the solution of the adhesive polymer of Synthesis Example 1, as a crosslinking agent, Takenate D-110N (75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals) was added to the adhesive polymer With respect to 100 parts by mass of the adhesive polymer in the solution of 1.1 parts by mass, as a compound colored with an acid, BLACK ND1 (leuco dye) with respect to 100 parts by mass of the adhesive polymer in the solution of the adhesive polymer, 1 part by mass, acid generator As CP-310B (photoacid generator) with respect to 100 mass parts of adhesive polymers in the solution of an adhesive polymer, 2 mass parts was added, it mixed uniformly, and the adhesive was prepared.

Next, on one side of a 50 μm thick polyethylene terephthalate film subjected to surface release treatment, the pressure-sensitive adhesive of Example 1 is applied with a fountain roll so that the thickness after drying becomes 25 μm, dried at 130° C. for 1 minute, and the solvent has been removed Thereby, the adhesion layer was formed. Furthermore, the release-processed surface of the peeling film (the 25-micrometer-thick polyethylene terephthalate film by which the surface was silicone release-processed) was pasted together to one side of an adhesive. Then, the aging process for 4 days was performed in 25 degreeC atmosphere, and the crosslinking reaction was advanced. Thereby, the 25-micrometer adhesive layer was manufactured.

Example 2

Two 25-micrometer adhesive layers obtained in Example 1 were laminated|stacked, and the 50-micrometer adhesive layer was obtained.

Example 3

Three 25-micrometer adhesive layers obtained in Example 1 were laminated|stacked, and the 75-micrometer adhesive layer was obtained.

Example 4

Four 25-micrometer adhesive layers obtained in Example 1 were laminated|stacked, and the 100-micrometer adhesive layer was obtained.

Example 5

According to Table 2, except having changed the formulation prescription, it carried out similarly to Example 1, and produced the adhesive sheet (25 micrometers adhesive layer).

Example 6

Two 25-micrometer adhesive layers obtained in Example 5 were laminated|stacked, and the 50-micrometer adhesive layer was obtained.

Example 7

Three 25-micrometer adhesive layers obtained in Example 5 were laminated|stacked, and the 75-micrometer adhesive layer was obtained.

Example 8

Four 25-micrometer adhesive layers obtained in Example 5 were laminated|stacked, and the 100-micrometer adhesive layer was obtained.

Example 9

According to Table 2, except having changed the formulation prescription, it carried out similarly to Example 1, and manufactured the adhesive sheet (25 micrometers adhesive layer).

Comparative Examples 1 to 3

According to Table 2, except having changed the formulation prescription, it carried out similarly to Example 1, and manufactured the adhesive sheet (25 micrometers adhesive layer).

On the other hand, in Comparative Example 3, Solvent Black29 was used as the dye.

4. Evaluation

(shear storage modulus and tanδ)

60 adhesive layers were prepared for the adhesive layer of Example 1, Example 5, and Example 9, this adhesive layer was laminated|stacked, and the sample for shear storage modulus measurement of 1.5 mm was produced. The shear storage modulus and tan δ were measured for the sample for shear storage modulus measurement under the following conditions using "Advanced Rheometric Expansion System (ARES)" manufactured by Rheometric Scientific. The results are shown in Table 2.

(Measuring conditions)

Deformation mode: torsion

Measuring frequency: 1Hz

Temperature increase rate: 5°C/min

Measuring temperature: -70℃ to 250℃

Shape: Parallel plate 8.0mmφ

(transmittance)

The adhesion layer of each Example and each comparative example was affixed on the glass substrate, and the transmittance|permeability in 550 nm before and behind irradiating LED (365 nm, 8000 mJ/□) was measured.

In addition, the data measured only with the glass substrate were made into the baseline.

The results are shown in Table 2.

(reflectivity)

The adhesive layer of the adhesive layer of each Example and each comparative example was affixed to the to-be-adhered body which affixed aluminum foil to the acrylic plate, and the reflectance in 550 nm before and behind irradiating LED (365 nm, 8000 mJ/□) was measured.

In addition, the data measured only with the to-be-adhered body which pasted the said aluminum foil on the acrylic plate was made into the baseline.

The results are shown in Table 2.

(color stability)

The adhesive layer of each Example and each comparative example was irradiated with light of 8000 mJ/□, left to stand at 85°C for 3 days, and the transmittance before and after standing for 3 days was measured in the same manner as in the above-described transmittance measurement method.

In addition, the pressure-sensitive adhesive sheet of each Example and each comparative example is irradiated with light of 8000 mJ/□, left at 85 ° C. and 85% relative humidity for 3 days, and the transmittance before and after leaving for 3 days is the same as the transmittance measurement method described above. measured in sequence.

The results are shown in Table 2.

(Transparent Stability)

The adhesive layer of each Example and each comparative example was left to stand for 3 days at 23 degreeC and 50% of relative humidity, and the transmittance|permeability before and after leaving it for 3 days was measured by the procedure similar to the above-mentioned transmittance|permeability measurement method.

The results are shown in Table 2.

In addition, although the said invention was provided as embodiment of the illustration of this invention, this is only a mere illustration and should not be interpreted limitedly. Modifications of the present invention that are obvious to those skilled in the art are included in the following claims.

The adhesive of this invention, the manufacturing method of an intermediate|middle laminated body, and an intermediate|middle laminated body are used suitably in an optical device, an electronic device, and its component.

1 adhesive layer
4 adherend
6 Intermediate Laminate
7 mask
8 first mask
9 second mask
10 High light transmittance part
11 Low light transmittance part
20 high irradiation part
21 non-irradiation/under-irradiation part
22 non-irradiated part
23 low-irradiation part
40 Part 1 Investigation
41 False Investigation Part
42 Part 2 of investigation
43 Part 3 Investigation
44 Part 4 Investigation
45 some
46 balance

Claims (18)

A tacky polymer that is a polymer of a monomer component, a compound colored with an acid, and an acid generator,
The glass transition temperature of the adhesive polymer is 0 ° C. or less,
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 pressure-sensitive adhesive. The method of claim 1,
The said monomer component contains the acidic vinyl monomer which has an anionic group, The adhesive characterized by the above-mentioned. 3. The method of claim 1 or 2,
The said monomer component does not contain the basic vinyl monomer which has a lone electron pair substantially, The adhesive characterized by the above-mentioned. A preparation step of preparing an adhesive layer made of the pressure-sensitive adhesive according to claim 1;
By irradiating actinic light to the adhesive layer, the adhesive layer has a relatively high irradiation amount of actinic light, and a relatively low irradiation amount of actinic light, or a non-irradiated/low irradiation part that is not irradiated with actinic light. an irradiation step of making the visible light transmittance of the highly irradiated portion at a wavelength of 550 nm smaller than the visible light transmittance of the non-irradiated/low irradiated portion at a wavelength of 550 nm by forming
A method for producing an intermediate laminate, comprising a bonding step of bonding the other side of the pressure-sensitive adhesive layer to an adherend. 5. The method of claim 4,
After the preparation process, the irradiation process is performed,
The manufacturing method of the intermediate|middle laminated body characterized by implementing the said sticking process after the said irradiation process. 5. The method of claim 4,
After the preparation step, the bonding step is performed,
The said irradiation process is implemented after the said sticking process, The manufacturing method of the intermediate|middle laminated body characterized by the above-mentioned. 7. The method of claim 6,
The said irradiation process WHEREIN: The manufacturing method of the intermediate|middle laminated body characterized by irradiating actinic light to the said adhesive layer from the surface side of the said adhesive layer. 7. The method of claim 6,
In the irradiating step, the adhesive layer is irradiated with actinic light from the surface side of the adherend, the method for producing an intermediate laminate. 9. The method of claim 8,
The average transmittance of the actinic light of the adherend is 60% or more,
In the irradiating step, a mask for blocking actinic light is disposed on a part of the other side of the adherend, and then the adhesive layer is irradiated with actinic light. 9. The method of claim 8,
The adherend blocks the actinic light,
The method for producing an intermediate laminate, wherein in the sticking step, the adherend is disposed on a part of the other surface of the pressure-sensitive adhesive layer. 5. The method of claim 4,
The non-irradiated/low irradiated portion is a non-irradiated portion to which actinic light is not irradiated,
The method for producing an intermediate laminate, wherein the non-irradiated portion has a visible light transmittance at a wavelength of 550 nm of 80% or more. 5. The method of claim 4,
The non-irradiated / low-irradiation part is a low-irradiation part with a low irradiation amount of actinic light,
In the irradiation step, after disposing a first mask that blocks actinic light, the adhesive layer is irradiated with actinic light. A first irradiation step of forming a temporary non-irradiated portion that is not
After arranging a second mask that blocks actinic light on the first irradiated portion, by irradiating the temporarily irradiated portion with actinic light on the temporarily irradiated portion of the adhesive layer, the provisionally irradiated portion is converted into a second irradiated portion and a second irradiation process to
One of the first irradiated portion and the second irradiated portion is the high irradiated portion, and the other is the low irradiated portion. 5. The method of claim 4,
The non-irradiated / low-irradiation part is a low-irradiation part with a low irradiation amount of actinic light,
The irradiation step comprises: a third irradiation step of irradiating all of the adhesion layer with actinic light, so that all of the adhesion layer is a third irradiation portion irradiated with actinic light;
After arranging a mask that blocks actinic light on a part of the third irradiated part, by irradiating the remaining part of the third irradiated part with actinic light, the remainder of the third irradiated part is converted into a fourth irradiated part and a fourth irradiation process to
The third irradiated portion is the low irradiated portion,
The said 4th irradiated part is the said highly irradiated part, The manufacturing method of the intermediate|middle laminated body characterized by the above-mentioned. 14. The method according to claim 12 or 13,
Visible light transmittance at a wavelength of 550 nm of the highly irradiated portion is less than 20%,
A method for producing an intermediate laminate, wherein the low-irradiation portion has a visible light transmittance at a wavelength of 550 nm of 20% or more and 70% or less. A pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 1 or 2, and an adherend disposed on the other side of the pressure-sensitive adhesive layer,
An intermediate laminate, characterized in that the adhesive layer includes a high light transmittance portion having a relatively large visible light transmittance at a wavelength of 550 nm and a low light transmittance portion having a relatively small visible light transmittance at a wavelength of 550 nm. 16. The method of claim 15,
The intermediate laminate, characterized in that the low light transmittance portion has a pattern shape. 16. The method of claim 15,
The intermediate laminate, characterized in that the high light transmittance portion has a visible light transmittance at a wavelength of 550 nm of 80% or more. 16. The method of claim 15,
Visible light transmittance at a wavelength of 550 nm of the low light transmittance portion is less than 20%,
A visible light transmittance of the high light transmittance portion at a wavelength of 550 nm is 20% or more and 70% or less.

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