Laminate and method for manufacturing a laminate

Abstract

The present invention provides a laminate in which the base material and the component including the resin layer do not separate during unintended processes, and the component including the resin layer can be easily peeled off from the base material during intended processes. [Solution] The laminate comprises a base material and a covering member including at least one resin layer, wherein the base material has a target region including at least a part of the surface of the base material, the covering member has a covering region in contact with the target region, the covering region includes a first region with an adhesion force of 0.1 kN / m or more and 1.0 kN / m or less to the target region, and a second region with an adhesion force of 0.0001 kN / m or more and 0.01 kN / m or less to the target region, and the area of ​​the first region is 1% or more and 30% or less to the total area of ​​the covering region.

Description

[Technical Field]

[0001] This invention relates to a laminate and a method for manufacturing a laminate. [Background technology]

[0002] In recent years, for example, in the manufacturing process of semiconductor devices, semiconductor substrates such as silicon wafers and compound semiconductor wafers have become thinner. Thin semiconductor substrates are susceptible to warping and cracking during transport and polishing. Therefore, adhesive tape is used to reinforce the semiconductor substrate by attaching a support substrate before transport and polishing, and then to allow the support substrate to be peeled off from the semiconductor substrate.

[0003] The adhesive tapes described above are required to have sufficient adhesive strength to the adherend during the prescribed process, to be easily peeled off the adherend after the prescribed process is completed, and to leave no adhesive residue on the adherend after peeling, or if any residue does remain, to be easily removed. However, conventional adhesive sheets have not satisfied all of the above conditions. In particular, when an adhesive sheet is applied to an adherend, the adherend is processed at a high temperature of about 260°C, and then peeled off after a prescribed operation such as UV irradiation, the adhesion strength does not decrease sufficiently after the process due to enhanced adhesion, making peeling difficult.

[0004] To solve the above problems, Patent Document 1 discloses an invention of a double-sided adhesive tape that can also be easily peeled off. According to this invention, by providing irregularities on the surface of the resin layer, the adhesion to the substrate can be adjusted, and because the surface of the resin layer has multiple concave shapes, each concave shape acts like a suction cup, making it easy to peel off even after the process. Furthermore, Patent Document 2 discloses an invention of an adhesive tape that achieves both process resistance and ease of peeling by examining the composition of the resin layer. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-033441 [Patent Document 2] Japanese Patent Publication No. 2011-032350 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the inventions disclosed in Patent Documents 1 and 2 do not mention processing the adherend at high temperatures of around 260°C, and the challenge remains of achieving both resistance to high-temperature processes and the ability to easily peel off the substrate after the process without enhancing adhesion of the resin layer due to heat.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a laminate in which the base material and the component including the resin layer do not peel off in unintended processes, and in which the component including the resin layer can be easily peeled off from the base material in intended processes, and a method for manufacturing the same. [Means for solving the problem]

[0008] The present invention comprises the following configuration. [1] comprising a base material and a covering member including at least one resin layer, The substrate has a target region that includes at least a portion of the surface of the substrate, The covering member has a covering area that is in contact with the target area, The covering region includes a first region having an adhesion force of 0.1 kN / m or more and 1.0 kN / m or less with respect to the target region, and a second region having an adhesion force of 0.0001 kN / m or more and 0.01 kN / m or less with respect to the target region. A laminate in which the area of ​​the first region is 1% or more and 30% or less of the total area of ​​the covered region. [2] The laminate according to [1], wherein the first region and the second region are in contact in the covering region. [3] The covering region includes only the first region and the second region, The laminate according to [1] or [2], wherein the sum of the area of ​​the first region and the area of ​​the second region is equal to the total area of ​​the covering region. [4] The laminate according to any one of [1] to [3], wherein the first region is located at the end or edge of the covering region. [5] The target area and the covering area are rectangular, The laminate according to any one of [1] to [4], wherein the first region is located on the four sides or four corners of the covering region. [6] The substrate is an intermediate of the finished product, a laminate according to any one of [1] to [5]. A method for manufacturing a laminate according to any one of [7] [1] to [6], The first step is to provide the covering member on the substrate so that the target area and the covering area are in contact, A second step is to provide the first region in the covering region, A method for manufacturing a laminate, comprising at least a third step of providing the second region in the covering region. [8] The method for manufacturing a laminate according to [7], wherein the second and / or third step comprises at least one treatment selected from the group consisting of UV irradiation, laser irradiation, pressure application, and solvent immersion. [Effects of the Invention]

[0009] The laminate of the present invention does not delaminate between the substrate and the component including the resin layer during unintended processes, and the component including the resin layer can be easily peeled off from the substrate during intended processes. Furthermore, the method for manufacturing the laminate of the present invention can produce a laminate in which the substrate and the component including the resin layer do not delaminate between the substrate and the component including the resin layer during unintended processes, and the component including the resin layer can be easily peeled off from the substrate during intended processes. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic plan view showing the arrangement (layout A) of the first and second regions within the covering area of ​​the covering member. [Figure 2]It is a plan view schematically showing the arrangement (layout B) of the first region and the second region in the covering area of the covering member. [Figure 3] It is a plan view schematically showing the arrangement (layout C) of the first region and the second region in the covering area of the covering member. [Figure 4] It is a plan view schematically showing the arrangement (layout D) of the first region and the second region in the covering area of the covering member. [Figure 5] It is a plan view schematically showing the arrangement (layout E) of the first region and the second region in the covering area of the covering member.

Embodiments for Carrying out the Invention

[0011] Hereinafter, embodiments which are an example of the present disclosure will be described. These descriptions and examples are illustrative of the embodiments and do not limit the scope of the invention. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and they do not limit the present disclosure. For example, the present disclosure can be added, omitted, substituted, changed, etc. with respect to numbers, amounts, positions, ratios, materials, configurations, types, orders, etc. without departing from the gist.

[0012] In the present disclosure, each component may include a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in a composition or the like, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition or the like, unless otherwise specified. In the present disclosure, the term "layer" includes not only the case where it is formed over the entire region when observing the region where the layer exists, but also the case where it is formed only in a part of the region.

[0013] In the present disclosure, the "weight average molecular weight" is a value in terms of pullulan calculated using gel permeation chromatography (GPC).

[0014] In this disclosure, a numerical range represented by "~" includes the numbers at both ends of that range.

[0015] ≪Laminated structure≫ The laminate of this disclosure comprises a substrate and a coating member including at least one resin layer.

[0016] <Base material> In the laminates of this disclosure, the substrate is not particularly limited, but may be any finished product manufactured by an industrial process, or an intermediate in the process of manufacturing a finished product.

[0017] The base material is not particularly limited, but for example, resin materials and inorganic materials can be used. Examples of resin materials include polyimide resin, polyamide-imide resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, polyarylate resin, polyacetal resin, acrylic resins such as poly(meth)acrylate, polyvinylidene fluoride resin, polytetrafluoroethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride resin obtained by graft copolymerization of acrylic resin, polyvinyl alcohol resin, polyethylene resin, polypropylene resin, urethane resin, cycloolefin resin, polystyrene, liquid crystal polymer (LCP), polyetheretherketone (PEEK) resin, polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), and cellulose nanofiber. Examples of inorganic materials include silicon, silicon carbide, gallium nitride, sapphire, ceramics, glass, metals, diamond-like carbon (DLC), and alumina.

[0018] Furthermore, a resin substrate containing a thermosetting resin and an inorganic filler can also be used as the base material. Examples of thermosetting resins include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, triazine resins, and melamine resins. Examples of inorganic fillers include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. These thermosetting resins and inorganic fillers can be used individually or in combination of two or more. In addition, a resin substrate containing a thermoplastic resin and an inorganic filler can also be suitably used as the base material, and the thermoplastic resin and inorganic filler can be used individually or in combination of two or more.

[0019] The form (shape) of the base material is not particularly limited, but examples include planar flexible materials, rigid materials, and rigid-flexible materials. More specifically, the form of the base material can be film-like, sheet-like, or plate-like, and commercially available materials molded into these shapes may be used as the base material. Alternatively, a material formed into a planar shape by coating and drying the above-mentioned resin solution may be used as the base material.

[0020] The substrate may consist of one type of material, or it may be a mixture or laminate of two or more types of materials. For example, the substrate may be a single layer of metal foil, or it may include metal foil and one or more resin layers, or it may have a layer structure other than the substrate and resin layers. Furthermore, the laminate of this disclosure may have resin layers on both sides of the substrate. As an example, when laminating multiple flat plate materials, they can be bonded together using an adhesive or the like. By combining two or more types of materials, the physical properties of the substrate, such as thickness, rigidity, modulus of elasticity, and coefficient of thermal expansion, can be adjusted as appropriate.

[0021] The thickness of the substrate is not particularly limited as long as it does not warp or crack during the manufacturing method described later, but it is preferably between 0.05 μm and 5000 μm.

[0022] The laminate of this disclosure has a target region (hereinafter simply referred to as the "target region") which includes at least a part of the surface of the substrate. Here, the target region is at least a part of the surface (region) of the substrate that is covered by a covering member described later and is not exposed to the atmosphere or the atmosphere of the process. The target region of the substrate surface that is covered by the covering member is not exposed during the industrial process and is therefore protected from the effects of processes such as oxidation of the resin layer due to heat or chemical treatment.

[0023] The shape of the target area is not particularly limited, but if the substrate is in the form of a film, sheet, or plate, it may be at least a part or the entire surface of one of these forms. Furthermore, the target area (surface of the substrate) may be flat, or it may have protrusions or uneven surfaces, as long as it does not affect the manufacturing method described later. The surface roughness (maximum height Sz) of the target area of ​​the substrate is preferably 3 μm or less, more preferably 1 μm or less, and even more preferably 0.1 μm or less. If the maximum height Sz of the target area of ​​the substrate is within the above range, the coating member can reliably fill in the unevenness on the surface of the target area of ​​the substrate. The maximum height Sz can be determined as a three-dimensional surface roughness obtained optically using a white light interferometer, laser microscope (for example, the VK-X3000 laser microscope manufactured by Keyence Corporation) or the like (ISO25178-2;2012).

[0024] The surface of the substrate (especially the target area) may be surface-treated to improve adhesion with the coating member described later. The surface treatment method for the substrate is not particularly limited, but examples include liquid-layer ozone treatment, corona treatment, and plasma treatment. These surface treatment methods may be performed individually or in combination of two or more methods.

[0025] <Covering material> The laminate of this disclosure comprises a covering member. The covering member has a covering region that is in contact with the target region of the substrate. The close contact between the target region of the substrate and the covering region of the covering member integrates the substrate and the covering member to form a laminate. The covering region constitutes at least a portion of the surface of the covering member. The covering member may function as a protective member that covers a target area of ​​the substrate to protect it from heat and chemicals during the process, or it may function as a reinforcing member that integrates with the substrate to reinforce its strength, or it may have both functions.

[0026] The covering member includes at least one resin layer. At least one resin layer is located on the surface of the covering member and constitutes a covering region that is in contact with the target region of the substrate. The resin layer constituting the covering region functions as an adhesion layer. The resin layer constituting the covering region may be a single layer or a laminate of two or more layers. The covering member may consist only of one or more resin layers constituting the covering region. The covering member may include resin layers other than the resin layer constituting the covering area. The covering member may also have a laminated structure of the resin layer constituting the covering area and the other resin layer. Examples of resin materials constituting the other resin layer are the same as those described for the substrate above. These resin materials may be appropriately selected according to the function required of the covering member (e.g., protective function, reinforcing function). The covering member may include other layers containing materials other than resin. The covering member may also have a laminated structure consisting of a resin layer constituting the covering region and other layers. Examples of materials constituting the other layers are the same as those described for the substrate above.

[0027] (1st area) The coated area includes at least a first area A having an adhesion force of 0.1 kN / m or more and 1.0 kN / m or less to the target area of ​​the substrate. Because the coated area includes the first area A, the target area of ​​the substrate and the coated area of ​​the coating member adhere strongly in the first area A, preventing the coating member from peeling off the substrate during industrial processes, thus making it applicable to industrial processes. The adhesion force in the first area A to the target area of ​​the substrate is 0.1 kN / m or more, preferably 0.3 kN / m or more, and more preferably 0.5 kN / m or more. Furthermore, the adhesion force in the first area A to the target area of ​​the substrate is 1.0 kN / m or less, preferably 0.5 kN / m or less, and more preferably 0.3 kN / m or less. When the adhesion force is 1.0 kN / m or less, adhesive residue from the coating member onto the target area of ​​the substrate can be suppressed when the coating member is peeled off the substrate during the peeling process.

[0028] (Second area) The coated area includes at least a second area B in which the adhesion force to the target area of ​​the substrate is 0.0001 kN / m or more and 0.01 kN / m or less. Because the coated area includes the second area B, the adhesion force between the target area of ​​the substrate and the coated area of ​​the coating member is small in the second area B, so that the coating member, which becomes unnecessary after being applied to an industrial process, can be easily peeled off from the substrate. The adhesion force between the target area of ​​the substrate in the second area B is 0.01 kN / m or less, preferably 0.007 kN / m or less, and more preferably 0.005 kN / m or less. Furthermore, the adhesion force between the target area of ​​the substrate in the second area B is 0.0001 kN / m or more, preferably 0.001 kN / m or more, and more preferably 0.005 kN / m or more. When the adhesion force is 0.0001 kN / m or greater, the target area of ​​the substrate and the coating member adhere sufficiently, so there are no problems with the conformability or lamination properties of the coating member, and the occurrence of blistering of the coating member during the heat-resistant process can be suppressed.

[0029] The resins contained in the resin layer constituting the coating region, that is, resin A contained in the first region A and resin B contained in the second region B, may be the same or they may be different. Here, resins A and B are not particularly limited, and resins that satisfy the adhesion force to the target area of ​​the substrate may be selected and applied as resins A and B, or resins that can adjust the adhesion force to the target area of ​​the substrate by applying the adhesion force adjustment process described later (hereinafter simply referred to as the "adhesion force adjustment process") may be applied as resins A and B, respectively.

[0030] When the resin contained in the first region A and the resin contained in the second region B are the same (i.e., when the coated region is composed of a single resin), the first region A may be formed by applying an adhesion strength adjustment treatment to a portion of the coated region formed using the resin, while the remainder forms the second region B. Alternatively, the second region B may be formed by applying an adhesion strength adjustment treatment to a portion of the formed coated region, while the remainder forms the first region A. Furthermore, one of the first region A and the second region B may be formed by applying an adhesion strength adjustment treatment to a portion of the formed coated region, and then the other of the first region A and the second region B may be formed by applying an adhesion strength adjustment treatment.

[0031] (Adhesion adjustment process) In the coated region, at least one adhesion adjustment treatment can be selected from the group consisting of ultraviolet irradiation, laser irradiation, pressure application, and solvent treatment. By performing the adhesion adjustment treatment on a part of the resin layer constituting the coated region of the coated member, it is possible to provide two or more regions in the coated region in which the adhesion strength of the resin to the target area of ​​the substrate differs. The details of the adhesion adjustment treatment described above will be explained below, as well as the resin material used as the resin layer constituting the coated region of the coated member when performing the adhesion adjustment treatment.

[0032] "Ultraviolet irradiation treatment" Ultraviolet irradiation treatment is a process that changes the adhesion strength of a resin to a target area of ​​a substrate by irradiating the resin layer constituting the coating area of ​​a coating member with ultraviolet light. The conditions for ultraviolet irradiation treatment can be appropriately set depending on the material used for the resin layer. Resin layers suitable for ultraviolet irradiation treatment can include resin compositions containing a gas generating agent that generates gas upon ultraviolet irradiation, and materials that harden upon ultraviolet irradiation and change in adhesion strength.

[0033] Examples of gas-generating agents that produce gas when irradiated with ultraviolet light include tetrazole compounds or their salts, triazole compounds or their salts, azo compounds, azide compounds, xanthone acetate, and carbonates. These gas-generating agents may be used individually or in combination of two or more. Among these, tetrazole compounds or their salts are particularly preferred due to their excellent heat resistance.

[0034] The amount of gas generating agent in the resin layer is not particularly limited, but is preferably 5 to 50 parts by mass, and more preferably 8 to 30 parts by mass, per 100 parts by mass of the total resin layer. By including the gas generating agent in the resin layer within the above range, the resin layer can exhibit particularly excellent adhesion adjustment capabilities through ultraviolet irradiation treatment.

[0035] The resin layer containing the gas generating agent is not particularly limited, but it is preferable to include a thermosetting resin from the viewpoint of heat resistance. The thermosetting resin is not particularly limited, but a polyimide resin having siloxane bonds is particularly preferred from the viewpoint of achieving both heat resistance and ultraviolet transmittance. The weight-average molecular weight of the thermosetting resin is preferably 5,000 to 500,000, and more preferably 10,000 to 200,000.

[0036] Furthermore, an example of a resin material that hardens and changes in adhesion strength upon UV irradiation is a photocurable adhesive containing a photopolymerization initiator, with a polymerizable polymer as the main component. A polymerizable polymer can be obtained, for example, by reacting a (meth)acrylic polymer having a functional group in its molecule (hereinafter referred to as a functional group-containing (meth)acrylic polymer) with a compound having a functional group that reacts with the functional group and a radically polymerizable unsaturated bond in its molecule (hereinafter referred to as a functional group-containing unsaturated compound). A functional group-containing (meth)acrylic polymer is a polymer that is adhesive at room temperature, and, as in the case of general (meth)acrylic polymers, uses alkyl acrylates and / or alkyl methacrylates with an alkyl group having a carbon number in the range of 2 to 18 as the main monomer, and is obtained by copolymerizing this with a functional group-containing monomer and, if necessary, other modifier monomers that can copolymerize with these, by a conventional method. The weight-average molecular weight of a functional group-containing (meth)acrylic polymer is usually around 200,000 to 2,000,000.

[0037] Examples of functional group-containing monomers include carboxyl group-containing monomers such as acrylic acid and methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate and hydroxyethyl methacrylate, epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, isocyanate group-containing monomers such as isocyanate ethyl acrylate and isocyanate ethyl methacrylate, and amino group-containing monomers such as aminoethyl acrylate and aminoethyl methacrylate. Other copolymerizable modifier monomers include, for example, various monomers used in general (meth)acrylic polymers such as vinyl acetate, acrylonitrile, and styrene.

[0038] As the functional group-containing unsaturated compound to be reacted with the functional group-containing (meth)acrylic polymer, the same as the functional group-containing monomers described above can be used depending on the functional group of the functional group-containing (meth)acrylic polymer. For example, if the functional group of the functional group-containing (meth)acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer can be used; if the functional group is a hydroxyl group, an isocyanate group-containing monomer can be used; if the functional group is an epoxy group, a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide can be used; and if the functional group is an amino group, an epoxy group-containing monomer can be used.

[0039] Examples of photopolymerization initiators include those activated by irradiation with light of a wavelength of 250 nm to 800 nm. Examples of such photopolymerization initiators include acetophenone derivative compounds such as methoxyacetophenone; benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether; ketal derivative compounds such as benzyldimethyl ketal and acetophenone diethyl ketal; phosphine oxide derivative compounds; bis(η5-cyclopentadienyl) titanocene derivative compounds; and photoradical polymerization initiators such as benzophenone, Michler ketone, chlorothioxanthone, todecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone or in combination of two or more.

[0040] "Laser irradiation treatment" Laser irradiation is a process that changes the adhesion strength of a resin to a target area of ​​a substrate by irradiating the resin layer constituting the coating area of ​​a coating member with a laser. The conditions for laser irradiation can be appropriately set according to the material used for the resin layer. For a resin layer suitable for laser irradiation, a combination of a resin having a photothermal conversion function that absorbs light of a predetermined wavelength and converts that light into heat, and a resin that is thermally decomposable can be used. That is, when laser light is irradiated, the photothermal conversion resin generates heat, and the generated heat is transmitted to the adjacent thermally decomposable resin, causing the thermally decomposable layer containing the thermally decomposable resin to decompose at the interface with the photothermal conversion layer containing the photothermal conversion resin. Due to this mechanism, the adhesion strength of the resin layer containing the photothermal conversion resin and the thermally decomposable resin decreases. In particular, the thickness of the photothermal conversion layer is preferably 5 μm to 200 μm, and more preferably 10 μm to 150 μm.

[0041] One embodiment of the photothermal conversion layer is one in which the transmittance of light with a wavelength of 355 nm is 50% or less, more preferably 40% or less, even more preferably 35% or less, and most preferably 0%. If the transmittance of light with a wavelength of 355 nm is within this range, a photothermal conversion layer that easily absorbs UV laser light and generates heat can be formed. Such a photothermal conversion resin is not particularly limited as long as it can absorb ultraviolet light, and examples include polyimide resins, polyether ether ketone resins, polyethylene naphthalate resins, acrylic resins, epoxy resins, etc. Among these, polyimide resins are preferred as the photothermal conversion resin.

[0042] The photothermal conversion resin may be a resin containing a pigment, dye, or UV absorber to absorb a predetermined amount of ultraviolet light. Any suitable UV absorber can be used as the UV absorber, as long as it is a compound that absorbs ultraviolet light (e.g., wavelength 355 nm). Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, salicylate-based UV absorbers, and cyanoacrylate-based UV absorbers. Among these, it is preferable to use a triazine-based UV absorber or a benzotriazole-based UV absorber, and it is more preferable to use a triazine-based UV absorber.

[0043] Examples of pigments that absorb specific ultraviolet light include azo, phthalocyanine, anthraquinone, lake, perylene, perinone, quinacridone, thioindigo, dioxandine, isoindolinone, and quinophthalone pigments. Examples of dyes that absorb specific ultraviolet light include azo, phthalocyanine, anthraquinone, carbonyl, indigo, quinoneimine, methine, quinoline, and nitro dyes.

[0044] In another embodiment of the photothermal conversion layer, the transmittance of light with a wavelength of 1032 nm is 50% or less, more preferably 40% or less, even more preferably 35% or less, and most preferably 0%. If the transmittance of light with a wavelength of 355 nm is within this range, a photothermal conversion layer that readily absorbs IR laser light and generates heat can be formed.

[0045] In this case, the photothermal conversion layer can be made of a resin containing a predetermined dye (pigment or dye) to absorb infrared rays of a predetermined wavelength. The photothermal conversion layer that absorbs ultraviolet rays may be a single layer containing a dye in the resin, or it may be a multi-layer structure consisting of a layer containing a predetermined dye and a resin layer. When a layer containing a dye is formed, it is preferable that the layer containing the dye and the thermal decomposition layer are adjacent to each other. As the dye that absorbs infrared rays, any suitable dye can be used in any suitable amount, as long as it can impart IR light absorption. Examples of such dyes include carbon black, tungsten cesium oxide, lanthanum hexaboride, tin-doped indium oxide, antimond-doped tin oxide, cyanine compounds, phthalocyanine compounds, dithiol metal complexes, naphthoquinone compounds, diimmonium compounds, azo compounds, etc. Examples of resins that constitute the resin layer include polyimide resins, polyethylene terephthalate resins, polyamide resins, polyether ether ketone resins, polyethylene naphthalate resins, acrylic resins, epoxy resins, etc. In particular, it is preferable to use a polyimide resin or a polyethylene terephthalate resin as the resin constituting the resin layer. Furthermore, a colored metal layer may be used as the photothermal conversion layer that absorbs infrared rays.

[0046] On the other hand, the pyrolysis layer containing the pyrolysis resin can be made of acrylic resin, urethane resin, polyester resin, etc., and the 5% weight loss temperature is preferably 250°C to 400°C, and more preferably 280°C to 370°C. The 5% weight loss temperature of the pyrolysis layer can be adjusted, for example, by the type and structure of the resin constituting the pyrolysis layer, the presence and type of additives, etc.

[0047] The tensile modulus of the pyrolysis layer at 25°C is preferably 0.05 MPa to 1 GPa, and more preferably 0.1 MPa to 300 MPa. If the tensile modulus of the pyrolysis layer at 25°C is within this range, it becomes easier to remove the pyrolysis layer remaining on the substrate after peeling the coating member off the substrate. For example, the pyrolysis layer remaining on the substrate can be swollen, and most of the pyrolysis layer as residue can be removed all at once.

[0048] The thickness of the pyrolysis layer is preferably 10 μm to 200 μm, more preferably 20 μm to 150 μm, and even more preferably 30 μm to 100 μm.

[0049] When the photothermal conversion layer absorbs ultraviolet light, in one embodiment, the thermal decomposition layer has a transmittance of 80% or more for light with a wavelength of 355 nm, more preferably 82% to 98%, and even more preferably 85% to 97%. Within this range, when peeling is performed by UV laser irradiation, the laser light can preferably reach the photothermal conversion layer, promoting a decrease in adhesion at the thermal decomposition layer / photothermal conversion layer interface of the photothermal conversion layer.

[0050] Furthermore, when the photothermal conversion layer absorbs infrared rays, in one embodiment, the thermal decomposition layer has a transmittance of 80% or more for light with a wavelength of 1032 nm, more preferably 85% to 98%, and even more preferably 90% to 96%. Within this range, when adjusting the adhesion force by irradiating with IR laser light, the laser light can be preferably directed to the photothermal conversion layer, thereby promoting the adjustment of the adhesion force at the thermal decomposition layer / photothermal conversion layer interface of the photothermal conversion layer.

[0051] In the laser irradiation process, the laser light used is of any appropriate wavelength depending on the configuration of the resin layer. The conditions for laser irradiation are also of any appropriate condition depending on the configuration of the resin layer. In one embodiment, UV laser light is used as the laser light. The wavelength of the UV laser light is preferably 150 nm to 380 nm, and more preferably 240 nm to 360 nm. The output power of the UV laser light is, for example, 0.1 W to 2.0 W. In another embodiment, IR laser light is used as the laser light. The wavelength of the IR laser light is preferably 800 nm to 10600 nm, and more preferably 900 nm to 1200 nm. The output power of the IR laser light is, for example, 0.01 W to 10 W.

[0052] "Pressure application" Pressure application is a process that changes the adhesion force of the resin to a target area of ​​the substrate by applying pressure (load) to the resin layer that constitutes the coating area of ​​a coating member. The conditions for pressure application can be appropriately set depending on the material used for the resin layer.

[0053] For a resin layer suitable for pressure application, a pressure-responsive resin containing pressure-responsive resin particles can be used. Preferably, the pressure-responsive resin particles are composite resin particles having a styrene-based resin and a (meth)acrylic acid ester-based resin internally, and a styrene-based resin on the surface.

[0054] From the viewpoint of adhesive strength during compression, the pressure-responsive resin particles preferably contain 90% or more of (meth)acrylic acid ester resin, more preferably 95% or more, and particularly preferably 99% or more. Furthermore, from the viewpoint of adhesive strength during compression, the mass ratio of styrene resin to (meth)acrylic acid ester resin contained in the entire resin particle is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.

[0055] From the viewpoint of adhesive strength during compression, the pressure-responsive resin particles preferably have a difference of 30°C or more between the lowest glass transition temperature and the highest glass transition temperature contained in the resin particles, more preferably 40°C or more, even more preferably 60°C or more, even more preferably 60°C or more, even more preferably 60°C to 200°C, and particularly preferably 80°C to 150°C. Furthermore, the lowest glass transition temperature contained in the resin particles is preferably the glass transition temperature of a (meth)acrylic acid ester resin. Moreover, the highest glass transition temperature contained in the resin particles is preferably the glass transition temperature of a styrene resin, and it is even more preferable that the lowest glass transition temperature contained in the resin particles is the glass transition temperature of a (meth)acrylic acid ester resin, and the highest glass transition temperature contained in the resin particles is the glass transition temperature of a styrene resin.

[0056] The above resin particles may optionally contain non-vinyl resins such as polystyrene, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, and modified rosin. These resins may be used individually or in combination of two or more. Furthermore, the resin particles are preferably pressure-responsive resin particles that undergo a phase transition in response to pressure. The pressure-responsive resin containing the pressure-responsive resin particles preferably contains a dispersion medium. Examples of dispersion mediums include water; alcohols such as propylene glycol, 1,3-propanediol, and diethylene glycol; and other aqueous media. These may be used individually or in combination of two or more. Furthermore, there are no particular restrictions on the content of the resin particles, but it is preferable that it be 10% by mass or more and 80% by mass or less relative to the resin. In addition, the resin particles may contain additives such as surfactants, dispersion stabilizers, viscosity modifiers, pH adjusters, antioxidants, and ultraviolet absorbers.

[0057] "Solvent treatment" Solvent treatment is a process that alters the adhesion of the resin to a target area of ​​the substrate by bringing a solvent into contact with the resin layer constituting the coating area of ​​a coating member. The conditions for solvent treatment can be appropriately set depending on the material used for the resin layer.

[0058] For resin layers suitable for solvent treatment, polyimide resin or its precursor can be used. The polyimide resin or its precursor has a tetracarboxylic anhydride residue and a diamine residue, and it is preferable that the diamine residue is a polysiloxane-based diamine residue and has a dicarboxylic anhydride residue and / or a monoamine residue at its terminus.

[0059] The diamine residues preferably consist of 50 mol% to 100 mol% polysiloxane-based diamine residues, and more preferably 60 mol% to 100 mol% of the total diamine residues. By including 50 mol% or more of polysiloxane-based diamine residues in the total diamine residues, good adhesion and solubility in solvents can be improved. Specific examples of polysiloxane-based diamines include α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydipropylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenoxysiloxane, α,ω-bis(2-aminoethyl)polydimethylsiloxane, and α,ω-bis(2- Examples include aminoethyl)polydiphenoxysiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydiphenoxysiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydiphenoxysiloxane, α,ω-bis(4-aminophenyl)polydimethylsiloxane, and α,ω-bis(4-aminophenyl)polydiphenoxysiloxane. The above polysiloxane-based diamines may be used individually or in combination of two or more.

[0060] The content of dicarboxylic acid anhydride residues is preferably 0.005 ≤ 0.5A / (0.5A+B) ≤ 0.1, and more preferably 0.01 ≤ 0.5A / (0.5A+B) ≤ 0.05, where A moles of dicarboxylic acid anhydride residues and B moles of tetracarboxylic acid anhydride residues. A value of 0.005 or higher calculated by 0.5A / (0.5A+B) improves solubility in volatile solvents. Furthermore, a value of 0.1 or lower calculated by 0.5A / (0.5A+B) maintains heat resistance.

[0061] Specific examples of dicarboxylic acid anhydrides include phthalic anhydride, 4-methylphthalic anhydride, 3-methylphthalic anhydride, 4-tert-butylphthalic anhydride, 4-fluorophthalic anhydride, 2-fluorophthalic anhydride, 3,4-difluorophthalic anhydride, 2,4-difluorophthalic anhydride, 2,3,4-trifluorophthalic anhydride, tetrafluorophthalic anhydride, 4-(trifluoromethyl)phthalic anhydride, and 2-(trifluoromethyl)phthalic anhydride. The above dicarboxylic acid anhydrides may be used individually or in combination of two or more.

[0062] The monoamine residue content is preferably 0.005 ≤ 0.5C / (0.5C+D) ≤ 0.1, and more preferably 0.01 ≤ 0.5C / (0.5C+D) ≤ 0.05, where C moles are monoamines and D moles are diamines. A value of 0.005 or higher calculated by 0.5C / (0.5C+D) improves solubility in volatile solvents. Furthermore, a value of 0.1 or lower calculated by 0.5C / (0.5C+D) maintains heat resistance.

[0063] Specific examples of monoamines include aniline, p-toluene, m-toluene, 3,4-dimethylaniline, 4-tert-butylaniline, 4-fluoroaniline, 3-fluoroaniline, 2-fluoroaniline, 2,4-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 3,5-difluoroaniline, 2,3-difluoroaniline, 2,4,6-trifluoroaniline, 2,3,5-trifluoroaniline, 2,3,4,5-tetrafluoroaniline, 2, Examples include 3,4,6-tetrafluoroaniline, 2,3,5,6-tetrafluoroaniline, pentafluoroaniline, 4-(trifluoromethyl)aniline, 3-(trifluoromethyl)aniline, 2-(trifluoromethyl)aniline, 3,5-bis(trifluoromethyl)aniline, 2,4-bis(trifluoromethyl)aniline, 2,5-bis(trifluoromethyl)aniline, 2,6-bis(trifluoromethyl)aniline, and 2,3-bis(trifluoromethyl)aniline. The above monoamines may be used individually or in combination of two or more.

[0064] The solvent used in the solvent treatment is preferably a volatile solvent. Specifically, the solvent preferably contains 90% by mass or more of a component with a boiling point of 160°C or lower, more preferably 95% by mass, and even more preferably 99% by mass or more. By containing 90% by mass or more of a component with a boiling point of 160°C or lower in the solvent, good volatility is achieved, and the laminate can be dried without adding a rinsing step with a highly volatile solvent after the solvent treatment.

[0065] Examples of solvents include dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and ethylene glycol monomethyl ether acetate. The solvent may be used alone or in combination of two or more. In particular, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and ethylene glycol monomethyl ether acetate, which have a boiling point of 160°C or lower, are preferred as solvents. Furthermore, from the viewpoint of solubility, propylene glycol monomethyl ether acetate and ethylene glycol monomethyl ether acetate, which have an acetyl group, are particularly preferred as solvents.

[0066] The thickness of the resin layer constituting the coating area is not particularly limited, and is preferably 0.1 μm to 500 μm, and more preferably 0.2 μm to 200 μm, from the viewpoint of being able to fill in the irregularities on the surface of the target area of ​​the substrate and facilitating the removal of the resin layer in the cleaning step in the manufacturing method described later. Furthermore, in order to fill in the irregularities on the surface of the target area of ​​the substrate, the thickness of the resin layer is preferably 0.5 times or more the maximum height Sz of the substrate surface, and more preferably 1 time or more. By having a resin layer thickness within the above range and reliably filling in the irregularities on the substrate surface, the occurrence of unintended peeling of the coating member in the manufacturing method described later can be suppressed.

[0067] In the laminate of this disclosure, the covering member may include other resin layers different from the resin layers constituting the covering region. Examples of other resin layers include protective layers for protecting the resin layers constituting the covering region.

[0068] <Laminate> In the laminate of the present disclosure, the area of ​​the first region is 1% to 30% of the total area of ​​the covered region, preferably 1% to 15%, and more preferably 1% to 5%. Because the ratio of the area of ​​the first region is within the above range, even when the laminate of the present disclosure is applied to an industrial process, the covered member does not peel off during the process, and after application to the industrial process, the covered member can be easily peeled off from the substrate.

[0069] The laminate of the present disclosure has a coating region of the coating member that includes a first region with adhesion force to the target region of 0.1 kN / m or more and 1.0 kN / m or less, and a second region with adhesion force to the target region of 0.0001 kN / m or more and 0.01 kN / m or less. Preferably, the first region A is provided outside the second region B so as to surround the second region B, and more preferably, the first region A is provided outside the second region B so as to surround the entire periphery of the second region B. More specifically, it is preferable that the first region A and the second region B are in contact with at least a part of the outer periphery of the second region B, and more preferably, the first region A and the second region B are in contact with the entire outer periphery of the second region. By providing the first region A, which has high adhesion force to the target region, in contact with the second region B, which has low adhesion force to the target region of the substrate, in the coating region, peeling of the coating member during the process can be prevented. Furthermore, if the first region A and the second region B are in contact along the outer perimeter of the second region B, the edges of the second region B will not be exposed to the outside during the process, preventing unintended peeling of the coating material and thus preventing lifting of the coating material.

[0070] In the laminate of the present disclosure, it is preferable that the covering area of ​​the covering member includes only the first region A and the second region B, and that the sum of the area of ​​the first region A and the area of ​​the second region B is equal to the total area of ​​the covering region. By configuring the laminate of the present disclosure so that the covering area of ​​the covering member includes only the first region A and the second region B, it is possible to easily manufacture a laminate that does not peel off in unintended processes and allows the covering member to be easily peeled off from the substrate in intended processes.

[0071] In the laminate of the present disclosure, it is preferable that the first region A, which has strong adhesion, is located at the end or edge of the covering region. When the target region of the base material and the covering region of the covering member are planar in shape, the first region A being located at the end of that shape can effectively suppress peeling of the covering member during unintended processes. Similarly, when the target region of the base material and the covering region of the covering member are three-dimensional in shape, or include three-dimensional parts, the first region A being located at the end and / or edge of that shape can effectively suppress peeling of the covering member during unintended processes.

[0072] In the laminate of the present disclosure, the target area of ​​the base material and the covering area of ​​the covering member are preferably rectangular, such as a square or rectangle, and it is preferable that the first area A, which has high adhesion force to the target area, is located on all four sides or corners of the rectangular covering area. When the first area A is located on all four sides of the rectangular covering area, the first area A may be located continuously along one side or intermittently. When the first area A is located at the four corners (squares) of the rectangular covering area, only one first area A may be located at each corner, or it may be divided into two or more areas. When the target area of ​​the base material and the covering area of ​​the covering member are rectangular, the positioning of the first area A on all four sides or corners can effectively suppress peeling of the covering member during unintended processes. The laminate of the present disclosure may have a two-dimensional structure or a three-dimensional structure as the substrate.

[0073] Furthermore, when peeling the coating member from the substrate of the laminate of this disclosure, whether the peeling occurs at the interface between the substrate and the resin layer constituting the coating region of the coating member, or due to material fracture within the resin layer, is not particularly limited as long as it does not affect the ease of removing components remaining on the substrate after peeling.

[0074] ≪Method for manufacturing laminates≫ The present disclosure is a method for manufacturing a laminate comprising a substrate and a coating member including at least one resin layer, and includes at least the following first to third steps.

[0075] <1st process> In the method for manufacturing a laminate according to the present disclosure, in the first step, a coating member is provided on the substrate such that the target area of ​​the substrate and the coating area of ​​the coating member are in contact.

[0076] Specifically, for example, if the covering member is a film-like member having a resin layer on its surface that constitutes a covering area, the base material and the covering member may be aligned so that the covering area of ​​the covering member covers the target area of ​​the base material (so that the target area and the covering area overlap), and then the base material and the covering member may be bonded together.

[0077] The bonding of the base material and the covering material may be done by lamination. If the covering material is in roll form, the bonding (lamination) of the base material and the covering material may be done continuously. If the covering material is in sheet form, the bonding (lamination) of the base material and the covering material may be done one sheet at a time.

[0078] Furthermore, for example, if the coating member is a liquid such as a resin composition for forming a resin layer constituting the coating area, the resin composition may be applied only to the target area of ​​the substrate and then dried to form the coating member on the substrate. If the substrate is in roll form, the application of the resin composition to the substrate may be carried out continuously. If the substrate is in sheet form, the application of the resin composition to the substrate may be carried out sheet by sheet.

[0079] <Second process> In the method for manufacturing a laminate according to the present disclosure, in the second step, a first region A is provided in the covering region of the covering member, wherein the adhesion force with the target region of the substrate is 0.1 kN / m or more and 1.0 kN / m or less.

[0080] <3rd process> In the method for manufacturing a laminate according to the present disclosure, in the third step, a second region B is provided in the covering region of the covering member, wherein the adhesion force with the target region of the substrate is 0.0001 kN / m or more and 0.01 kN / m or less.

[0081] In the method for manufacturing the laminate according to the present disclosure, the second and / or third step may include at least one treatment selected from the group consisting of UV irradiation, laser irradiation, pressure application, and solvent immersion described above. This makes it possible to form a first region A or a second region B in the resin layer constituting the coating region of the coating member. In the manufacturing method of the laminate according to this disclosure, in the second and / or third step, the area to which the above-described treatment is applied is adjusted such that the area of ​​the first region is 1% or more and 30% or less of the total area of ​​the covered region. The method for adjusting the area is not particularly limited, and known claims can be appropriately selected and used.

[0082] In the method for manufacturing a laminate according to this disclosure, the order of the first, second, and third steps is not particularly limited. Examples of the order of each step are as follows: The first and second steps are carried out simultaneously, followed by the third step. The first and third steps are carried out simultaneously, followed by the second step. • Perform the first step, and then perform the second and third steps simultaneously. The first, second, and third steps will be carried out in order. The second and third steps are performed simultaneously or sequentially, followed by the first step.

[0083] In other words, the method for manufacturing a laminate according to the present disclosure provides a coating member to a substrate by applying the above-mentioned laminate or resin composition. In this case, if the adhesion force between the target area of ​​the substrate and the coating area of ​​the coating member is greater than 0.01 kN / m and less than 0.1 kN / m, the above-mentioned adhesion force adjustment process is performed by selecting an arbitrary position and range of the coating area of ​​the coating member to sequentially form the first area A and the second area B.

[0084] On the other hand, when a coating member is provided on the substrate by applying the aforementioned laminate or resin composition, if the adhesion force between the target area of ​​the substrate and the coating area of ​​the coating member is 0.0001 kN / m or more and 0.01 kN / m or less, then the second area B is formed over the entire surface of the coating area. In other words, the first and third steps are performed simultaneously. In this example, an arbitrary position and range of the coating area of ​​the coating member is selected, and the adhesion-improving process among the adhesion force adjustment processes described above is performed to form the first area A.

[0085] Furthermore, when a coating member is provided on the substrate by applying the aforementioned laminate or resin composition, if the adhesion force between the target area of ​​the substrate and the coating area of ​​the coating member is between 0.1 kN / m and 1.0 kN / m, then the first area A is formed over the entire coating area. In other words, the first and second steps are performed simultaneously. In this example, an arbitrary position and range of the coating area of ​​the coating member is selected, and the adhesion force adjustment process described above, which reduces the adhesion force, is performed to form the second area B.

[0086] Furthermore, the method for manufacturing the laminate according to this disclosure may involve performing the above-described adhesion force adjustment process on the coating region of the coating member to form the first region A and the second region B, and then bonding the substrate and the coating member. In other words, the second and third steps may be performed simultaneously or sequentially, followed by the first step.

[0087] As described above, the laminate of the present disclosure comprises a substrate and a coating member including at least one resin layer, wherein the coating region of the coating member includes a first region A with an adhesion force of 0.1 kN / m or more and 1.0 kN / m or less to the target region of the substrate, and a second region B with an adhesion force of 0.0001 kN / m or more and 0.01 kN / m or less to the target region of the substrate, and the area of ​​the first region is 1% or more and 30% or less to the total area of ​​the coating region. In such a laminate, the target region of the substrate and the coating region of the coating member adhere strongly in the first region A, and the coating member does not peel off from the substrate at an unintended timing during industrial processes. Furthermore, because the coating region of the present disclosure includes a second region B, the adhesion force between the target region of the substrate and the coating region of the coating member is small in the second region B, so that the coating member that is no longer needed after being applied to industrial processes can be easily peeled off from the substrate.

[0088] Furthermore, the method for manufacturing a laminate according to the present disclosure includes at least a first step of providing a coating member to a substrate so that the target area of ​​the substrate and the coating area of ​​the coating member are in contact; a second step of providing a first area A in the coating area of ​​the coating member having an adhesion force of 0.1 kN / m or more and 1.0 kN / m or less; and a third step of providing a second area B in the coating area of ​​the coating member having an adhesion force of 0.0001 kN / m or more and 0.01 kN / m or less. As a result, the method for manufacturing a laminate according to the present disclosure makes it possible to manufacture a laminate in which the substrate and the member including the resin layer do not peel off in unintended processes, and the member including the resin layer can be easily peeled off from the substrate in intended processes.

[0089] Furthermore, after being applied to any industrial process, the laminate of this disclosure can be used to remove unwanted coatings from the substrate, for example, in a coating removal process. When removing the coating from the substrate, it is not particularly limited whether the removal occurs at the interface between the target area of ​​the substrate and the coating area of ​​the coating, or whether it occurs due to material fracture within the resin layer constituting the coating area.

[0090] Furthermore, after the above-described peeling step of the coating member, a cleaning step may be provided to clean the surface of the substrate, including the target area after the coating member has been peeled off.

[0091] The laminates of this disclosure can be suitably used when manufacturing electronic components such as printed circuit boards, conductive films for touch panels, metal meshes for touch panels, organic solar cells, organic EL elements, organic transistors, RFID such as contactless IC cards, electromagnetic shielding, LED lighting substrates, and digital signage. [Examples]

[0092] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" all refer to mass unless otherwise specified.

[0093] <Fabrication of test boards> The following resin layers 1 to 4 were prepared as covering materials. • Resin layer 1: Somatack UV manufactured by Somar Co., Ltd. • Resin layer 2: Denka Co., Ltd.'s Elegrip Tape • Resin layer 3: ClearPresto CP3722 manufactured by Sekisui Fuller Co., Ltd. • Resin layer 4: Temporary fixing agents TZNR-CTRL9 and TZNR-A7005 manufactured by Tokyo Ohka Kogyo Co., Ltd.

[0094] <Layout of the first and second areas> For the resin layers 1 to 4 used as covering members, the layouts A to E shown in Figures 1 to 5 were used for the arrangement (layout) of the first region A and the second region B in the covering area. (Layout A) • First area A: It has a shape that follows the edges (four sides) of the rectangular covering area and is arranged around the entire circumference of the edges of the covering area. • Second region B: It has a rectangular shape and is positioned in the central part of the covering area so as to be in contact with the first region A around its entire circumference. (Layout B) • First area A: It has a shape that follows the edges (four sides) of the rectangular covering area and is arranged around the entire circumference of the edges of the covering area. • Second region B: It has a rectangular shape, and is positioned in the central part of the covered area such that only one of its four edges touches the first region A. (Layout C) • First area A: It has an L-shape with a predetermined width extending inward from the end, and is positioned at each of the four corners of the rectangular covering area. • Second area B: Within the rectangular covering area, the portion other than the first area A is positioned so that each corner of the covering area touches the edges of the first area A. (Layout D) • A rectangular covering member (covering area) with a smaller area than the base material is placed on one surface of the base material. • First area A: It has a shape that follows the edges (four sides) of the rectangular covering area and is arranged around the entire circumference of the edges of the covering area. • Second region B: It has a rectangular shape and is positioned in the central part of the covering area so as to be in contact with the first region A around its entire circumference. (Layout E) • A circular covering member (covering area) with a smaller surface area than the base material is placed on one surface of the base material. • First region A: It has a shape that follows the edge (outer circumference) of the circular covering region and is arranged around the entire circumference of the edge of the covering region. • Second region B: It has a circular shape and is positioned in the central part of the covering area so as to be in contact with the first region A around its entire circumference.

[0095] (Example 1) A resin layer 1 was laminated onto the entire surface of one of the 0.7 mm thick soda glass substrates using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 60°C, 0.5 MPa, and a speed of 0.1 m / min. Light-shielding tape was applied to all four sides of the resin layer 1 to form a light-shielding layer, and UV light was applied at an irradiance of 120 W / cm using a UV conveyor manufactured by Oak Manufacturing Co., Ltd. 2 , 1000 mJ / cm 2The material was irradiated with UV light. This created areas on all four sides of the resin layer 1 that were not irradiated with UV light, with an area equal to 1% of the UV-irradiated area. Note that the adhesion strength of the resin layer 1 decreases due to the UV irradiation treatment. In other words, the UV-irradiated area is the second area B, where the adhesion strength to the substrate has decreased, and the area that was not irradiated with UV light is the first area A (layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0096] (Example 2) A resin layer 1 was laminated onto the entire surface of one of the surfaces of a 1.0 mm thick SUS substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 60°C, 0.5 MPa, and a speed of 0.1 m / min. Light-shielding tape was applied to all four sides of the resin layer 1 to form a light-shielding layer, and UV light at an irradiance of 120 W / cm² was applied using a UV conveyor manufactured by Oak Manufacturing Co., Ltd. 2 , 1000 mJ / cm 2 The material was irradiated with UV light. This created areas on all four sides of the resin layer 1 that were not irradiated with UV light, with the area of ​​these areas being 1% of the area that was irradiated with UV light. Note that the adhesion strength of the resin layer 1 decreases due to the UV irradiation treatment. In other words, the area that was irradiated with UV light is the second region B, where the adhesion strength to the substrate has decreased, and the area that was not irradiated with UV light is the first region A (layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0097] (Example 3) A resin layer 1 was laminated onto the entire surface of one of the surfaces of a 1.0 mm thick SUS substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 60°C, 0.5 MPa, and a speed of 0.1 m / min. Light-shielding tape was applied to all four sides of the resin layer 1 to form a light-shielding layer, and UV light at an irradiance of 120 W / cm² was applied using a UV conveyor manufactured by Oak Manufacturing Co., Ltd. 2 , 1000 mJ / cm 2 The resin layer was irradiated with UV light. This created areas on all four sides of the resin layer 1 that were not irradiated with UV light, with an area of ​​30% of the UV-irradiated area. Note that the adhesion strength of the resin layer 1 decreases due to the UV irradiation treatment. In other words, the UV-irradiated area is the second area B, where the adhesion strength to the substrate has decreased, and the area that was not irradiated with UV light is the first area A (layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0098] (Example 4) A resin layer 2 was laminated to the entire surface of one of the surfaces of a 0.7 mm thick glass substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 23°C, 0.2 MPa, and a speed of 1.0 m / min. A jig was placed on all four sides of the resin layer 2, and the layer was laminated again using the roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 60°C, 0.5 MPa, and a speed of 0.1 m / min, thereby forming a first region A on all four sides of the resin layer 2. The area of ​​the jig was set to 1% of the total area of ​​the glass substrate. The four sides of the resin layer 2 with the jig on them are the first region A, where strong pressure is applied during the second lamination, resulting in increased adhesion. The central part of the resin layer 2 without the jig on it is the second region B (layout A), where strong pressure is not applied during the second lamination. Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0099] (Example 5) On one surface of a 0.7 mm thick soda glass substrate, resin layer 3 was applied to the entire surface using a spin coater (MS-B100, manufactured by Mikasa Corporation) at a rotation speed of 3000 rpm for 60 seconds. Then, using a hot plate, it was heated at 90°C for 10 minutes, followed by drying at 250°C for 6 minutes. Masking tape was applied to all four sides of resin layer 3 to form a shielding layer, and the substrate was immersed in PGMEA for 120 seconds. In this way, areas unaffected by the solvent were created on all four sides of resin layer 3, with an area equal to 1% of the area affected by the solvent. Note that the adhesion strength of resin layer 3 decreases with solvent treatment. The solvent-treated area is the second region B, where adhesion to the substrate is reduced, and the untreated area is the first region A, where adhesion to the substrate is not reduced (Layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0100] (Example 6) A resin layer 4 was applied to the entire surface of one of the 0.7 mm thick soda glass substrates using a spin coater (MS-B100, manufactured by Mikasa Corporation) at a rotation speed of 3000 rpm for 60 seconds. Then, it was heated on a hot plate at 90°C for 4 minutes, followed by drying at 250°C for 6 minutes. A light-shielding layer was formed by attaching light-shielding tape to all four sides of the resin layer 4. The beam had a wavelength of 355 nm, a beam width of approximately 10 μm, a beam length of approximately 1.5 mm, and an energy density of 0.5 J / cm². 2Using a line laser, the laser was irradiated under pulse scan conditions at a power output of 0.75W and a frequency of 10kHz, such that the spacing between the center lines was approximately 10μm in the width direction and overlapped by approximately 0.2mm or more in the length direction. As a result, areas not irradiated by the laser were created on all four sides of the resin layer 4, and the area of ​​these areas was 1% of the laser-irradiated area. Note that the adhesion strength of the resin layer 4 decreases due to the laser irradiation treatment. In other words, the laser-irradiated area is the second area B, where the adhesion strength to the substrate has decreased, and the area not irradiated by the laser is the first area A (layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0101] (Example 7) On the surface of a 0.7 mm thick glass substrate, resin layer 1 and resin layer 2 were simultaneously formed on the entire surface of one side using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 23°C, 0.2 MPa, and a speed of 1.0 m / min. Resin layer 1 was formed on all four sides of the substrate surface, with a ratio of 1:99 between the area where resin layer 1 was formed and the area where resin layer 2 was formed. Resin layer 1 and resin layer 2 were in contact, and the sum of the areas where resin layer 1 and resin layer 2 were formed was equal to the total area of ​​one side of the glass substrate surface. The region where resin layer 1, which has strong adhesion to the substrate, was formed is region 1A, and the region where resin layer 2, which has weak adhesion to the substrate, was formed is region 2B (layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0102] (Example 8) On the surface of a 0.7 mm thick glass substrate, resin layer 1 and resin layer 2 were simultaneously formed on the entire surface of one side using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 23°C, 0.2 MPa, and a speed of 1.0 m / min. Resin layer 1 was formed on all four sides of the substrate surface, with a ratio of 1:99 between the area where resin layer 1 was formed and the area where resin layer 2 was formed. Resin layer 1 and resin layer 2 were not in contact in some areas, and the sum of the areas where resin layer 1 and resin layer 2 were formed was equal to 90% of the total surface area of ​​one side of the glass substrate. The area where resin layer 1, which has strong adhesion to the substrate, was formed is the first region A, and the area where resin layer 2, which has weak adhesion to the substrate, was formed is the second region B (layout B). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0103] (Example 9) On the surface of a 0.7 mm thick glass substrate, resin layer 1 and resin layer 2 were simultaneously formed on the entire surface of one of the surfaces using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 23°C, 0.2 MPa, and a speed of 1.0 m / min. Resin layer 1 was formed at the four corners of the substrate surface, and the ratio of the area where resin layer 1 was formed to the area where resin layer 2 was formed was 1:99. Resin layer 1 and resin layer 2 were not in contact in some areas, and the sum of the areas where resin layer 1 and resin layer 2 were formed was equal to the total surface area of ​​one of the glass substrate surfaces. The area where resin layer 1, which has strong adhesion to the substrate, was formed is the first region A, and the area where resin layer 2, which has weak adhesion to the substrate, was formed is the second region B (layout C). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0104] (Example 10) On the surface of a 0.7 mm thick glass substrate, resin layer 1 and resin layer 2 were simultaneously formed on the entire surface of one side using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 23°C, 0.2 MPa, and a speed of 1.0 m / min. Resin layer 1 was formed on all four sides of the substrate surface, with a ratio of 1:99 between the area where resin layer 1 was formed and the area where resin layer 2 was formed. Resin layer 1 and resin layer 2 were in contact, and the sum of the areas where resin layer 1 and resin layer 2 were formed was 50% of the surface of one side of the glass substrate. The area where resin layer 1, which has strong adhesion to the substrate, was formed is the first region A, and the area where resin layer 2, which has weak adhesion to the substrate, was formed is the second region B (layout D). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0105] (Example 11) On the surface of a 0.7 mm thick glass substrate, resin layer 1 and resin layer 2 were simultaneously formed on the entire surface of one side using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 23°C, 0.2 MPa, and a speed of 1.0 m / min. Resin layer 1 was formed in a circular shape on the surface of the substrate, with a ratio of the area where resin layer 1 was formed to the area where resin layer 2 was formed being 1:99. Resin layer 1 and resin layer 2 were in contact, and the sum of the areas where resin layer 1 and resin layer 2 were formed was 50% of the surface of one side of the glass substrate. The area where resin layer 1, which has strong adhesion to the substrate, was formed is the first region A, and the area where resin layer 2, which has weak adhesion to the substrate, was formed is the second region B (layout E). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0106] (Comparative Example 1) Of the surfaces of a soda glass substrate with a thickness of 0.7 mm, on the entire surface of one surface, using a roll laminator (VA-770 manufactured by Daisheng Laminator Co., Ltd.), the resin layer 1 was laminated at 60 °C, 0.5 MPa, and a speed of 0.1 m per minute. On the entire surface of the resin layer 1, using a UV conveyor manufactured by Oak Manufacturing Co., Ltd., UV was irradiated at an illuminance of 120 W / cm 2 , 1000 mJ / cm 2 . Note that the adhesion of the resin layer 1 decreases due to the UV irradiation treatment. That is, all regions of the resin layer 1 irradiated with UV are the second region B where the adhesion to the substrate has decreased. After that, using a roll laminator (VA-770 manufactured by Daisheng Laminator Co., Ltd.) on the entire surface of the substrate, copper foil was laminated at 100 °C, 0.3 MPa, and a speed of 1.0 m per minute. Next, a heat resistance test and a chemical resistance test were conducted at 260 °C for 15 minutes to obtain a test substrate.

[0107] (Comparative Example 2) Of the surfaces of a soda glass substrate with a thickness of 0.7 mm, on the entire surface of one surface, using a roll laminator (VA-770 manufactured by Daisheng Laminator Co., Ltd.), the resin layer 1 was laminated at 60 °C, 0.5 MPa, and a speed of 0.1 m per minute. Note that the adhesion of the resin layer 1 decreases due to the UV irradiation treatment. That is, all regions of the resin layer 1 not irradiated with UV are the first region A. After that, using a roll laminator (VA-770 manufactured by Daisheng Laminator Co., Ltd.) on the entire surface of the substrate, copper foil was laminated at 100 °C, 0.3 MPa, and a speed of 1.0 m per minute. Next, a heat resistance test and a chemical resistance test were conducted at 260 °C for 15 minutes to obtain a test substrate.

[0108] (Comparative Example 3) Of the surfaces of a soda glass substrate with a thickness of 0.7 mm, on the entire surface of one surface, using a roll laminator (VA-770 manufactured by Daisheng Laminator Co., Ltd.), the resin layer 1 was laminated at 60 °C, 0.5 MPa, and a speed of 0.1 m per minute. A light-shielding layer was formed by laminating light-shielding tape on the four sides of the resin layer 1, and using a UV conveyor manufactured by Oak Manufacturing Co., Ltd., UV was irradiated at an illuminance of 120 W / cm 2 , 1000 mJ / cm 2The material was irradiated with UV light. This created areas on all four sides of the resin layer 1 that were not irradiated with UV light, with an area of ​​0.1% of the UV-irradiated area. Note that the adhesion strength of the resin layer 1 decreases due to the UV irradiation treatment. In other words, the UV-irradiated area is the second area B, where the adhesion strength to the substrate has decreased, and the area that was not irradiated with UV light is the first area A (layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0109] (Comparative Example 4) A resin layer 1 was laminated onto the entire surface of one of the 0.7 mm thick soda glass substrates using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 60°C, 0.5 MPa, and a speed of 0.1 m / min. Light-shielding tape was applied to all four sides of the resin layer 1 to form a light-shielding layer, and UV light was applied at an irradiance of 120 W / cm using a UV conveyor manufactured by Oak Manufacturing Co., Ltd. 2 , 1000 mJ / cm 2 The resin layer 1 was irradiated with UV light. This created areas on all four sides of the resin layer 1 that were not irradiated with UV light, with an area equal to 60% of the UV-irradiated area. Note that the adhesion strength of the resin layer 1 decreases due to the UV irradiation treatment. In other words, the UV-irradiated area is the second area B, where the adhesion strength to the substrate has decreased, and the area that was not irradiated with UV light is the first area A (layout A). Subsequently, copper foil was laminated over the entire surface of the substrate using a roll laminator (VA-770, manufactured by Taisei Laminator Co., Ltd.) at 100°C, 0.3 MPa, and a speed of 1.0 m / min. Next, a heat resistance test and a chemical resistance test were performed at 260°C for 15 minutes to obtain the test substrate.

[0110] <Measurement results of adhesion strength> Using the test substrates obtained in the examples and comparative examples, adhesion strength was measured in the first region A and the second region B. Specifically, the adhesion strength was defined as the 90° peel strength measured in accordance with JIS-C64811996 using a NordsonDAGE 4000Plus under room temperature conditions (23°C). The measurement results of the peel strength are shown in Tables 1 and 2.

[0111] <Evaluation of process tolerance> The process resistance of the examples and comparative examples was evaluated in the heat resistance test at 260°C for 15 minutes and the chemical resistance test described above, according to the following evaluation criteria. In the chemical resistance test, the evaluation substrate was immersed in an aqueous copper(II) sulfate solution for 30 minutes. The evaluation results are shown in Tables 1 and 2. (Evaluation Criteria) ◎: After chemical resistance and heat resistance tests, the coating material (resin layers 1-4) did not peel off from the substrate at all. ○: After the chemical resistance and heat resistance tests, some lifting of the coating material was observed on a portion of the edge of the base material, but the coating material did not peel off. △: After chemical resistance and heat resistance tests, some lifting of the coating material was observed on a portion of the edge of the base material, and some peeling of the coating material was present. ×: After chemical resistance and heat resistance tests, peeling of the coating material from the substrate was observed, exposing a portion of the substrate surface.

[0112] <Evaluation of peelability> For the examples and comparative examples, peel tests were performed using test substrates that had undergone the chemical resistance test described above, followed by a heat resistance test at 260°C for 15 minutes. The peel test was performed by fixing the test substrate with the substrate side down to an adsorption plate and lifting the copper foil surface with a vacuum adsorption pad. The ease of peeling the coating material (resin layers 1-4) from the substrate (peelability) was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 and 2. (Evaluation Criteria) ◎: The coating material can be smoothly peeled off the surface of the substrate using a vacuum suction pad. ○: When peeling the coating material from the surface of the substrate using a vacuum suction pad, there are some areas where it is difficult, but it can be peeled off. ×: Only a portion of the coating material can be peeled off. Alternatively, cracks or wrinkles may appear in the base material when peeling off the coating material.

[0113] [Table 1]

[0114] [Table 2]

[0115] As shown in Tables 1 and 2, the laminates of Examples 1 to 11 demonstrate that process resistance and peelability can be achieved because the coated area of ​​the coating member includes a first region A with an adhesion force to the substrate of 0.1 kN / m or more and 1.0 kN / m or less, and a second region B with an adhesion force to the substrate of 0.0001 kN / m or more and 0.01 kN / m or less. In contrast, the laminate of Comparative Example 1 showed excellent peelability between the substrate and the coating member because the coating region of the coating member included the second region B, but it was shown that it did not include the first region A, resulting in problems with process resistance. Furthermore, it was shown that while the laminate of Comparative Example 2 exhibits excellent process resistance because the coating region of the coating member includes the first region A, it does not include the second region B, resulting in problems with the peelability between the substrate and the coating member. Furthermore, in Comparative Examples 3 and 4, the laminates of the coating member include a first region A with an adhesion force to the substrate of 0.1 kN / m or more and 1.0 kN / m or less, and a second region B with an adhesion force to the substrate of 0.0001 kN / m or more and 0.01 kN / m or less. However, the area of ​​the first region A relative to the total area of ​​the coating region is not between 1% and 30%, thus demonstrating that it is not possible to achieve both process resistance and peelability.

Claims

1. It comprises a base material and a covering member including at least one resin layer, The substrate has a target region that includes at least a portion of the surface of the substrate, The covering member has a covering area that is in contact with the target area, The covering region includes a first region having an adhesion force of 0.1 kN / m or more and 1.0 kN / m or less with respect to the target region, and a second region having an adhesion force of 0.0001 kN / m or more and 0.01 kN / m or less with respect to the target region. A laminate in which the area of ​​the first region is 1% or more and 30% or less of the total area of ​​the covered region.

2. The laminate according to claim 1, wherein the first region and the second region are in contact in the covered region.

3. The covering region includes only the first region and the second region, The laminate according to claim 1, wherein the sum of the area of ​​the first region and the area of ​​the second region is equal to the total area of ​​the covering region.

4. The laminate according to claim 1, wherein the first region is located at the end or edge of the covering region.

5. The target area and the covering area are rectangular. The laminate according to claim 1, wherein the first region is located on all four sides or at all four corners of the covering region.

6. The laminate according to claim 1, wherein the substrate is an intermediate of the finished product.

7. A method for manufacturing a laminate according to any one of claims 1 to 6, The first step is to provide the covering member on the substrate so that the target area and the covering area are in contact, A second step is to provide the first region in the covering region, A method for manufacturing a laminate, comprising at least a third step of providing the second region in the covering region.

8. The method for manufacturing a laminate according to claim 7, wherein the second and / or third step includes at least one treatment selected from the group consisting of UV irradiation, laser irradiation, pressure application, and solvent immersion.

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