JP2001212900A - Easy peeling laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in easy releasability which has high adhesion properties when the laminate is in use, and from which a base is released without adhering an adhesive layer to the base after the laminate is irradiated with energy. SOLUTION: The laminate is formed by sequentially laminating (A) the base, (B) a crosslinking polymer containing an expanding agent, and (C) a crosslinking polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate obtained by sequentially laminating a substrate, a crosslinkable polymer containing a foaming agent, and a crosslinkable polymer, and has high adhesiveness when the laminate is used. The present invention relates to a laminate having excellent peelability, in which an adhesive layer does not adhere to a substrate after irradiating energy to the laminate, and a method of recovering a recyclable (reusable) substrate from the laminate.

[0002]

2. Description of the Related Art A laminate obtained by laminating a substrate with an adhesive is known as a component for automobiles,
It is used for many products such as home appliances, electronics products, office supplies, and daily necessities. Recently, in order to recycle (reuse) the base material, a method of collecting the base material from the laminate has been required. For example, JP-A-5-26990
No. 6 discloses a laminate composed of a substrate / crosslinkable polymer / crosslinkable polymer containing a foaming agent / crosslinkable polymer / substrate, and a substrate / crosslinkable polymer containing a foaming agent / substrate. A laminate is disclosed, and it is reported that the substrate can be peeled and recovered by irradiating the laminate with energy. Therefore, when the present inventors irradiate energy to these laminates, the substrate is peeled from the laminate, but the peeled substrate has an adhesive layer attached thereto, and the substrate is reused as it is. It turned out to be difficult.

[0003]

Under these circumstances, the present inventors have conducted intensive studies on a base material, a crosslinkable polymer containing a foaming agent, and a laminate comprising the crosslinkable polymer. When the laminate is used, the substrate is strongly adhered to the laminate and the laminate is formed by laminating the cross-linkable polymer in a specific order. The present invention was found to be a laminate excellent in easy peelability, in which an adhesive layer was not adhered to the substrate or could be easily peeled off even if it was adhered to the substrate, and the present invention was completed.

That is, the present invention provides a laminate characterized by sequentially laminating (A): a base material (B): a crosslinkable polymer containing a foaming agent, and (C): a crosslinkable polymer. An object of the present invention is to provide a method for recovering a substrate that can be reused from a laminate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) used in the present invention includes, for example,
Metals such as iron, steel, gold, silver, copper, and aluminum; inorganic substances such as glass, gypsum, ceramics, and ceramics; polyolefins, polycarbonate, polystyrene, polyester, polyether, polyimide, polyamide, epoxy, polyurethane, ABS, and rubber Examples include plastics or synthetic fibers, natural fibers such as cotton, hemp, and silk; synthetic fibers such as viscose rayon and cellulose acetate; wood, paper, and leather. Among them, metals and plastics are preferred.

As (A), a composite material such as a fiber-reinforced composite material and a plastic containing an inorganic filler may be used. In addition, in (A), if necessary, the bonding surface of (B) may be subjected to coating such as plating, surface modification using plasma or laser, surface treatment such as surface oxidation, and etching.

The crosslinkable polymers (B) and (C) are melts which can be applied before bonding and which are bonded and then crosslinked intramolecularly to become three-dimensional polymers.
For example, a photocurable resin, a thermosetting resin, and the like can be given. The photocurable resin is usually a resin containing a photocurable oligomer and / or monomer and a photopolymerization initiator. Examples of the oligomer and / or monomer having photocurability include an oligomer and / or monomer having at least one unsaturated carbon-carbon bond capable of photoradical polymerization, and a molecular terminal capable of photo Michael addition polymerization. Examples include a combination of an oligomer having a double bond and a polythiol, and an alicyclic epoxy compound capable of photocationically polymerizing. Among them, it is preferable to use an oligomer and / or a monomer having at least one unsaturated carbon-carbon bond.

As the oligomer having an unsaturated carbon-carbon bond, an oligomer having at least one unsaturated group selected from an acryloyl group, a methacryloyl group and a vinyl group is usually used. Specifically, urethane acrylates, urethane acrylates such as urethane methacrylate, epoxy acrylates, epoxy acrylates such as epoxy methacrylate, polyester acrylates, polyester acrylates such as polyester methacrylate, melamine acrylate, melamine acrylates such as melamine methacrylate, Acrylic resin acrylates, unsaturated polyesters and polyenes are exemplified.

As urethane acrylates, for example, those obtained by reacting an organic polyisocyanate, a polyol and a hydroxy acrylate compound, etc., are obtained by reacting an organic polyisocyanate and a hydroxy acrylate compound. It may be something. Examples of epoxy acrylates include those obtained by reacting acrylic resin and / or methacrylic acid with an epoxy resin such as a bisphenol A epoxy resin and a novolak type epoxy resin. As polyester acrylates, for example,
Examples thereof include those obtained by reacting acrylic acid and / or methacrylic acid with a polyester polyol synthesized from a polyhydric alcohol and a polycarboxylic acid.
As melamine acrylates, for example, melamine,
Examples thereof include those obtained by subjecting melamine resin obtained by condensation polymerization of urea, benzogamine and the like with formalin and the like to a dealcoholation reaction with β-hydroxyethyl acrylate and the like, and the like. As acrylic resin acrylates, for example, carboxylic acid group, hydroxyl group, contained in acrylic resin,
Examples thereof include those obtained by reacting acrylic acid and / or methacrylic acid with a functional group such as a glycidyl group. Examples of unsaturated polyesters include those obtained by reacting a polyol with an α, β-unsaturated dicarboxylic acid such as fumaric acid and maleic anhydride. Examples of the polyenes include those obtained by reacting an organic polyisocyanate with allyl alcohol and / or vinyl alcohol.

On the other hand, the monomer having an unsaturated carbon-carbon bond is usually at least one kind of unsaturated group-containing monomer selected from monofunctional acrylic monomers, polyfunctional acrylic monomers and vinyl group-containing monomers. Monomers and the like are used.

As the monofunctional acrylic monomers, compounds containing one acrylate group or methacrylate group in the molecule are usually used, and specific examples include isobornyl acrylate, isobornyl methacrylate, and dicycloalkyl methacrylate. Monomers having a ring structure such as pentenyl acrylate, dicyclopentenyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate and benzyl methacrylate, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate , 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate,
-Hydroxybutyl methacrylate, 2-hydroxy-
Examples include monomers having a hydroxyl group such as 3-phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate. Further, monofunctional acrylic monomers in which the raw material alcohol or phenol in the above-mentioned monomers having a ring structure is modified with an alkylene oxide in advance can also be used.
Particularly, a modified product of alkylene oxide having 2 to 3 carbon atoms is preferable, and examples thereof include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, phenyloxyethyl acrylate, and phenyloxyethyl acrylate.

As the polyfunctional acrylic monomers, compounds containing two or more acrylate groups or methacrylate groups in the molecule are usually used.
Examples of the acrylate group-containing compound include polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, and trimethylol. Examples include propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and tris [acryloxyethyl] isocyanate.

The vinyl group-containing monomers include, for example, vinyl esters such as vinyl acetate, vinyl propionate and branched fatty acid vinyl; aromatic vinyls such as styrene, chlorostyrene, alkylstyrene and divinylbenzene;
Nitrogen-containing vinyls such as N-vinylpyrrolidone and N-vinylcaprolactam.

Examples of the photocurable resin include one or more monomers, one or more oligomers, and a mixture of one or more monomers and one or more oligomers. It is preferable to use a mixture of one or more oligomers and one or more monomers in terms of viscosity, curability, adhesiveness, and the like.

The photopolymerization initiator contained in the photocurable resin includes, for example, carbonyl compounds, sulfur compounds, azo compounds, peroxides and the like. Among them, carbonyl compounds are preferred, and specifically, benzophenone, benzyl, Michler's ketone, 2-chlorothioxanthone,
2,4-diethylthioxanthone, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and 2,
Carbonyl compounds such as 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine which absorb ultraviolet light; camphorquinone;
And carbonyl compounds that absorb visible light, such as ketocoumarin.

As the photopolymerization initiator, two or more photopolymerization initiators may be used. In addition, the photocurable resin, if necessary, N, N-dimethylaminoacetophenone, pN,
A photopolymerization initiation aid such as ethyl N-dimethylbenzoate or a photosensitizer may be contained. The amount of the photopolymerization initiator used in the photocurable resin is based on 100 parts by weight of the photocurable oligomer and / or monomer.
Usually, it is about 0.5 to 20 parts by weight.

As the photocurable resin, for example, "Sumiflash XR-235, XR-98" (photocurable resin manufactured by Sumitomo Chemical Co., Ltd.), "DAICURE SD170"
A commercially available photocurable resin such as “0” (photocurable resin manufactured by Dainippon Ink and Chemicals, Inc.) may be used.

Examples of the thermosetting resin used as the crosslinkable polymer of the present invention include novolak resin, resol resin, urea resin, melamine resin, alkyd resin, imide resin, urethane resin, epoxy resin, Modified silicone resins such as a silyl group-terminated polyether into which a silyl group has been introduced, unsaturated polyester resins, and the like, among which epoxy resins and modified silicone resins are preferred.

Examples of the thermosetting resin include “Araldite Rapid” (epoxy adhesive manufactured by Ciba Specialty Chemicals), “ER-10” (epoxy tree adhesive manufactured by NSC Japan), and “Bond Quick 5” (KONISHI) Epoxy adhesive manufactured by Epson Corporation), "EP-330" (epoxy adhesive manufactured by Cemedine), "Super X" (modified silicone adhesive manufactured by Cemedine), "Bond Silex Clear" (modified silicone adhesive manufactured by Konishi), A commercially available thermosetting resin such as “Takelac A-385 + Takenate A-50” (urethane adhesive manufactured by Takeda Pharmaceutical Co., Ltd.) may be used.

The thermosetting resin may contain a curing agent, if necessary. Specifically, such as hexamethylenetetramine used for novolak resins, polyamines and acid anhydrides used for epoxy resins, isocyanates used for urethane resins, resole resins, acids used for alkyd resins, and modified silicone resins. Examples include peroxides and styrene used in unsaturated polyester resins such as tin compounds and amine compounds used.

The crosslinkable polymer used in the present invention includes:
Solvents such as organic solvents and water, thermoplastic resins such as polyvinyl alcohol, polyamide, and polyester having gas barrier properties, fillers, antioxidants, polymerization inhibitors, and adhesion-imparting agents as long as the adhesiveness and easy-peelability are not reduced. And a surface conditioner such as a surfactant, an ultraviolet absorber, an antioxidant and an antistatic agent.

The (B) of the present invention is a crosslinkable polymer containing a foaming agent. Among them, a photocurable resin containing a foaming agent is preferable. Examples of the foaming agent contained in (B) include those which expand in volume upon heating, and specific examples thereof include an inorganic foaming agent, an organic foaming agent, and a heat-expandable hollow sphere.

As the inorganic foaming agent, sodium bicarbonate,
Carbonate compounds such as ammonium carbonate, ammonium bicarbonate and ammonium nitrite; phosphate compounds such as polyphosphoramide, ammonium polyphosphate and melamine phosphate;
Carbonized materials such as starch, cellulose, saccharides and dipentaerythritol; light metals such as magnesium powder and aluminum powder; hydrides such as sodium borohydride and sodium hydride; and azides such as sodium azide. Examples of the organic foaming agent include azo compounds such as azodicarbonamide and azobisisobutyronitrile; nitroso compounds such as dinitrosopentamethylenetetramine and N, N'-dinitroso-N, N-dimethylterephthalamide; p-toluene Hydrazide compounds such as sulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), hydrazolcarbonamide and the like; p-toluenesulfonyl azide, acetone-p-sulfonyl hydrazone, melamine, urea, dicyandiamide and the like.

Examples of the heat-expandable hollow spheres include polyvinylidene chloride, a copolymer of vinylidene chloride and acrylonitrile, polyacrylonitrile, acrylonitrile and acrylic acid such as "Microsphere" manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Particle size 1 containing low boiling hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane inside a shell made of a methyl copolymer, etc.
５０50 μ spheres and the like.

As the foaming agent of the present invention, two or more kinds of foaming agents may be used in combination. As the foaming agent, a heat-expandable hollow sphere is particularly preferable. The content of the foaming agent in (B) is such that the adhesive layer has sufficient adhesive strength when the laminate is used, and the adhesive layer can be easily peeled off from (A) when recovering (A) by irradiating energy. The amount is necessary to reduce the adhesive force, specifically, depending on the type of foaming agent, for example, when the foaming agent is a heat-expandable hollow sphere, 100 parts by weight of the crosslinkable polymer On the other hand, it is usually about 10 to 80 parts by weight, preferably about 30 to 70 parts by weight.

(C) of the present invention is a crosslinkable polymer containing no foaming agent. (C) uses a crosslinkable polymer that can be used for (B), such as a photocurable resin or a thermosetting resin. The crosslinkable polymers that can be used in (C) and (B) may be the same or different types of crosslinkable polymers, and a mixture of two or more types of crosslinkable polymers is used as the crosslinkable polymer (C). You may. Among them, a thermosetting resin is preferable, and an epoxy resin and a modified silicone resin are particularly preferable.

The laminate of the present invention is obtained by sequentially laminating (A), (B) and (C). (B) of the present invention
Usually, a desired adherend is adhered to the surface of (C) where is not laminated. Here, the adherend can adhere to (C), and includes, for example, the base material as described in (A) and articles such as automobile bodies and home electric appliances. Also,
A laminate including an adhesive may be used as the adherend. For example, a laminate in which (B ′) and (A ′) are sequentially laminated on the surface (C) where (B) is not laminated, that is,
(A) / (B) / (C) / (B ′) / (A ′). Here, (B ′) represents a crosslinkable polymer containing a blowing agent that may be different from (B), and (A ′) represents a substrate that may be different from (A). The laminate of (A) / (B) / (C) / (B ′) / (A ′) is preferable because both of the substrates (A) and (A ′) can be collected and reused. .

As a method for producing the laminate of the present invention, for example, an adherend is placed on the surface of the adhesive layer (B) of the laminate (1) comprising (A) and (B) via (C). How to laminate with
(2) A method of sequentially laminating (C), (B) and (A) on an adherend, (3) a laminate comprising (A) and (B), and (A ′) and (B ′) (A), (B), a method of laminating the surfaces of the adhesive layers (B) and (B ′) with each other via (C).
(C), (B ') and (A') are sequentially laminated. If necessary, the obtained laminate may be subjected to treatment such as pressing and post-curing. here,
As a method of laminating the adhesive layers such as (B), (C) and (B '), bar coat coating, roll coater coating, spray coating, blade coater coating, screen coating, and hot melt applicator are used. And a method using spin coating. The method for producing a laminate according to the present invention will be described with reference to the case of (3) as a specific example. After spin-coating the reactive resins ((B) and (B ')), they are light-cured,
(A) / (B) and (A ′) / (B ′) are obtained. Next, after the surface of (B) is coated with a thermosetting resin (C) by bar coating, (A ′) / (B ′) is laminated via (C) and left standing at room temperature, (A) / (B) / (C)
/ (B ′) / (A ′).

The laminate thus obtained is used for articles requiring reuse of the base material, such as refrigerators, washing machines, air conditioners,
Home appliances such as microwave ovens, vacuum cleaners, televisions, and batteries; office supplies such as personal computers, printers, copiers, fixed phones, and mobile phones; automobiles such as bumpers and battery containers; furniture; Panels, semiconductors,
Used for electronic products such as printed wiring boards, integrated circuits, and secondary battery containers.

By irradiating the laminated body of the present invention with energy, the substrate can be easily peeled off and recovered from the laminated body, and can be reused. The recovered base material such as metal and plastic may be melt-molded and reused. Here, the energy to irradiate the laminated body includes, for example, light energy such as ultraviolet light, visible light, infrared light, laser light, electromagnetic energy such as microwave, ultrasonic wave, shock wave, radio wave, magnetic field, and heat such as heating and cooling. Energy, etc., among which light energy and heat energy are preferred, and heating is particularly preferred.

The method for recovering the substrate in the present invention includes:
For example, put the laminate in an oven, hot water tank, etc., usually,
A method in which (B) is foamed by heating at about 80 to 300 ° C., preferably about 100 to 200 ° C. to recover the base material, and the article is irradiated with flame, infrared rays, steam, ultrasonic waves, electromagnetic waves, or the like ( A method of foaming B) to recover the base material, and the like. Among them, a method in which (B) is foamed by heating in an oven preheated to about 100 to 200 ° C. to collect the base material is preferable. The base material thus recovered is easily peeled off from the laminate, and the base material is hardly adhered to the adhesive layer, or even if the adhesive layer is adhered, the base material is easily peeled off from the base material. To the extent that it can be obtained, and the substrate can be reused.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

(Substrates: A and A ') The following test pieces were used as substrates. A-1: Aluminum (AL) plate 25 mm X 100 mm, thickness 1 mm (Sumitomo Light Metal Co., Ltd. A1050P HB (mirror finish)) A-2: Polycarbonate (PC) plate 25 mm X 100 mm, thickness 2 mm (Takiron 1600 manufactured by Teijin Limited)

(Crosslinkable Polymers Containing Blowing Agent: B and B ') The following crosslinkable polymers were used as crosslinkable polymers containing a foaming agent. B-1: 100 parts by weight of an acrylate-based photocurable resin "Sumiflash XR-98" (manufactured by Sumitomo Chemical Co., Ltd.) is a thermally expandable hollow sphere "Microsphere F-30D (hereinafter referred to as F30)" (Matsumoto). Yushi Pharmaceutical Co., Ltd.) 50
Parts by weight were blended. B-2: 50 parts by weight of "F30" was blended with 100 parts by weight of the epoxy thermosetting resin "ER-10" (manufactured by NSC). B-3: "Urethane adhesive + foaming agent" 50 parts by weight of two-part urethane adhesive "Takelac A385" and 50 parts by weight of "Takenate A-50" (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) F30 "was blended in an amount of 50 parts by weight.

(Crosslinkable polymer: C) The following was used as (C). C-1: Epoxy-based thermosetting resin "Araldite Rapid" (manufactured by Ciba Specialty Chemicals Co., Ltd.) C-2: Epoxy-based thermosetting resin "ER-10" (manufactured by NSC) C-3: Acrylate-based Photo-curable resin "Sumiflash XR-98" (manufactured by Sumitomo Chemical Co., Ltd.)

(Adhesion test) The laminate was put into a 25 mm X 20
mm (= 500 mm ² ), and measured by a tensile test according to JIS K 6850.

(Example 1) On one side of (A-1), (B-
1) was laminated with a bar coat so as to have a thickness of about 300 μm, and was cured by UV irradiation at an irradiation amount of 400 mJ / cm ² . Next, the surface of (B-1) and (A-2) were adhered to each other through (C-1) of about 70 μm, fixed with a clip, and kept at 23 ° C. and 50% RH while the clip was kept.
After standing for 4 hours, (A-1) / (B-1) / (C-1) /
A laminated body obtained by laminating in the order of (A-2) was obtained. When an adhesion test was performed on the obtained laminate, it was 1.6.
The adhesive layer (B-1) was finally peeled at a tensile strength of 4.5 N / mm without peeling even at a tensile strength of N / mm. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes. When this laminate was taken out, (B-
1) is foamed to peel off (A-1), and the collected (A-1) hardly has an adhesive layer attached thereto,
It could be reused. No need for reuse (A-
In (2), the adhesive layers (B-1) and (C-1) adhered, and could not be easily peeled off.

(Example 2) On one side of (A-1), (B-
2) was laminated by a bar coat so as to have a thickness of about 70 μm, and was allowed to stand at 23 ° C. and 50% RH for 24 hours to cure. Next, through (C-1) of about 70 μm, (B-2)
The surface of (A-1) was adhered to the surface of (A-1), fixed with a clip, and allowed to stand at 23 ° C. and 50% RH for 24 hours while keeping the clip, so that (A-1) / (B-2) / (C) -1) / (A-2)
Was obtained in this order. When the obtained laminate was subjected to an adhesiveness test, it did not peel even at a tensile strength of 0.5 N / mm, and finally the adhesive layer (B-2) peeled at a tensile strength of 4.7 N / mm. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes. When the laminate was taken out, B-2 was foamed and A-1 was peeled off. The adhesive layer was hardly adhered to the collected A-1 and was in a reusable state. (A-2), which does not need to be reused, could not be easily peeled off because the adhesive layers (B-2) and (C-1) adhered.

(Embodiment 3) On one side of (A-1), (B-
1) was laminated by spin coating so as to have a thickness of about 300 μm, and was cured by irradiation with UV at an irradiation dose of 400 mJ / cm ² , and (A-1) / (B-1) was laminated. Next, except that A-1 is changed to A-2, (A-
2) / (B-1) was laminated. Then, (A-1) /
(B-1) and (A-2) / (B-1) are adhered to each other via a C-2 of about 70 μm between the surfaces of B-1 and fixed with a clip. 23 ℃, 50% R
H for 24 hours, and (A-1) / (B-1) / (C
-2) / (B-1) / (A-2) to obtain a laminate. When an adhesion test was performed on the obtained laminate, a tensile strength of 1.6 N / mm was obtained (A-1).
The adhesive layer on the side (B-1) was peeled off. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes.
When this laminate was taken out, all of (B-1) was foamed and (A-1) and (A-2) were peeled off, and the recovered (A-1) contained an adhesive. Almost no adhesion. (A-2) had the adhesive layers (B-1) and (C-2) attached thereto, but the adhesive layer was peeled off during removal from the oven. (A-1) and (A)
-2) was in a reusable state.

(Embodiment 4) On one side of (A-1), (B-
1) was laminated by spin coating so as to have a thickness of about 300 μm, and was cured by irradiation with UV at an irradiation dose of 400 mJ / cm ² , and (A-1) / (B-1) was laminated. Next, (A-2) / (B-1) was laminated in the same manner except that (A-1) was changed to (A-2). Then, (A
-1) / (B-1) and (A-2) / (B-1) as (B
(A-1) / (B-1) / (C-1) / (B-1)
-1) / (A-2) are fixed by clips laminated in the order of, and the clips are kept at 23 ° C. and 50% RH for 2 hours.
It was left still for 4 hours to obtain a laminate. When an adhesion test was performed on the obtained laminate, the adhesive layer of (B-1) on the (A-2) side was peeled at a tensile strength of 0.7 N / mm. The laminate prepared in the same manner was placed in an oven at 150 ° C. for 5 minutes.
Heated for minutes. When this laminate was taken out, B-1
All foamed to peel off A-1 and A-2, and the adhesive layer hardly adhered to the recovered A-2. (A-1) includes (B-1) and (C
Although the adhesive layer of -1) was adhered, the adhesive layer was peeled off during removal from the oven. (A-1) and (A-
2) was in a reusable state.

(Comparative Example 1) Example 1 was repeated except that B-1 having a thickness of about 300 μm in Example 1 was spin-coated so as to have a thickness of about 20 μm in (C-3). And (A-1) / (C-3) / (C-1) /
A laminated body obtained by laminating in the order of (A-2) was obtained. When an adhesion test was performed on the laminate, the adhesive layer (C-3) was peeled off at a tensile strength of 1.6 N / mm. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes. When this laminate was taken out, the appearance was the same as before heating, and (A-1) and (A-2) were not peeled off. When an adhesion test was performed on the heated laminate, a tensile strength of 1.6 N / mm (C-
The adhesive layer of 3) was peeled off.

(Comparative Example 2) The same operation as in Example 2 was carried out except that B-2 in Example 2 was not laminated.
1) / (C-2) / (A-2) was obtained in a laminated manner. When an adhesion test was performed on the laminate, the C-2 adhesive layer was peeled at a tensile strength of 0.5 N / mm. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes. When this laminate was taken out, the appearance was the same as before heating, and (A-1) and (A-2) were not peeled off. When the adhesion test was performed on the heated laminate, the C-3 adhesive layer was peeled at a tensile strength of 0.5 N / mm.

(Comparative Example 3) One side of A-1 was coated with about 2 C-3.
Lamination by spin coating to a thickness of 0 μm, 4
UV irradiation at a dose of 00 mJ / cm ² for curing,
(A-1) / (C-3) were laminated. Next, A-1 is A
(A-2) / (C-
3) was laminated. Subsequently, through (B-2) of about 70 μm, (A-1) / (C-3) and (A-2) / (C-
3) and the surfaces of C-3 were adhered to each other, fixed with a clip, and allowed to stand at 23 ° C. and 50% RH for 24 hours while keeping the clip, so that (A-1) / (C-3) / (B-2) / (C
-3) / (A-2) to obtain a laminated body. When an adhesion test was performed on the obtained laminate, the C-3 adhesive layer was peeled at a tensile strength of 1.6 N / mm. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes. When the laminate was taken out, the adhesive layer of (B-2) was peeled off, but the adhesive layer of (C-3) adhered to the surfaces of (A-1) and (A-2). The adhesive layer could not be easily peeled.

(Comparative Example 4) (A-1) and (A-2) were adhered to each other via (C-1) of about 70 μm and fixed with a clip. (A-1) / (C-1) / (A-2)
Was obtained in this order. When an adhesion test was performed on the obtained laminate, the adhesive layer (C-1) was peeled at a tensile strength of 1.6 N / mm. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes. When this laminate was taken out, the appearance was the same as before heating, and (A-1) and (A-2) were not peeled off. When an adhesion test was performed on the heated laminate, the laminate had a tensile strength of 1.6 N / mm (C-1).
Was peeled off.

(Comparative Example 5) About 3 times of C-3 was applied to one side of A-1.
Laminated by spin coating to a thickness of 00 μm,
UV irradiation was performed at an irradiation amount of 400 mJ / cm ² to cure, and (A-1) / (C-3) was laminated. Next, A-1
Is changed to A-2, and (A-2) / (C
-3) was laminated. Subsequently, the above two laminates are referred to as (C-
The surfaces of 3) are adhered to each other via 70 μm (C-1),
Fix with a clip and leave the clip at 23 ° C, 5
After standing at 0% RH for 24 hours, (A-1) / (C-3) /
A laminate was obtained by laminating in the order of (C-1) / (C-3) / (A-2). When an adhesion test was performed on the obtained laminate, a tensile strength of 0.2 N / mm (A-
The adhesive layer of (C-3) on the 2) side was peeled off. Peeled (C
In -3), an uncured portion was observed.

(Comparative Example 6) On one side of (A-1), (B-
3) is coated with a bar coat so as to have a thickness of about 200 μm, immediately adhered to (A-2), fixed with a clip, and kept at 23 ° C. and 50% RH for 7 days while the clip is kept. It left still and obtained the laminated body laminated | stacked in order of (A-1) / (B-3) / (A-2). When an adhesion test was performed on the obtained laminate, (B-3) was peeled off at a tensile strength of 1.2 N / mm. The laminate thus produced was heated in an oven at 150 ° C. for 5 minutes. When this laminate was taken out, the appearance was the same as before heating, and each substrate was not peeled off. When an adhesion test was performed on the heated laminate, (B-3) peeled off at a tensile strength of 0.2 N / mm, but (A-1) and (A)
In -2), the adhesive layer (B-3) remained, and it was difficult to peel it off.

[0047]

The laminate of the present invention has high adhesiveness when the laminate is used, and the substrate is peeled off from the laminate after irradiating the laminate with energy, and the adhesive layer adheres to the substrate. It is a laminate with excellent peelability that can be easily peeled off from the substrate even if the adhesive layer is attached, so it can be used for automobiles, home appliances, electronics products, office supplies or household goods. It can be used for articles that require recycling of the substrate.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB10 AK01B AK01C AK25 AK45 AK53 AT00A BA03 BA10A BA10C CA01B EH46 EJ05 EJ08 EJ423 EJ533 EJ543 GB41 JB02B JB02C JB13 JB14 JK06 JL06 JL11 JL16

Claims (8)

[Claims] 1. A laminate comprising: (A): a substrate (B): a crosslinkable polymer containing a foaming agent; and (C): a crosslinkable polymer. 2. The laminate according to claim 1, wherein (B)
(B ′) and (A ′) are sequentially laminated on the surface of (C) not facing (c). here,
(B ′) is a crosslinkable polymer containing a blowing agent that may be different from (B), and (A ′) represents a substrate that may be different from (A). 3. The method according to claim 1, wherein (A) and / or (A ′) is a metal, an inorganic substance, a plastic, a synthetic fiber, a natural fiber, a synthetic fiber, wood,
The laminate according to claim 1 or 2, wherein the laminate is at least one selected from paper and leather. 4. The laminate according to claim 1, wherein the crosslinkable polymer is a thermosetting resin and / or a photocurable resin. 5. The crosslinkable polymer of (B) and / or (B ′) is a photocurable resin, wherein (C) and / or (C ′)
The laminate according to any one of claims 1 to 4, wherein the crosslinkable polymer is a thermosetting resin. 6. The laminate according to claim 1, wherein the foaming agent is at least one selected from the group consisting of a heat-expandable hollow sphere, an inorganic foaming agent and an organic foaming agent. 7. An article comprising the laminate according to any one of claims 1 to 6. 8. A method for recovering a substrate, comprising irradiating the laminate according to claim 1 with at least one kind of energy selected from light energy, electromagnetic energy and heat energy.