TW202103915A - Laminate and reinforcing film - Google Patents

Abstract

The laminated body 1 of the present invention includes a reinforcing film 4 and a flexible adherend 5 arranged on one surface of the reinforcing film 4. The reinforcing film 4 includes a base material 2 and an adhesive layer 3 arranged on one surface of the base material 2 and containing high-adhesion components and low-adhesion components. The reinforcing film 4 includes a first reinforcing film portion 6 and a second reinforcing film portion 7 that are arranged at a distance from each other in the surface direction of the flexible adherend 5. In each of the adhesive layer 3 of the first reinforcing film portion 6 and the adhesive layer 3 of the second reinforcing film portion 7, in the thickness direction, a high-adhesive component is at the interface between the soft adherend 5 and the adhesive layer 3 Partial set exists.

Description

Laminated body and reinforcing film

The present invention relates to a laminated body and a reinforcing film.

It is known that the adhesive film is temporarily adhered to the surface of the device before the steps of assembling, processing, and transporting various devices such as electronic devices, so as to protect the surface or impart impact resistance.

As such an adhesive film, a curable adhesive sheet is known, which has a weak adhesive force before heating or before irradiation with ultraviolet rays, and exhibits adhesiveness by heating or irradiation with ultraviolet rays (for example, refer to Patent Document 1).

By leaving such an adhesive film in a state where it is attached to the device, a laminate with excellent reinforcement can be obtained.

[Prior Technical Literature] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2011-127054

[The problem to be solved by the invention]

On the other hand, in order to increase the degree of freedom of component placement, such an adhesive film is attached to a soft adherend to produce a laminated body.

In addition, there are cases in which the adhesive film at the central part is removed in order to bend such a laminate (in other words, only two adhesive films remain at both ends in the surface direction of the soft adherend).

In addition, there is a defect that if the laminate is bent as described above, the two adhesive films are easily peeled off.

The present invention provides a laminated body formed by firmly bonding a reinforcing film and a soft adherend, and a reinforcing film used in the laminated body. [Technical means to solve the problem]

The present invention [1] is a laminated body, which is provided with a reinforcing film and a flexible adherend arranged on one side of the above-mentioned reinforcing film, and the above-mentioned reinforcing film is provided with a substrate and arranged on one side of the above-mentioned substrate and includes high adhesion An adhesive layer of ingredients and low-adhesion ingredients, the reinforcing film is provided with a first reinforcing film part and a second reinforcing film part arranged at intervals in the surface direction of the soft adherend, in the first reinforcing film part In each of the adhesive layer and the adhesive layer of the second reinforcing film portion, in the thickness direction, the high-adhesive component is concentrated in the interface between the soft adherend and the adhesive layer.

The present invention [2] includes the layered product described in [1] above, wherein each of the adhesive layer of the first reinforcing film portion and the adhesive layer of the second reinforcing film portion is relatively thinner in the thickness direction The interface is further on the adhesive layer side, and the high-viscosity component and the low-viscosity component are mixed.

The present invention [3] includes the laminate according to [1] or [2], wherein the high-adhesive component is a cured product of polyfunctional (meth)acrylate, and the low-adhesive component is an acrylic polymer.

The present invention [4] includes the laminate as described in [1] or [2], wherein the high-viscosity component is an acrylic polymer, and the low-viscosity component is a component containing organosiloxane.

The present invention [5] is a laminated body, which is provided with a reinforcing film and a flexible adherend arranged on one side of the above-mentioned reinforcing film, and the above-mentioned reinforcing film is provided with a substrate and arranged on one side of the above-mentioned substrate and includes high adhesion The adhesive layer of ingredients and low-adhesion ingredients, the above-mentioned reinforcing film has a first reinforcing film part and a second reinforcing film part arranged at intervals in the surface direction of the soft adherend, and the adhesive force of the above-mentioned adhesive layer It is 5 N/25 mm or more, and the thickness of the above-mentioned adhesive layer is 5 μm or more.

The present invention [6] is a reinforcing film used in a laminate, the laminate having a reinforcing film and a flexible adherend arranged on one side of the reinforcing film, and the reinforcing film includes a base material and is arranged on the base material One side of the adhesive layer containing high-viscosity components and low-viscosity components, the reinforcing film is provided with a first reinforcing film portion and a second reinforcing film portion arranged at intervals in the direction of the surface of the soft adherend. [Effects of Invention]

In this laminated system, a first reinforcing film portion and a second reinforcing film portion are arranged at intervals in the surface direction of the soft adherend.

Therefore, the laminate can be bent between the first reinforcing film portion and the second reinforcing film portion.

In addition, in each of the adhesive layer of the first reinforcing film portion and the adhesive layer of the second reinforcing film portion, in the thickness direction, high-adhesive components are concentrated in the interface between the soft adherend and the adhesive layer.

Therefore, in this laminate, the adhesive layer and the flexible adherend are firmly bonded, and in particular, even if the laminate is bent as described above, peeling of the first and second reinforcing film portions can be suppressed.

An embodiment of the laminated body of the present invention will be described with reference to FIG. 1.

1. a layered body As shown in FIG. 1, the laminated body 1 includes a reinforcing film 4 including a base material 2 and an adhesive layer 3 arranged on one surface of the base material 2, and a flexible adherend 5 arranged on one surface of the reinforcing film 4.

The details will be described later, but the laminated body 1 is obtained by attaching the reinforcing film 4 to the flexible adherend 5.

Hereinafter, each layer will be described in detail.

2. Reinforcing film The reinforcing film 4 has a first reinforcing film portion 6 and a second reinforcing film portion 7 arranged at intervals in the surface direction of the flexible adherend 5.

The first reinforcing film portion 6 and the second reinforcing film portion 7 have a film shape (including a sheet shape) with a specific thickness, extend in a direction (surface direction) orthogonal to the thickness direction, and have a flat upper surface and a flat bottom surface.

In addition, the first reinforcing film portion 6 and the second reinforcing film portion 7 respectively include a base 2 and an adhesive layer 3 arranged on one surface of the base 2.

That is, the reinforcing film 4 includes a base 2 and an adhesive layer 3 arranged on one surface of the base 2.

2-1. Substrate The base material 2 is a supporting layer (supporting material) that ensures the mechanical strength of the reinforcing film 4. In addition, the base material 2 is a reinforcing material for reinforcing the soft adherend 5 in the laminated body 1. In addition, the substrate 2 has a film shape extending in the surface direction, and has a flat plane and a flat lower surface.

The substrate 2 includes a flexible plastic material.

Examples of such plastic materials include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, such as polymethacrylate. (Meth)acrylic resins (acrylic resins and/or methacrylic resins), such as polyethylene, polypropylene, polyolefin resins such as cycloolefin polymers (COP), such as polycarbonate resins, such as polyethers A resin such as a polyarylate resin, such as a melamine resin, such as a polyamide resin, such as a polyimide resin, such as a cellulose resin, such as a polystyrene resin, a synthetic resin such as an ene resin, and the like.

The details will be described later, but when the adhesive layer 3 is cured by irradiating light from the side of the substrate 2, it is preferable that the substrate 2 has transparency to light.

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

The thickness of the base material 2 is, for example, 4 μm or more. From the viewpoint of reinforcing the soft adherend 5 (described later), it is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 45 μm or more. For example, it is 500 μm or less, and from the viewpoint of flexibility and handleability, it is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less.

2-2. Adhesive layer The adhesive layer 3 is disposed on the entire surface of one surface of the substrate 2.

The adhesive layer 3 is a pressure-sensitive adhesive layer for bonding the reinforcing film 4 to the soft adherend 5. In addition, the adhesive layer 3 has a film shape extending along the surface direction, and has a flat plane and a flat lower surface.

The adhesive layer 3 is formed of an adhesive composition.

The adhesive composition is a composition that can irreversibly change its state from a state with low adhesion to a state with high adhesion.

As such an adhesive composition, for example, a first adhesive composition that can irreversibly change its state from a state with a low adhesive force to a state with a high adhesive force by light irradiation, such as A second adhesive composition that irreversibly changes its state from a state with low adhesive force to a state with high adhesive force when heated.

The first adhesive composition contains a base polymer, a photocuring agent, and a photopolymerization initiator.

As the base polymer, for example, acrylic polymer, natural rubber, styrene-isoprene-styrene block copolymer (SIS block copolymer), styrene-butadiene-styrene block copolymer, Segment copolymer (SBS block copolymer), styrene-ethylene-butylene-styrene block copolymer (SEBS block copolymer), styrene-butadiene rubber, polybutadiene, polyisoprene From the viewpoint of controlling the adhesive force of olefin, polyisobutylene, butyl rubber, chloroprene rubber, silicone rubber, etc., preferably, an acrylic polymer may be mentioned.

The acrylic polymer is obtained by the polymerization of the first monomer component containing alkyl (meth)acrylate as the main component.

Alkyl (meth)acrylate is acrylate and/or methacrylate, for example: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate Base) butyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate Ester, amyl (meth)acrylate, isoamyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid 2 -Ethylhexyl ester, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylate Base) isodecyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, isotri(dodecyl)(meth)acrylate, ten (meth)acrylate Tetraalkyl ester, isotetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, (meth)acrylate Yl)octadecyl acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate and other linear or branched The (meth)acrylate C1-20 alkyl ester and so on.

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

As the alkyl (meth)acrylate, from the viewpoint of adjusting the glass transition temperature and the shear storage modulus G', it is preferable to use a combination of methyl methacrylate and C4-12 alkyl acrylate.

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

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

In addition, the first monomer component preferably contains a functional group-containing vinyl monomer copolymerizable with the alkyl (meth)acrylate.

Examples of functional group-containing vinyl monomers include: hydroxyl-containing vinyl monomers, carboxyl-containing vinyl monomers, nitrogen-containing vinyl monomers, cyano group-containing vinyl monomers, and condensation-containing vinyl monomers. Glyceryl vinyl monomers, sulfo group-containing vinyl monomers, phosphoric acid group-containing vinyl monomers, aromatic vinyl monomers, vinyl ester monomers, vinyl ether monomers, etc.

Examples of hydroxyl-containing vinyl monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 4-(hydroxymethyl)acrylate (meth) Cyclohexyl)methyl and the like, preferably 2-hydroxyethyl (meth)acrylate, more preferably 2-hydroxyethyl acrylate.

Examples of carboxyl group-containing vinyl monomers include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, and maleic acid. , Fumaric acid, crotonic acid, etc.

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

Examples of nitrogen-containing vinyl monomers include: N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidone, vinyl Pyridine, vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl pyridine, N-acrylamide, N-vinyl carboxamides, N-vinyl caprolactam and the like.

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

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

As a sulfo group-containing vinyl monomer, for example, styrene sulfonic acid, allyl sulfonic acid, etc. may be mentioned.

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

As the aromatic vinyl monomer, for example, styrene, p-methylstyrene, o-methylstyrene, α-methylstyrene, etc. may be mentioned.

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.

As the functional group-containing vinyl monomer, it can be used alone or in combination of two or more. In the case of formulating a cross-linking agent (described below), from the viewpoint of introducing a cross-linked structure into the acrylic polymer, preferably, hydroxyl-containing vinyl monomers and carboxyl-containing vinyl monomers can be cited. Also, from the viewpoint of improving the cohesive force, nitrogen-containing vinyl monomers are preferably exemplified, and it is more preferred to combine hydroxyl-containing vinyl monomers and/or carboxyl-containing vinyl monomers with nitrogen-containing vinyl monomers. Combination of vinyl monomers.

When the hydroxyl-containing vinyl monomer and/or the carboxyl-containing vinyl monomer and the nitrogen-containing vinyl monomer are used together, it is relative to the hydroxyl-containing vinyl monomer and/or the carboxyl-containing vinyl monomer. The total amount of the monomer and the nitrogen-containing vinyl monomer is 100 parts by mass, and the mixing ratio of the hydroxyl-containing vinyl monomer and/or the carboxyl-containing vinyl monomer is, for example, 40 parts by mass or more, and for example, 60 Parts by mass or less, and the compounding ratio of the nitrogen-containing vinyl monomer is, for example, 40 parts by mass or more, and, for example, 60 parts by mass or less.

The blending ratio of the functional group-containing vinyl monomer relative to the first monomer component is, for example, 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, and, for example, 30 mass% or less , Preferably it is 20% by mass or less.

In addition, the acrylic polymer is a polymer obtained by polymerizing the above-mentioned first monomer component.

When the first monomer component is polymerized, for example, an alkyl (meth)acrylate and, if necessary, a vinyl monomer containing a functional group are prepared to prepare the first monomer component, for example, by solution polymerization or block It is prepared by known polymerization methods such as polymerization and emulsion polymerization.

As the polymerization method, preferably, solution polymerization is exemplified.

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

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

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

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

The mixing ratio of the solvent relative to 100 parts by mass of the first monomer component 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.

The polymerization initiator may, for example, be a peroxide-based polymerization initiator or an azo-based polymerization initiator.

As a peroxide-based polymerization initiator, for example, peroxycarbonate, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester And other organic peroxides.

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

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

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

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

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

Thereby, the first monomer component is polymerized to obtain an acrylic polymer solution containing an acrylic polymer.

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

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

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

In the first adhesive composition, the glass transition temperature (Tg) of the base polymer is, for example, -100°C or higher, preferably -80°C or higher, more preferably -40°C or higher, and, for example, -10°C or lower , Preferably -5°C or less, more preferably 0°C or less.

This structure is suitable for ensuring the fluidity of the base polymer in the first adhesive composition. Therefore, the first adhesive composition is brought to a state of high adhesive force by means of active energy rays (described below) Appropriate in terms of change.

In addition, the glass transition temperature is a value described in a document, a catalog, etc., or a value calculated based on the following formula (1) (Fox formula). The same is true for the glass transition temperature of other polymers described below.

1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +…+W _n /Tg _n (1)

In the above formula (1), Tg represents the glass transition temperature (unit: K) of the polymer (A), and Tg _i (i=1, 2,...n) represents the glass transition temperature when the monomer i forms a homopolymer (Unit: K), W _i (i=1, 2,...n) represents the mass fraction of monomer i in all monomer components.

In the first adhesive composition, the blending ratio of the base polymer relative to the total amount of the base polymer, light hardener, and photopolymerization initiator is, for example, 70% by mass or more, and, for example, 95% by mass or less.

From the viewpoint of sufficiently improving the adhesive force of the adhesive layer 3 by light irradiation, the light curing agent may, for example, be a polyfunctional (meth)acrylate having a functional group number of 2 or more and 3 or less. Specifically, Examples include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, bisphenol A ethylene oxide modified two ( Meth) acrylate, bisphenol A propylene oxide modified di(meth)acrylate, alkanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, pentaerythritol di( Difunctional (meth)acrylates such as meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate, such as ethoxylated isocyanuric acid tri(meth)acrylic acid Trifunctional (meth)acrylates such as esters, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc., preferably bifunctional (meth)acrylates.

In addition, as the light curing agent, for example, acrylic-based photoreactive oligomers, urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based photoreactive oligomers, urethane-based, and polybutadiene-based photoreactive agents may also be mentioned.性oligomers.

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

In addition, the functional group equivalent of the light curing agent is, for example, 50 g/eq or more, and, for example, 500 g/eq or less.

The viscosity of the light hardener at 25°C is, for example, 5 mPa·s or more, and, for example, 1000 mPa·s or less.

From the viewpoint of compatibility, the molecular weight of the light curing agent is, for example, 200 or less, and, for example, 1,000 or more.

Moreover, it is preferable to select a light hardening agent which is not compatible with a base polymer (preferably an acrylic polymer).

If the light hardener is not compatible with the base polymer (preferably an acrylic polymer), the adhesive force (described below) of the adhesive layer 3 that has not been irradiated with light can be lowered.

The compounding ratio of the light hardener is, for example, 10 parts by mass or more with respect to 100 parts by mass of the base polymer, and is, for example, 50 parts by mass or less, preferably 30 parts by mass or less.

In addition, the blending ratio of the light curing agent is, for example, 5% by mass or more, and, for example, 30% by mass or less with respect to the total amount of the base polymer, the light curing agent, and the photopolymerization initiator.

The photopolymerization initiator promotes the curing reaction of the photohardener, and is appropriately selected according to the type of the photohardener, etc., for example, a photocation initiator (photoacid generator), such as 1-hydroxycyclohexylphenyl Hydroxy ketones such as ketones, benzyl dimethyl ketals, amino ketones, phosphine oxides, benzophenones, trichloromethyl-containing tertiary derivatives and other photo-radical initiators , For example, a photoanion initiator (photobase generator) and the like.

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

Among such photopolymerization initiators, when a multifunctional (meth)acrylate is used as the photohardener, a photoradical initiator is preferably used, and hydroxyketones are more preferably used.

The light absorption region of the photopolymerization initiator is, for example, 300 nm or more, and for example, 450 nm or less.

The compounding ratio of the photopolymerization initiator is, for example, 0.01 part by mass or more with respect to 100 parts by mass of the base polymer, and is, for example, 1 part by mass or less, and preferably 0.5 parts by mass or less.

In addition, the blending ratio of the photopolymerization initiator relative to the total amount of the base polymer, the photohardener, and the photopolymerization initiator is, for example, 0.01% by mass or more, and, for example, 1% by mass or less, preferably 0.5% by mass %the following.

In addition, when preparing the first adhesive composition, a base polymer (preferably an acrylic polymer (in the case of preparing an acrylic polymer by solution polymerization, an acrylic polymer solution)), light The curing agent and the photopolymerization initiator are blended and mixed in the above-mentioned ratio.

In the first adhesive composition, from the viewpoint of introducing a cross-linked structure into the base polymer (preferably an acrylic polymer), it is preferable to formulate a cross-linking agent.

As the crosslinking agent, for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an azoline-based crosslinking agent, an aziridine-based crosslinking agent, a carbodiimide-based crosslinking agent, and a metal chelate may be mentioned. A compound-based crosslinking agent, etc., preferably an isocyanate-based crosslinking agent.

Examples of the isocyanate-based crosslinking agent include aliphatic diisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate. Alicyclic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and other aromatic diisocyanates.

In addition, as the isocyanate-based crosslinking agent, derivatives of the above-mentioned isocyanate (for example, an isocyanurate modified product, a polyol modified product, etc.) may also be exemplified.

As the isocyanate-based crosslinking agent, commercially available products can also be used, for example, Coronaate L (trimethylolpropane adduct of toluene diisocyanate, manufactured by Tosoh), Coronate HL (hexamethylene diisocyanate three Methylolpropane adduct, manufactured by Tosoh), Coronaate HX (isocyanurate of hexamethylene diisocyanate), Takenate D110N (trimethylolpropane adduct of xylylene diisocyanate, Mitsui Chemical manufacturing) and so on.

The crosslinking agent can be used alone or in combination of two or more kinds.

If a crosslinking agent is blended in the first adhesive composition, functional groups such as hydroxyl in the base polymer (preferably acrylic polymer) react with the crosslinking agent, and the base polymer (preferably Acrylic polymer) introduces a cross-linked structure.

The functional group equivalent of the crosslinking agent is, for example, 50 g/eq or more, and, for example, 500 g/eq or less.

The blending ratio of the crosslinking agent relative to 100 parts by mass of the base polymer is, for example, 0.1 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, and even more preferably 2.0 parts by mass or more, and, for example, It is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 4 parts by mass or less.

In addition, when a cross-linking agent is blended in the first adhesive composition, a cross-linking catalyst may be blended in order to promote the cross-linking reaction.

Examples of the crosslinking catalyst include metal crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, iron triacetone, butyl tin oxide, and dioctyl tin dilaurate.

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

The blending 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 base polymer.

In addition, the first adhesive composition may optionally contain a silane coupling agent, an adhesive imparting agent, a plasticizer, a softening agent, an anti-deterioration agent, a filler, a coloring agent, and the like within a range that does not impair the effects of the present invention. Various additives such as ultraviolet absorbers from the viewpoint of stabilization under fluorescent lamps or under natural light, antioxidants, surfactants, antistatic agents and other additives from the viewpoint of stabilization under fluorescent lamps or under natural light.

In this way, the first adhesive composition was obtained.

The blending ratio of the base polymer relative to the first adhesive composition is, for example, 50% by mass or more, preferably 80% by mass or more, and, for example, 90% by mass or less.

The blending ratio of the light curing agent relative to the first adhesive composition is, for example, 10% by mass or more, and, for example, 50% by mass or less.

The blending ratio of the photopolymerization initiator relative to the first adhesive composition is, for example, 0.01% by mass or more, and, for example, 0.5% by mass or less, and preferably 0.1% by mass or less.

The second adhesive composition contains the above-mentioned base polymer and an organosiloxane-containing component.

As the base polymer, an acrylic polymer is preferably mentioned.

In the second adhesive composition, the glass transition temperature (Tg) of the base polymer is, for example, -100°C or higher, preferably -80°C or higher, more preferably -40°C or higher, and, for example, -10°C or lower , Preferably -5°C or less, more preferably 0°C or less.

Such a structure is suitable in terms of ensuring the fluidity of the base polymer in the second adhesive composition, and therefore, in terms of changing the second adhesive composition to a high adhesive force state by heating.

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

The blending ratio of the base polymer relative to the total amount of the base polymer and the organosiloxane-containing component is, for example, 70% by mass or more, and, for example, 99% by mass or less, and preferably 90% by mass or less.

As components containing organosiloxanes, for example, acrylic polymers having organosiloxane skeletons, urethane-based polymers, polyether-based polymers, polyester-based polymers, and polycarbonate-based polymers can be mentioned. For polymers, polybutadiene-based polymers, etc., from the viewpoint of controlling adhesion, preferably, acrylic polymers having an organosiloxane skeleton are exemplified.

The acrylic polymer having an organosiloxane skeleton is obtained by polymerization of a monomer having an organosiloxane skeleton and the second monomer component of the above-mentioned alkyl (meth)acrylate.

The monomer having an organosiloxane skeleton is not particularly limited, and any monomer containing an organosiloxane skeleton can be used.

As a monomer having an organosiloxane skeleton, for example, a compound represented by the following general formula (1) or (2) can be used.

[化1]

In the above formula (1), R ¹ represents hydrogen or methyl, and m represents an integer of 0 or more.

[化2]

In the above formula (2), R ^{1 and m have the same meaning as R 1} and m in the above formula (1) ^{, R 2} represents a methyl group or a monovalent organic group, and n represents an integer of 0 or more.

In addition, as a monomer having an organosiloxane skeleton, commercially available products may also be used. Specifically, X-22-174ASX, X-22-2426, X-22-2475, KF-2012 (above It is a single-end reactive silicone, manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

The functional group equivalent of the monomer having an organosiloxane skeleton is, for example, 700 g/mol or more, preferably 800 g/mol or more, more preferably 850 g/mol or more, and still more preferably 1500 g/mol or more, and , For example, less than 20000 g/mol, preferably less than 15000 g/mol, more preferably less than 10000 g/mol, still more preferably less than 6000 g/mol, particularly preferably less than 5000 g/mol .

The blending ratio of the monomer having the organosiloxane skeleton relative to the total amount of the monomer having the organosiloxane skeleton and the alkyl (meth)acrylate is, for example, 10% by mass or more, preferably 15% by mass or more , More preferably 20% by mass or more, and, for example, 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

In addition, it is preferable that the second monomer component may also include the above-mentioned functional group-containing vinyl monomer.

In addition, the acrylic polymer having an organosiloxane skeleton is a polymer obtained by polymerizing the above-mentioned second monomer component.

When the second monomer component is polymerized, for example, a monomer having an organosiloxane skeleton and an alkyl (meth)acrylate are blended, and a vinyl monomer containing a functional group is blended as necessary to prepare the second monomer component. It is prepared by, for example, a known polymerization method such as solution polymerization, bulk polymerization, and emulsion polymerization.

As the polymerization method, preferably, solution polymerization is exemplified.

In the solution polymerization, for example, the second monomer component and the above-mentioned polymerization initiator are prepared in a solvent to prepare a monomer solution, and then the monomer solution is heated.

In addition, in the above polymerization, in order to adjust the molecular weight, a known chain transfer agent can be used.

Thereby, an acrylic polymer with organosiloxane skeleton is obtained.

The acrylic polymer having an organosiloxane skeleton has an organosiloxane skeleton in the side chain. Therefore, the acrylic polymer having the organosiloxane skeleton has low initial adhesive force (adhesive force before heating) due to the mobility and mobility of the side chain, and the adhesive force increases by heating.

In addition, the second adhesive composition is obtained by mixing a base polymer and an organosiloxane-containing component.

In addition, in the second adhesive composition, the above-mentioned cross-linking agent and the above-mentioned cross-linking catalyst may be blended.

In addition, the second adhesive composition may optionally contain a silane coupling agent, an adhesive imparting agent, a plasticizer, a softening agent, an anti-deterioration agent, a filler, a coloring agent, and the like within a range that does not impair the effects of the present invention. Various additives such as ultraviolet absorbers from the viewpoint of stabilization under fluorescent lamps or under natural light, antioxidants, surfactants, antistatic agents and other additives from the viewpoint of stabilization under fluorescent lamps or under natural light.

In this way, the second adhesive composition was obtained.

In the second adhesive composition, the blending ratio of the organosiloxane-containing components relative to 100 parts by mass of the base polymer is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, more preferably 0.4 parts by mass or more , More preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, most preferably 2 parts by mass or more, and, for example, 75 parts by mass or less, preferably 50 parts by mass or less, more preferably 20 parts by mass or less , More preferably, it is 10 parts by mass or less, particularly preferably 8 parts by mass or less, and most preferably 5 parts by mass or less.

In addition, the adhesive layer 3 is formed from the adhesive composition (the first adhesive composition or the second adhesive composition) by the following method.

From the viewpoint of adhesiveness, the thickness of the adhesive layer 3 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more, and from the viewpoint of handleability For example, it is 300 μm or less, preferably 100 μm or less, more preferably 50 μm or less, still more preferably 40 μm or less, and particularly preferably 30 μm or less.

2-3. Manufacturing method of reinforcing film Next, a method of manufacturing the reinforcing film 4 will be described with reference to FIG. 2.

The method of manufacturing the reinforcing film 4 includes the first step of preparing the base material 2 and the second step of disposing the adhesive layer 3 on one surface of the base material 2.

In the first step, as shown in FIG. 2A, the substrate 2 is prepared.

In the second step, as shown in FIG. 2B, an adhesive layer 3 is disposed on one surface of the substrate 2.

When disposing the adhesive layer 3 on one surface of the substrate 2, for example, the above-mentioned adhesive composition is applied to one surface of the substrate 2, and the solvent is dried and removed as necessary.

As the coating method of the adhesive composition, for example, roll coating, touch roll coating, gravure coating, reverse coating, roll brush coating, spray coating, dip roll coating, bar coating Coating, knife coating, air knife coating, curtain coating, die lip coating, die nozzle coating, etc.

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 150°C or lower, drying time For example, it is 5 seconds or more, preferably 10 seconds or more, and for example, it is 20 minutes or less, preferably 15 minutes or less, and more preferably 10 minutes or less.

In this way, the adhesive layer 3 is formed on one surface of the substrate 2, and the reinforcing film 4 including the substrate 2 and the adhesive layer 3 arranged on one surface of the substrate 2 is obtained.

Furthermore, when the adhesive composition contains a crosslinking agent, it is preferably removed simultaneously with drying or after drying of the solvent (after peeling off the film 8 (described below) in an area of the adhesive layer 3). The cross-linking proceeds by aging.

The aging conditions are appropriately set according to the type of crosslinking agent. The aging temperature is, for example, 20°C or higher, and, for example, 160°C or lower, preferably 100°C or lower, and the aging time is 1 minute or longer, preferably 12 hours or longer. , More preferably 1 day or more, and, for example, 7 days or less.

In addition, as shown in FIG. 2C, the reinforcing film 4 may also peel off the film 8 in an area of the adhesive layer 3 as needed.

In this case, the reinforcing film 4 includes a base material 2, an adhesive layer 3, and a release film 8 in this order.

The release film 8 may, for example, be a flexible plastic film such as polyethylene, polypropylene, polyethylene terephthalate, or polyester film.

The thickness of the release film 8 is, for example, 3 μm or more, preferably 10 μm or more, and for example, 200 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.

The release film 8 is preferably subjected to a mold release treatment using a silicone-based, fluorine-based, long-chain alkyl-based, fatty acid amide-based mold release agent, or silica powder.

3. Soft adherend The flexible adherend 5 is a reinforced body that has flexibility and is reinforced by a reinforcing film 4, for example, flexible optical devices such as flexible display panels, flexible electronic devices such as flexible printed wiring boards (FPC), and The soft base material of these components. When the flexible adherend 5 is a soft optical device, for example, a pixel area including a plurality of pixels existing in an array, a circuit area including various circuit elements such as a driving circuit are formed on one surface of the flexible adherend 5, And the wiring pattern of these electrical connections. When the flexible adherend 5 is a flexible electronic device, for example, various circuit elements and wiring patterns are formed on one surface of the flexible adherend 5. In FIG. 1, the flexible adherend 5 has a flat plate shape, but various top-view shapes can be obtained according to the design of the manufacturing target device.

4. Manufacturing method of laminated body An embodiment of the method of manufacturing the laminate 1 will be described with reference to FIG. 3.

The manufacturing method of the laminated body 1 includes: the step of preparing the reinforcing film 4 (the third step); the step of arranging the soft adherend 5 on one side of the reinforcing film 4 (the fourth step); and the step of removing a part of the reinforcing film 4 The step of forming the first reinforcing film portion 6 and the second reinforcing film portion 7 (the fifth step); the step of improving the adhesive force of the adhesive layer 3 (the sixth step).

As mentioned above, the common point of the first adhesive composition and the second adhesive composition is that the composition can irreversibly change the state from a state with low adhesive force to a state with high adhesive force, and the following points Difference: the first adhesive composition changes its state by light, on the other hand, the second adhesive composition changes its state by heat.

In addition, the details will be described later, but in the first adhesive composition, the cured product of a light hardener (preferably a polyfunctional (meth)acrylate) becomes a highly adhesive component with relatively high adhesive force. The polymer (preferably acrylic polymer) becomes a low-adhesive component with relatively low adhesion. On the other hand, in the second adhesive composition, the base polymer (preferably acrylic polymer) becomes the adhesive Relatively high high-viscosity components, components containing organosiloxanes (preferably acrylic polymers with organosiloxane skeletons) become low-viscosity components with relatively low adhesion. That is, depending on which of the first adhesive composition or the second adhesive composition the adhesive layer 3 is formed of, the high-viscosity component and the low-viscosity component in the adhesive layer 3 are determined.

Therefore, the following description is divided into the case where the adhesive layer 3 is formed from the first adhesive composition and the case where the adhesive layer 3 is formed from the second adhesive composition.

4-1. Manufacturing method of laminate in which adhesive layer is formed from first adhesive composition First, with reference to FIG. 3, the manufacturing method (manufacturing method 1) of the laminated body 1 which forms the adhesive layer 3 from a 1st adhesive composition is demonstrated.

In the third step, as shown in FIG. 3A, a reinforcing film 4 is prepared.

Then, in the fourth step, as shown in FIG. 3B, the reinforcing film 4 is attached to the flexible adherend 5 in such a manner that the adhesive layer 3 disposed on one surface of the substrate 2 is in contact with the soft adherend 5.

At this time, at the interface between the adhesive layer 3 and the soft adherend 5, a light hardener (preferably a polyfunctional (meth)acrylate) is concentrated and present.

In addition, such a light hardener inhibits the adhesion between the adhesive layer 3 and the soft adherend 5.

Therefore, the adhesive force of the adhesive layer 3 to the soft adherend 5 can be reduced. Specifically, the adhesive force of the adhesive layer 3 is, for example, 4 N/25 mm or less, preferably 1 N/25 mm or less.

If the adhesive force of the adhesive layer 3 is less than the above upper limit, a part of the reinforcing film 4 can be easily removed in the fifth step described below.

In addition, the above-mentioned adhesive force was measured by bonding the reinforcing film 4 to the polyimide film at 25° C., and performing a 180-degree peel test at a peeling speed of 300 mm/min.

Then, in the fifth step, a part of the reinforcing film 4 is removed.

Specifically, only one part of the central part (hereinafter referred to as the removed part 9) that divides the reinforcing film 4 into three parts in the surface direction is removed.

When removing a part of the reinforcing film 4, first, as shown in FIG. 3C, the removed part 9 is removed by _{laser light such as CO 2} laser or YAG laser, such as Thomson knife, Pinnock knife, rotary knife, and scraper. , Blades and other cutting tools, and then only the removed part 9 is peeled off with the end of the removed part 9 as the starting point.

Thereby, as shown in FIG. 3C, the 1st reinforcement film part 6 and the 2nd reinforcement film part 7 remain.

Then, in the sixth step, the adhesive force of the adhesive layer 3 is improved.

Specifically, the adhesive layer 3 of the first reinforcing film portion and the adhesive layer 3 of the second reinforcing film portion 7 are respectively irradiated with light. The light includes active energy rays such as ultraviolet rays and electron beams.

Thereby, the light hardening agent (preferably a polyfunctional (meth)acrylate) concentrated at the interface between the adhesive layer 3 and the soft adherend 5 hardens, and the adhesive force of the hardened material becomes higher.

That is, in the first adhesive composition, the adhesive force of the cured product of a light curing agent (preferably a polyfunctional (meth)acrylate) is improved. On the other hand, the base polymer (preferably an acrylic polymer) ) The adhesion is not improved.

As a result, compared with the base polymer (preferably acrylic polymer), the adhesive force of the cured product of the light hardener (preferably polyfunctional (meth)acrylate) is relatively higher, so the light hardener (preferably Preferably, the cured product of multifunctional (meth)acrylate) becomes a high-viscosity component, and the base polymer (preferably an acrylic polymer) becomes a low-viscosity component.

In addition, a hardened product of a light hardening agent (preferably a polyfunctional (meth)acrylate) as a high-adhesive component is segregated at the interface between the adhesive layer 3 and the soft adherend 5.

Specifically, in the following TOF-SIMS (Time of Flight Secondary Ion Mass Spectrometry) measurement, the interface between the adhesive layer 3 and the soft adherend 5 is taken as the starting point and taken from the The ratio of the high-viscosity component in the region where the interface is toward the adhesive layer 3 side and the depth corresponding to 5% of the thickness of the adhesive layer 3 is the end point is, for example, 2 times or more, preferably 3 times or more of the low-viscosity component.

Thereby, the adhesive layer 3 and the soft adherend 5 can be firmly bonded.

Specifically, the adhesive force of the adhesive layer 3 after light irradiation is, for example, 5 N/25 mm or more, preferably 8 N/25 mm or more, more preferably 10 N/25 mm or more, and more preferably 12 N /25 mm or more.

On the other hand, a part of the hardened product of the light hardener (preferably polyfunctional (meth)acrylate) is compatible with the base polymer (preferably acrylic polymer), and the self-adhesive layer 3 is adhered to the soft The interface of the body 5 spreads toward the adhesive layer 3 side. In this way, on the side of the adhesive layer 3 in the thickness direction than the interface between the adhesive layer 3 and the soft adherend 5, a cured product (highly adhesive) of a light curing agent (preferably a polyfunctional (meth)acrylate) Ingredients) and base polymers (preferably acrylic polymers) (low-viscosity ingredients) are mixed.

Specifically, in the following TOF-SIMS measurement, a depth corresponding to 30% of the thickness of the adhesive layer 3 from the interface of the adhesive layer 3 and the soft adherend 5 toward the adhesive layer 3 side is taken as the starting point And the ratio of the high-viscosity component in the region where the depth equivalent to 70% of the thickness of the adhesive layer 3 is the end point is, for example, 0.8 times or more, preferably 1 time or more, and, for example, 1.5 times or less of the low-viscosity component .

This improves the shear creep characteristics.

Based on the above, a laminate 1 is obtained.

4-2. Manufacturing method of a laminate in which the adhesive layer is formed from the second adhesive composition Secondly, with reference to Fig. 3, a method for manufacturing the laminate 1 (manufacturing method 2) in which the adhesive layer 3 is formed from the second adhesive composition will be described.

As described above, the second adhesive composition includes a base polymer and an organosiloxane-containing component.

Hereinafter, the case where the base polymer is an acrylic polymer and the organosiloxane-containing component is an acrylic polymer having an organosiloxane skeleton will be described in detail.

In the second adhesive composition, the adhesive force of the acrylic polymer is relatively higher than that of the acrylic polymer having an organosiloxane skeleton. That is, in the second adhesive composition, the acrylic polymer is a high-viscosity component, and the acrylic polymer having an organosiloxane skeleton is a low-viscosity component.

In the third step, as shown in FIG. 3A, a reinforcing film 4 is prepared.

Then, in the fourth step, as shown in FIG. 3B, the reinforcing film 4 is attached to the flexible adherend 5 in such a manner that the adhesive layer 3 disposed on one surface of the substrate 2 is in contact with the soft adherend 5.

Here, at the interface between the adhesive layer 3 and the soft adherend 5, acrylic polymers having an organosiloxane skeleton are concentrated and present.

In addition, the acrylic polymer having an organosiloxane skeleton hinders the adhesion between the adhesive layer 3 and the soft adherend 5.

Therefore, the adhesive force of the adhesive layer 3 to the soft adherend 5 can be reduced. Specifically, the adhesive force of the adhesive layer 3 is, for example, 4 N/25 mm or less, preferably 1 N/25 mm or less.

If the adhesive force of the adhesive layer 3 is less than the above upper limit, a part of the reinforcing film 4 can be easily removed in the fifth step described below.

Then, in the fifth step, as described above, a part of the reinforcing film 4 is removed.

Thereby, as shown in FIG. 3C, the 1st reinforcement film part 6 and the 2nd reinforcement film part 7 remain.

Then, in the sixth step, the adhesive force of the adhesive layer 3 is improved.

Specifically, the adhesive layer 3 of the first reinforcing film portion and the adhesive layer 3 of the second reinforcing film portion 7 are respectively heated.

As heating conditions, the heating temperature is, for example, 40°C or higher, preferably 50°C or higher, more preferably 60°C or higher, and, for example, less than 150°C, preferably 120°C or lower, more preferably 100°C or lower, and more It is preferably 80°C or less, and the heating time is not particularly limited. For example, it is 1 hour or less, preferably 30 minutes or less, more preferably 10 minutes or less, more preferably 5 minutes or less, and, for example, 1 minute or more . In addition, it is also possible to perform heating for a longer time (for example, 2 hours or more, preferably 5 hours or more) within the limit that the reinforcing film 4 or the adherend 5 does not cause significant thermal deterioration. Furthermore, the above-mentioned heating may be implemented multiple times.

As a result, the acrylic polymer having an organosiloxane skeleton and the acrylic polymer having an organosiloxane skeleton that are concentrated at the interface between the adhesive layer 3 and the soft adherend 5, and the acrylic polymer having an organosiloxane skeleton are improved. The polymer is diffused from the interface between the adhesive layer 3 and the soft adherend 5 to the adhesive layer 3 side.

In this way, at the interface between the adhesive layer 3 and the soft adherend 5, the ratio of acrylic polymer segregation is relatively increased (in other words, the acrylic polymer as a high-viscosity component is in the adhesive layer 3 and the soft adherend 5 The interface deflection of 5 exists).

Specifically, in the following TOF-SIMS measurement, the interface between the adhesive layer 3 and the flexible adherend 5 is taken as the starting point, and the thickness from the interface to the adhesive layer 3 side is equivalent to the thickness of the adhesive layer 3 The ratio of the high-viscosity component in the region with a depth of 5% as the end point is, for example, 2 times or more, preferably 3 times or more of the low-viscosity component.

Thereby, the adhesive layer 3 and the soft adherend 5 can be firmly bonded.

Specifically, the adhesive force of the heated adhesive layer 3 is, for example, 5 N/25 mm or more, preferably 8 N/25 mm or more, more preferably 10 N/25 mm or more, and more preferably 12 N/25 mm or more. Above 25 mm.

On the other hand, if an acrylic polymer having an organosiloxane skeleton is diffused from the interface between the adhesive layer 3 and the soft adherend 5 to the adhesive layer 3 side, the adhesive layer 3 and The interface of the soft adherend 5 is on the side of the adhesive layer 3, and the acrylic polymer (high-viscosity component) and the acrylic polymer (low-viscosity component) with an organosiloxane skeleton are mixed.

Specifically, in the following TOF-SIMS measurement, a depth corresponding to 30% of the thickness of the adhesive layer 3 from the interface of the adhesive layer 3 and the soft adherend 5 toward the adhesive layer 3 side is taken as the starting point And the ratio of the high-viscosity component in the region where the depth equivalent to 70% of the thickness of the adhesive layer 3 is the end point is, for example, 0.8 times or more, preferably 1 time or more, and, for example, 1.5 times or less of the low-viscosity component .

This improves the shear creep characteristics.

Based on the above, a laminate 1 is obtained.

7. The effect of the layered body In this laminated body 1, the 1st reinforcement film part 6 and the 2nd reinforcement film part 7 are arrange|positioned at intervals in the surface direction of the soft to-be-adhered body 5, and are spaced apart.

Therefore, as shown in FIG. 4, the laminated body 1 can be bent between the first reinforcing film portion 6 and the second reinforcing film portion 7 so that the first reinforcing film portion 6 and the second reinforcing film portion 7 face each other outside. In addition, the laminated body 1 may be bent between the first reinforcing film section 6 and the second reinforcing film section 7 so that the first reinforcing film section 6 and the second reinforcing film section 7 face each other inward.

In addition, in each of the adhesive layer 3 of the first reinforcing film portion 6 and the adhesive layer 3 of the second reinforcing film portion 7, in the thickness direction, high-adhesive components are present in the soft adherend 5 and the adhesive layer The interface deflection of 3 exists.

Therefore, in this laminated body 1, the adhesive layer 3 and the flexible adherend 5 are firmly bonded, especially even if the laminated body 1 is made such that the first reinforcing film portion 6 and the second reinforcing film portion 7 face each other outwards. The bending can also suppress peeling due to the shear force from the reinforcing film 4 toward the central part of the adhesive layer 3, and even if the laminated body 1 is made such that the first reinforcing film portion 6 and the second reinforcing film portion 7 face each other inwardly The bending can also suppress peeling due to the shear force from the central part of the adhesive layer 3 toward the reinforcing film 4.

In addition, in the laminated body 1, on the side of the adhesive layer 3 in the thickness direction from the interface between the adhesive layer 3 and the soft adherend 5, the high-adhesive component and the low-adhesive component are mixed.

Therefore, even if the layered body 1 is made as described above, the stress generated by bending is dispersed, and the damage of the layered body 1 can be suppressed.

That is, the laminate 1 has excellent shear creep characteristics.

8. Variations In the above-mentioned method for producing a laminate in which an adhesive layer is formed from the second adhesive composition, an acrylic polymer having an organosiloxane skeleton is exemplified as a low-viscosity component, but it is not limited to this. For example, there are the following Situation: By heating in the sixth step, the organosiloxane skeleton as a side chain in the acrylic polymer with organosiloxane skeleton moves from the interface between the adhesive layer 3 and the soft adherend 5 to the adhesive layer 3 Molecules move on the side, and on the other hand, the main chain (acrylic skeleton) continues to be segregated at the interface between the adhesive layer 3 and the soft adherend 5.

In this case, the side chain of the acrylic polymer with the organosiloxane skeleton becomes the low-viscosity component, and the main chain of the acrylic polymer with the organosiloxane skeleton becomes the high-viscosity component.

[Example] Hereinafter, examples and comparative examples are shown to further specifically explain the present invention. Furthermore, the present invention is not limited in any way by the examples and comparative examples. In addition, specific numerical values such as the blending ratio (content ratio), physical property values, and parameters used in the following description can be replaced with the blending ratios (content ratio), physical property values, parameters, etc. corresponding to them described in the above-mentioned "embodiment". The record upper limit (defined as "below" or "not reached") or lower limit (defined as "above" or "exceeding").

Furthermore, "parts" and "%" are quality standards as long as they are not specifically mentioned.

1. Details of ingredients Each component used in each Example and each comparative example is described below. Takenate D110N: 75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals APG700: Polypropylene glycol #700 (n=12) diacrylate; functional group equivalent 404 g/eq Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF

2. Preparation of polymer Synthesis example 1

9 parts by weight of methyl methacrylate (MMA), 63 parts by weight of 2-ethylhexyl acrylate (2EHA), and acrylic hydroxy 13 parts by weight of ethyl ester (HEA), 15 parts by weight of N-vinylpyrrolidone (NVP), 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, and 233 parts by weight of ethyl acetate as a solvent, Pour in nitrogen, and perform nitrogen replacement for about 1 hour while stirring. Then, it heated to 60 degreeC, it reacted for 7 hours, and the weight average molecular weight (Mw) of the acrylic polymer solution of 1,200,000 was obtained.

3. Preparation of adhesive composition Preparation Example 1 (Preparation of the first adhesive composition)

To the acrylic polymer solution of Synthesis Example 1, Takenate D110N (75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals) was added as a cross-linking agent and compared to the polymerization 100 parts by weight of the solid content of the polymer is 2.5 parts by mass, and APG700 (polypropylene glycol #700 (n=12) diacrylate) is added as a light hardening agent and is 20 parts by mass relative to 100 parts by weight of the solid content of the polymer. Add Irgacure 184 (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Corporation) as a photopolymerization initiator and 0.1 parts by mass relative to 100 parts by weight of the solid content of the polymer, and mix them uniformly to prepare the first adhesive combination Things.

4. Manufacture of reinforcing film Manufacturing example 1

A 75 μm thick polyethylene terephthalate film (“Lumirror S10” manufactured by Toray) without surface treatment was used as a substrate, and the photocurable composition of Preparation Example 1 was dried on the substrate After that, the thickness is 25 μm and is coated with a grooved roll. The solvent was removed by drying at 130°C for 1 minute. In this way, an adhesive layer is formed on one surface of the substrate. Furthermore, the release treatment surface of a release film (a 25 μm-thick polyethylene terephthalate film with a silicone release treatment on the surface) was attached to one surface of the adhesive layer. Then, an aging treatment was carried out for 4 days in an atmosphere of 25°C to allow the crosslinking reaction of the polymer and the crosslinking agent to proceed. This produces a reinforcing film.

5. Manufacturing of laminated body Example 1

After the peeling film was peeled from the reinforcing film of Production Example 1, the reinforcing film was attached to a polyimide film having a thickness of 12.5 μm ("Kapton 50EN" manufactured by Toray DuPont).

Then, the reinforcing film is divided into three parts in the surface direction using laser light, and one part of the central part is peeled off.

Thereby, the two parts (that is, the first reinforcing film part and the second reinforcing film part) of the two ends of the three parts divided into the three parts in the surface direction remain.

Then, the adhesive layer in the first reinforcing film portion and the adhesive layer in the second reinforcing film portion are irradiated with light to increase the adhesive force of the adhesive layer.

In this way, a laminated body is manufactured.

6. Evaluation (Distribution of high-viscosity components and low-viscosity components in the adhesive layer) (TOF-SIMS measurement)

For the laminate of Example 1, TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry, TRIFT V) equipped with an Ar-GCIB (Ar Gas Cluster Ion Beam) gun manufactured by ULVAC-PHI was used. nano TOF) Measure the distribution of high-viscosity components and low-viscosity components in the adhesive layer. As the primary ion source, Bi ₃ ⁺⁺ (30 kV) was used. A 25 eV electron gun is used in the electrification and neutralization. Ar-GCIB (Ar2500 ⁺ , 20 kV) is used for depth analysis.

The results are shown in Table 1.

7. Explore As shown in Table 1, at 0 nm from the penetration depth of the adhesive layer, the peak intensity (a.u.) of the cured product of the light hardener is 0.13. From this, it can be seen that the hardened substance (high-adhesion component) of the light hardener is concentrated and present at the interface between the polyimide film and the adhesive layer.

In addition, at a distance of 500 nm from the penetration depth of the adhesive layer, the peak intensity (a.u.) of the cured product of the light hardener and the peak intensity (a.u.) of the acrylic polymer are both 0.025.

It can be seen that, on the side of the adhesive layer more than the interface between the polyimide film and the adhesive layer, the cured product of the light hardener (high adhesion component) and acrylic polymer (low adhesion component) are mixed.

[Table 1] Example No. Hardening of light hardener Acrylic polymer Penetration depth (nm) Peak intensity (au) Penetration depth (nm) Peak intensity (au) Example 1 0 0.13 0 0.02 500 0.025 500 0.025 1200 0.034 1200 0.023

In addition, the above-mentioned invention is provided as an exemplary embodiment of the present invention, but it is only a mere example and should not be interpreted limitedly. Variations of the present invention known to practitioners in this technical field are included in the scope of the following invention applications. [Industrial availability]

The laminate and the reinforcing film of the present invention are suitably used for optical devices, electronic devices and their constituent parts.

1: Layered body 2: Substrate 3: Adhesive layer 4: Reinforcing film 5: Soft adherend 6: The first reinforcing membrane part 7: The second reinforcing membrane part 9: Remove part

Fig. 1 shows a schematic view of an embodiment of the laminate of the present invention. Fig. 2 is a schematic diagram showing an embodiment of a method for manufacturing a reinforcing film, and Fig. 2A shows the first step of preparing the substrate, Fig. 2B shows the second step of laminating an adhesive layer on an area of the substrate, and Fig. 2C shows in The step of peeling off the film from one area of the adhesive layer. Fig. 3 is a schematic diagram showing an embodiment of a method for manufacturing a laminate, and Fig. 3A shows the third step of preparing a reinforcing film, Fig. 3B shows the fourth step of arranging a flexible adherend on one side of the reinforcing film, and Fig. 3C shows The fifth step of forming the first reinforcing film portion and the second reinforcing film portion by removing a part of the reinforcing film. FIG. 3D shows the sixth step of improving the adhesive force of the adhesive layer. Fig. 4 shows a laminated body formed by bending the first reinforcing film portion and the second reinforcing film portion so that the first reinforcing film portion and the second reinforcing film portion face each other outwards.

1: Layered body

2: Substrate

3: Adhesive layer

5: Soft adherend

6: The first reinforcing membrane part

7: The second reinforcing membrane part

Claims (6)

A laminated body characterized in that it is provided with a reinforcing film and a soft adherend arranged on one side of the reinforcing film, and The reinforcing film includes a base material and an adhesive layer arranged on one side of the base material and containing high-adhesion components and low-adhesion components, The reinforcing film is provided with a first reinforcing film portion and a second reinforcing film portion arranged at intervals in the surface direction of the soft adherend, and In each of the adhesive layer of the first reinforcing film portion and the adhesive layer of the second reinforcing film portion, in the thickness direction, the high-adhesive component is biased at the interface between the soft adherend and the adhesive layer Set exists. The laminate of claim 1, wherein in each of the adhesive layer of the first reinforcing film portion and the adhesive layer of the second reinforcing film portion, the adhesive layer is greater than the interface in the thickness direction On the other hand, the above-mentioned high-viscosity component and the above-mentioned low-viscosity component are mixed. Such as the laminate of claim 1 or 2, wherein the high-adhesion component is a cured product of multifunctional (meth)acrylate, The aforementioned low-viscosity component is an acrylic polymer. Such as the laminate of claim 1 or 2, wherein the above-mentioned high-viscosity component is an acrylic polymer, The aforementioned low-viscosity component is a component containing organosiloxane. A laminated body characterized in that it is provided with a reinforcing film and a soft adherend arranged on one side of the reinforcing film, and The reinforcing film includes a base material and an adhesive layer arranged on one side of the base material and containing high-adhesion components and low-adhesion components, The reinforcing film is provided with a first reinforcing film portion and a second reinforcing film portion arranged at intervals in the surface direction of the soft adherend, and The adhesive force of the above adhesive layer is above 5 N/25 mm, The thickness of the adhesive layer is 5 μm or more. A reinforcing film, characterized in that it is used in a laminate, the laminate is provided with a reinforcing film and a soft adherend arranged on one side of the reinforcing film, and The reinforcing film includes a base material and an adhesive layer arranged on one side of the base material and containing high-adhesion components and low-adhesion components, The said reinforcing film is provided with the 1st reinforcing film part and the 2nd reinforcing film part arrange|positioned at intervals in the surface direction of the said flexible to-be-adhered body.

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