JP2017165092A - Laminate having projection and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having a projection having a high aspect structure, and to provide a method for manufacturing the same.SOLUTION: There are provided a laminate having a projection 23 which has at least a first resin layer 21 and a second resin layer 22, where a resin constituting the first resin layer 21 is a resin having thermoplasticity, a resin constituting the second resin layer 22 is a thermosetting or photocurable resin, the laminate has a projection 23 on the surface of the first resin layer 21, when a thickness of the second resin layer of the projection 23 is represented by t2, a thickness of the first resin layer 21 in a base 20 is represented by t1' and a thickness of the second resin layer 22 in the base 20 is represented by t2', a relationship of (t1'+t2')≤t2 holds; and a method for manufacturing a laminate having a projection which includes heating at least one of a mold having a recessed shape thereon and the laminate to Tg1 of the resin constituting the first resin layer 21 or higher, pressing a mold from the side of the first resin 21 to form the projection 23 having a recessed reversal shape.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate having protrusions and a method for manufacturing the same.

  In recent years, the importance of a technique for forming a fine structure is increasing in various fields such as the optical field and the semiconductor field. In the optical field, a high-precision fine structure forming technique is required. In the semiconductor field, in addition to a high-precision fine structure forming technique, miniaturization of processing dimensions is required to improve the integration degree of a semiconductor integrated circuit. As a microstructure forming technology for resin, heat is applied to heat the resin to a temperature above the glass transition temperature, soften it, and press the heated mold on the surface of the laminate to transfer the shape of the mold to the surface of the laminate Imprint technology has been proposed and applied to the development of products such as biochips and optical elements.

  In particular, as a method for forming a high aspect protrusion having a high protrusion height relative to the protrusion width by thermal imprinting, a surface layer resin having a low heat distortion temperature of a laminate in which two resin layers having different heat deformation temperatures are laminated. Surface layer resin showing low viscoelasticity at or above glass transition temperature of a method of forming protrusions on a layer (for example, see Patent Document 1) or a laminate obtained by laminating two resin layers showing different viscoelasticity at or above glass transition temperature A method for forming a protrusion on a layer (see, for example, Patent Document 2) has been proposed. Further, as a method for forming a laminate having a thermosetting resin, a method of forming in an uncured state (for example, see Patent Document 3) has been proposed.

International Publication No. 2011/090139 JP 2006-269919 A JP 2008-105198 A

  However, it is intended to form protrusions mainly using softening of the surface resin layer having a low thermal deformation temperature, or to mainly use softening of surface resin layers exhibiting low viscoelasticity above the glass transition temperature. In the case of the above, since the surface layer of the obtained protrusion is a layer having lower heat resistance than the inner layer, the heat resistance of the entire obtained protrusion cannot be sufficiently obtained. In addition, when trying to mold high aspect protrusions with high heat resistance temperature, the inner layer resin has to have higher heat resistance and must be molded at a higher temperature, which makes the thermal imprint molding itself difficult. It was.

  Also, especially when the surface resin layer is thin, when trying to mold high aspect protrusions or discrete structure protrusions, the thickness of the softening resin is small, so when the mold is pressed, The softened resin does not spread to the back of the concave shape, and the height of the protrusion is insufficient, or the softened surface layer resin is divided into a concave shape on the mold surface, and the resin surface shape deteriorates at the divided portion There was a problem such as. In addition, even if the inner layer resin slightly penetrates into the base of the softened resin, the inner layer resin is not sufficiently deformed, resulting in problems such as insufficient protrusion height or fragmentation of the softened surface resin. Even when the surface layer resin is not divided, there is a problem that a sufficient strength cannot be obtained by thinning at the base of the protrusion. In addition, since the laminate is made of thermoplastic resin for both the surface layer and the inner layer, the thin laminate has low rigidity and the strength of the laminate cannot be secured sufficiently. There was a problem such as. Furthermore, the surface resin layer thickness and the inner resin layer thickness are made larger than the protrusion height, and it is difficult to form a high aspect structure on the surface of a thin laminate.

  In addition, in molding with a laminate including a thermosetting resin, a thermosetting resin layer is used to bond a thermoplastic resin layer and a metal layer, thus forming a high aspect structure. The resin layer is a surface resin layer, and it is difficult to form a high aspect structure particularly when the surface resin layer is thin.

  In order to solve the above problems, the present invention provides a laminate having the following protrusions and a method for producing the same.

  It has at least a first resin layer and a second resin layer, the resin constituting the first resin layer is a thermoplastic resin, and the resin constituting the second resin layer is thermosetting. Or it is resin which has photocurability, has a processus | protrusion on the surface of the said 1st resin layer, the thickness of the 2nd resin layer in this processus | protrusion is t2, the thickness of the 1st resin layer in a base part is t1 ', a base part A laminate having protrusions, wherein (t1 ′ + t2 ′) ≦ t2 when the thickness of the second resin layer is t2 ′.

  At least one of a mold having a concave shape at least on the surface or a laminate having the first resin layer and the second resin layer, the glass transition temperature Tg1 [° C.] of the resin constituting the first resin layer The first heating step of heating as described above, and the pressure transfer step of pressing the mold from the first resin layer side of the laminate and transferring the projections having the inverted shape of the concave shape to the laminate. And the second heating step or the light irradiation step, the cooling step for cooling the laminate and the mold to less than Tg1 [° C.], and the peeling step for peeling the die and the laminate. A process for producing a laminate having protrusions, wherein protrusions are formed on the surface of the first resin layer of the body.

  According to the present invention, at least the first resin layer and the second resin layer are included, the resin constituting the first resin layer is a thermoplastic resin, and the second resin layer is configured. The resin to be cured is a thermosetting or photo-curing resin, has a protrusion on the surface of the first resin layer, the thickness of the second resin layer in the protrusion is t2, and the first resin layer in the base When the thickness is t1 ′ and the thickness of the second resin layer at the base is t2 ′, it is possible to provide a laminated body having a protrusion characterized by (t1 ′ + t2 ′) ≦ t2.

FIG. 1 is a schematic cross-sectional view illustrating protrusions in a laminate having protrusions according to the present invention. 2A to 2E schematically illustrate protrusions in the laminate having the protrusions of the present invention. 3A to 3E schematically illustrate a method for producing a laminate having protrusions of the present invention. FIG. 4 is a schematic cross-sectional view showing an example of a production apparatus for producing a laminate having protrusions of the present invention. FIG. 5 is a schematic cross-sectional view showing an example of a production apparatus for producing a laminate having protrusions of the present invention. 6A to 6E exemplify mold shapes used when molding a laminate having projections of the present invention. FIG. 7 illustrates a cross-sectional shape of a laminate having protrusions in the example of the present invention.

  Embodiments of the present invention will be described below with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view schematically illustrating protrusions in a laminate having protrusions according to the present invention.

  As shown in FIG. 1, the protrusion 23 in the laminate 20 having the protrusion of the present invention is the first resin layer 21 of the laminate 20 having at least a first resin layer 21 and a second resin layer 22. It is the shape which protruded on the surface. As shown in FIG. 1, it is preferable that the protrusions 23 on the stacked body 20 are discretely arranged independently.

  Here, in the laminate 20, a shape protruding from the surface is called a protrusion, and a portion where no protrusion is present is called a base. Further, the surface of the second resin layer opposite to the first resin layer is referred to as a base portion.

  The thickness t1 of the first resin layer 21 in the protrusion of the laminated body 20 having the protrusion according to the present invention refers to the thickness of the first resin layer at the position where the protrusion from the base portion is maximum in the protrusion. The thickness t2 of the second resin layer refers to the thickness of the second resin layer at the same position (the position where the protrusion from the base is maximum in the protrusion), and the height t of the protrusion is the thickness t of the protrusion. The sum (t1 + t2) of the thickness t1 of the first resin layer and the thickness t2 of the second resin layer at the protrusion.

  In the laminate having the protrusion of the present invention, the width w of the protrusion 23 is the protrusion at a height t / 2 that is half of the height t of the protrusion in the cross section passing through the position where the protrusion from the base portion is maximum. The width (full width at half maximum). Here, when the width of the protrusion varies depending on the way of taking the cross section, the width of the protrusion when the cross section is taken in the direction in which the width of the protrusion becomes the smallest through the position where the protrusion from the base portion becomes the maximum is calculated. Let width w. In the laminate having protrusions of the present invention, the width w2 of the second resin layer in the protrusions is a height that is half the thickness t2 of the second resin layer in the protrusions in the same cross section as that defining the width w of the protrusions. The width (half width full value) of the protrusion formed by the second resin layer at t / 2.

  In the laminate having the protrusions of the present invention, the cross-sectional area A of the protrusions 23 is a product (t × w) of the protrusion height t and the protrusion width w, and the second resin layer of the protrusions The cross-sectional area A2 is a product (t2 × w2) of the thickness t2 of the second resin layer in the protrusion and the width w2 of the second resin layer in the protrusion.

  The protrusions 23 in the laminate having the protrusions of the present invention may be periodically repeated in the in-plane direction perpendicular to the protrusion height, or may not be periodically repeated.

  In the present invention, the thickness t1 ′ of the first resin layer 21 in the base portion refers to the thickness of the first resin layer in the portion without the protrusion, and the thickness t2 ′ of the second resin layer 22 in the base portion is It refers to the thickness of the second resin layer in a portion where there is no protrusion.

  In the present invention, the resin constituting the first resin layer 21 is preferably a resin having thermoplasticity, and the resin constituting the second resin layer 22 is preferably a thermosetting or photocurable resin, The relationship between the thickness of the protrusion and the base is preferably (t1 ′ + t2 ′) ≦ t2. The relationship between the thickness of the protrusion and the base is (t1 ′ + t2 ′) ≦ t2, which means that the structure of the resin constituting the second resin layer 22 enters the protrusion 23, and this structure Thus, it is possible to obtain a laminated body having both a thin base and a projection having a high aspect structure.

  Here, the resin constituting the first resin layer being a resin having thermoplasticity means that the main resin constituting the first resin layer is a resin having thermoplasticity. The resin constituting the second resin layer is a thermosetting or photocurable resin means that the main resin constituting the second resin layer is a thermosetting or photocurable resin. That means. Furthermore, the main resin means a resin that occupies 60% by mass or more when the first resin layer and the second resin layer are 100% by mass as a whole.

  In the present invention, since the resin constituting the second resin layer is a thermosetting or photocurable resin, the laminate and the protrusions can have rigidity even in the case of a thin laminate. . In addition, when it is desired to impart characteristics such as chemical resistance to the surface of the laminate, it is sufficient to impart chemical resistance only to the first resin layer. Even if the first resin layer is thin, the first It is possible to obtain a protrusion having both a high aspect ratio and rigidity that does not easily impair the characteristics of the resin layer. Further, since the resin constituting the second resin layer is a thermosetting or photocurable resin, the second resin layer is constituted by controlling the temperature, light intensity, time, etc. during curing. Compared with the case where the resin is a thermoplastic resin, the resin can have any rigidity. In addition, even in a high aspect structure in which the height t of the protrusion is higher than the width w of the protrusion, the resin constituting the second resin layer that has penetrated into the protrusion is thermally or photocured, so that the inner layer The strength is increased, and even a laminate composed of a thin resin layer can be obtained with a high strength. Here, strength / rigidity is a compression elastic modulus measured under conditions according to JIS K7181: 2011, and high strength means a high compression elastic modulus.

  In addition, according to the method for manufacturing a laminate having protrusions of the present invention, even when the protrusions have a high aspect structure, the semi-cured second resin layer flows before the first resin layer. By this, the penetration | invasion to the back of the metal mold | die shape of a 1st resin layer is supported. When the second resin layer enters the protrusions of the first resin layer, deformation of the first resin layer is relatively reduced. Although the thickness of the first resin layer is reduced due to the increase in the local surface area due to the protrusion, the second resin layer compensates for the volumetric deformation of the protrusion, whereby the first resin between the protrusion and the base portion is obtained. Local thinning of the layer is suppressed. In addition, even in a high aspect structure in which the height t of the protrusion is higher than the width w of the protrusion, the strength of the inner layer is increased by heat or photocuring of the second resin layer that has entered the protrusion. Even in the case of a laminate composed of a thin resin layer, the protrusions are not easily broken when peeled off from the mold, and a protrusion having a high aspect structure can be suitably manufactured on the surface of the thin base portion.

  The sectional shape of the protrusions of the laminate in the present invention is determined by the required shape and the thickness of the laminate. As shown in FIGS. 2 (a) and 2 (d), the protrusion may have a rectangular shape with a flat tip of the second resin layer, or the second protrusion as shown in FIGS. 2 (b) and 2 (e). The tip of the resin layer may have a sharp shape or a shape having a curvature as shown in FIG. The height t of the protrusion 23 is preferably 1 to 500 μm, more preferably 5 to 300 μm, and still more preferably 10 to 100 μm.

  In the present invention, when the width of the second resin layer 22 is w2, it is preferable that 2.0 ≦ (t2 / w2). That is, the protrusion 23 of the laminate 20 in the present invention preferably has a high aspect structure in which the thickness t2 of the second resin layer in the protrusion is 2.0 times or more the width w2 of the second resin layer in the protrusion. . As described above, since the second resin layer has a high aspect structure, the resin constituting the first resin layer 21 can form a high aspect protrusion with only a relatively small deformation in the protrusion. Become. At this time, the deformation of the first resin layer is a surface deformation pushed up by the deformation of the second resin layer, and is not accompanied by a large thickness fluctuation. The phenomenon that the thickness is reduced or the first resin layer is torn and the second resin layer is exposed hardly occurs. Furthermore, when the second resin layer is a thermosetting or photocurable resin, it is possible to preferably achieve both a high aspect structure and a high strength.

  In particular, when the sectional area of the protrusion 23 is A and the sectional area of the second resin layer in the protrusion is A2, the sectional area ratio A2 / A preferably satisfies 0.25 or more. That is, it is preferable that the cross-sectional area A2 of the second resin layer in the protrusion occupies 1/4 or more with respect to the cross-sectional area A of the protrusion (A2 / A ≧ 1/4). More preferably, it is 1/2 or more. Further, it is preferable that the thickness t2 of the second resin layer in the protrusion is 1/2 or more with respect to the height t of the protrusion (t2 / t ≧ 1/2). That is, a desired protrusion can be obtained without greatly deforming the first resin layer serving as the surface layer by deforming the second resin layer serving as the inner layer largely. If it is a shape, the resin of the first resin layer is divided in the middle of the protrusion, and the protrusion is less likely to locally reduce the thickness of the first resin layer, and has a sufficient strength. It is suitable as.

  In the present invention, the main resin constituting the first resin layer is a resin having thermoplasticity. When the entire first resin layer is 100% by mass, the resin occupying 60% by mass or more has thermoplasticity. It means that the resin has. In particular, the content is preferably 80% by mass or more. The main resin constituting the second resin layer is a resin having thermosetting property or photo-curing property. When the entire second resin layer is 100% by mass, the resin occupying 60% by mass or more is thermosetting. It is a resin having the property or photocurability. In particular, it is preferable to contain 80% by mass or more. In addition, although an upper limit is not specifically limited, 100 mass% becomes a substantial upper limit.

  When the glass transition temperature Tg1 of the resin constituting the first resin layer in the present invention is measured by a method according to JIS K-7244: 1998 for a sheet made of the resin constituting the first resin layer, tan δ Is the temperature at which becomes the maximum. Note that the glass transition temperature Tg1 [° C.] of the resin constituting the first resin layer when the resin constituting the first resin layer includes a plurality of resins is the glass transition of the plurality of resins as a whole. Refers to temperature. Here, when a plurality of resins are included in the first resin layer, there may be a plurality of temperatures at which tan δ is maximized depending on the mixed state. In that case, the dynamic storage elastic modulus at a plurality of temperatures at which tan δ is maximized is measured by a method according to JIS K-7244: 1998, and the temperature at which the dynamic storage elastic modulus is minimized is the glass transition temperature. Tg1 [° C.].

  The glass transition temperature Tg1 [° C.] of the resin constituting the first resin layer in the laminate having the protrusions of the present invention is preferably in the range of −120 to 250 ° C. both before and after molding. More preferably, it is 50-200 degreeC, More preferably, it is 100-150 degreeC. When the resin constituting the second resin layer in the protrusion of the present invention is a thermosetting resin, the temperature at which the curing reaction starts is not particularly limited, but the glass transition temperature Tg1 of the resin constituting the first resin layer is not limited. Lower is preferred.

  Specific examples of the thermoplastic resin constituting the first resin layer 21 include polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, and polymethylpentene, polyethylene terephthalate, and polyethylene-2,6. -Polyester resins such as naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyamide resins, polyimide resins, polyether resins, polyesteramide resins, polyetherester resins, acrylic resins, polyurethane resins, polycarbonate resins Alternatively, a polyvinyl chloride resin or the like is used.

  Specific examples of the thermosetting resin constituting the second resin layer 22 include conventionally known phenol resins, urea resins, epoxy resins, melamine resins, and alkyd resins. Also, thermosetting acrylic resins, thermosetting polyimide resins, thermosetting polyurethane resins that become thermosetting resins by changing polymerization conditions, such as acrylic resins, polyimide resins, polyurethane resins, etc. Etc. can also be used suitably. Furthermore, for example, an unsaturated polyester resin obtained by diluting and dissolving a reactive monomer such as styrene in an unsaturated polyester can also be suitably used because it has thermosetting properties.

  Examples of the photo-curing resin constituting the second resin layer 22 include a resin having a carbon-carbon double bond site in the molecule, a urethane resin, and the like. Specific examples of the resin having a carbon-carbon double bond site in the molecule include urethane acrylate, polyol (meth) acrylate, (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups, and photopolymerization start. Mention may be made of a mixture of agents. Also, a resin having a maleimide structure in the molecule can be suitably used.

  The first resin layer and the second resin layer may contain various other additives as long as the effects of the present invention are not lost. Examples of the additive that can be added and blended include, for example, a dispersant, an antioxidant, a weathering agent, an antistatic agent, a polymerization inhibitor, a release agent, a thickener, a pH adjuster, and a salt. . It is also possible to add various functional materials such as dyes, pigments, electromagnetic wave absorbers, conductive materials, magnetic materials, liquid crystal materials, and light emitting materials, and components that promote effects by crosslinking with light or heat.

  The resin constituting the first resin layer and the resin constituting the second resin layer may both be a uniform single resin or a mixture of resins made of different materials. In the laminate of the present invention, it is also possible to provide a base material layer as a resin layer other than the first resin layer and the second resin layer. The laminated structure in this case is a structure of a first resin layer, a second resin layer, and a base material layer from the surface layer side. Examples of preferred substrate layers include film substrates such as polyester resins, polyolefin resins, acrylic resins, metal substrates such as stainless steel, aluminum, aluminum alloys, iron, steel, titanium, silicon, and various glasses such as quartz glass, Examples thereof include inorganic base materials such as concrete. The thickness of the base material layer is not particularly limited. In addition, the base material layer may be subjected to a treatment such as a base preparation material or a primer.

  The detail of an example of the manufacturing method of the laminated body which has the processus | protrusion of this invention is demonstrated using FIG.

  In the first heating step, a laminate 10 in which at least a first resin layer and a semi-cured second resin layer are laminated, and a mold 30 having a concave shape 31 in which the shape of a projection to be transferred is reversed. Is heated to a glass transition temperature Tg1 [° C.] or higher of the resin constituting the first resin layer (FIG. 3A), and in the pressure transfer step, the first resin layer 21 and the gold The mold 30 is approached and pressed as it is for a predetermined time with a predetermined pressing pressure to transfer the protrusions to be transferred onto the surface of the first resin layer (FIG. 3B). In the second heating step or the light irradiation step, the second resin layer 22 is cured by heating or light irradiation while maintaining the pressed state (FIG. 3C). Next, in the cooling step, the laminate 20 and the mold 30 are cooled to below Tg1 [° C.] while maintaining the pressed state (FIG. 3D). Finally, in the peeling step, the laminated body 20 having the protrusions 23 can be obtained by releasing the pressing pressure and peeling the laminated body 20 from the mold 30 (FIG. 3E).

  Here, in the first heating step, it is preferable that at least one of the mold temperature and the laminate temperature is a temperature equal to or higher than the glass transition temperature Tg1 [° C.] of the resin constituting the first resin layer. Preferably, it is in the range of Tg1 [° C.] to (Tg1 + 50 [° C.]). Moreover, it is more preferable that both the mold temperature and the laminate temperature are Tg1 [° C] or higher, and both the mold temperature and the laminate temperature are within the range of Tg1 [° C] to (Tg1 + 50 [° C]). It is particularly preferred that When both the mold temperature and the laminate temperature are lower than the glass transition temperature Tg1 [° C.] of the resin constituting the first resin layer, the dynamic storage of the resin constituting the first resin layer in the pressure transfer step This is because the elastic modulus is not sufficiently lowered, and even if the mold is pressed, the first resin layer is hardly deformed and may be difficult to mold. In addition, when both the mold temperature and the laminate temperature are sufficiently higher than (Tg1 + 50 [° C.]), it becomes difficult to melt and thin the first resin layer or to peel the laminate from the die. It may become. Further, when the resin constituting the second resin layer is a thermosetting resin, the flow into the concave shape 31 is suppressed by rapid thermosetting, which may make molding difficult.

  The pressing pressure at the time of pressure transfer depends on the shape of the protrusion to be transferred and the viscoelastic characteristics of the resin layer constituting the laminate, and the preferable range of the pressing pressure is generally 0.1 to 100 MPa. A more preferable range is 1 to 10 MPa.

  Furthermore, the press pressure holding time can be arbitrarily determined according to various conditions such as the press pressure at the time of pressure transfer, the concave shape 31 of the mold 30, the thickness of the first resin layer 21 and the second resin layer 22.

  In the second heating step and the light irradiation step, heating or light irradiation for completely curing the resin constituting the second resin layer 22 may be performed, and the temperature and light intensity required for curing, and the time until curing. These may be arbitrary depending on the resin constituting the second resin layer 22.

  In the cooling step, the mold temperature and the laminate temperature after cooling are preferably less than Tg1 [° C.]. More preferably, it is within the temperature range of (Tg1-80) to (Tg1-5) [° C.].

  In addition, the press pressure release temperature when releasing the press pressure in the peeling step is substantially equal to the mold temperature and the laminate temperature after cooling, and is preferably less than Tg1 [° C.]. More preferably, it is within the temperature range of (Tg1-80) to (Tg1-5) [° C.]. If this range is exceeded, the resin constituting the first resin layer 21 of the laminate 20 when the press pressure is released is in a fluid state, and thus the protrusion 23 may be deformed and accuracy may be reduced. It is. Moreover, it is preferable that the metal mold temperature and laminated body temperature when peeling the laminated body 20 from the metal mold | die 30 are in the temperature range from normal temperature to press pressure release temperature.

  As a manufacturing method of the laminated body 10 used for the production of the laminated body 20 having the protrusions 23 of the present invention, for example, a completely uncured thermosetting resin or a photocurable resin is applied on the base material layer. Then, the film or sheet | seat of the 1st resin layer 21 which has thermoplasticity is bonded together, and it presses using a flat plate press apparatus etc. The thickness of the second resin layer 22 is made uniform by pressing, and then the first resin layer and the semi-cured resin layer 22 are made to be in a semi-cured state by heating or light irradiation. The laminated body 10 which consists of can be obtained. Moreover, the laminated body 10 is obtained by apply | coating the resin which has thermosetting or photocurable property as the 2nd resin layer 22 with uniform thickness on the 1st resin layer 21 with a die coater, and making it heat or photocure. You can also. When the second resin layer is a thermosetting resin, the cured state of the second resin layer is not completely determined depending on the heating temperature and heating time. It can be widely controlled from a cured state to a semi-cured state.

  Here, the second resin layer being in a completely uncured state is a state before the curing reaction of the curable resin starts. Further, even after heating at which the curing reaction starts or after irradiation with light, when the hardness when all the curable resins are cured is 100%, a state where the hardness is less than 90% is defined as a semi-cured state. , 90% or more of the state is a fully cured state.

  In the method for manufacturing the laminate 20 having the protrusions 23 of the present invention, the surface of the first resin layer 21 is deformed by pressing the mold 30 having the concave shape 31 against the surface of the first resin layer 21. The laminated body 20 having the protrusions 23 is manufactured by allowing the resin constituting the second resin layer 22 to enter the interior of one resin layer 21. At this time, a flat plate mold may be pressed, or roll-to-roll continuous forming using a roll-shaped mold may be performed. In the case of roll-to-roll continuous forming, there is a feature that it is superior to the flat plate pressing method in terms of productivity.

  The laminated body 20 having the protrusions 23 of the present invention can be manufactured by a process through an apparatus as shown in FIGS. 4 and 5, for example.

  FIG. 4 is a schematic cross-sectional view showing an example of a manufacturing apparatus for manufacturing the laminate 20 having the protrusions 23, and illustrates an apparatus for pressing a flat plate mold. In the example shown in FIG. 4, in the unwinding unit 52, a film-like laminate 50 in which a thermosetting or photocurable resin is semi-cured as a second resin layer on the surface of the first resin layer is unrolled. 51, and then, in the press unit 54, the mold 53 having a concave shape formed on the surface heated by the heating means 61 is pressed against the film-like laminate 50 fed intermittently and pressed. After the thermosetting resin or photo-curing resin is completely cured by the curing means 62, the inverted inverted shape of the mold 53 is transferred to the surface of the film-like laminate 50 by cooling while maintaining the contact state. To do.

  The pressure transfer unit includes a press unit 54 that forms predetermined protrusions, and a peeling unit 55 that peels the film-like laminate 50 attached to the mold 53 from the mold 53. One surface of the film-like laminate 50 sent intermittently is pressure-transferred by the die 53 in the press unit 54 and, after the pressure-transfer, is attached to the die 53 by the peeling means 55. 50 are sequentially peeled from the mold 53, and the peeled film-like laminate 50 is taken up by a take-up roll 56. By such a process, it is possible to form the film-like laminate 50 having protrusions.

  In FIG. 4, 57 and 58 denote press plates, and 59 and 60 denote buffer means provided to smoothly perform intermittent conveyance in the mold 53 portion of the film-like laminate 50.

  FIG. 5 is a schematic cross-sectional view showing an example of a production apparatus for producing a laminate having protrusions, and illustrates an apparatus that performs roll-to-roll continuous forming. In the example shown in FIG. 5, a film-like laminate 70 obtained by semi-curing a thermosetting or photocurable resin as the second resin layer on the surface of the first resin layer is drawn out from the unwinding roll 71 and heated. It is supplied onto an endless belt-shaped mold 73 heated by a roll 72.

  The mold 73 has a fine concave shape that is discretely arranged on the outer surface independently, and is heated by the heating roll 72 immediately before coming into contact with the film-like laminate 70. The continuously supplied film-like laminate 70 is pressed against the surface of the mold 73 with the concave shape processed by the nip roll 74, and a predetermined protrusion is formed on the surface of the film-like laminate 70, and then the curing means 75. Thus, the resin having thermosetting property or photo-curing property is completely cured.

  Thereafter, the film-like laminate 70 is conveyed to the outer surface position of the cooling roll 76 in a state of being in close contact with the surface of the mold 73. The film-like laminate 70 is cooled by heat conduction through the mold 73 by the cooling roll 76, and then peeled off from the mold 73 by the peeling roll 77 and taken up by the winding roll 78. Such a process makes it possible to manufacture the film-like laminate 70 having protrusions continuously with high productivity.

  In the present invention, the mold 30 refers to a structure having a concave shape 31 for forming the protrusion 23 and having rigidity and strength capable of withstanding pressure in the thickness direction. The preferable concave shape 31 in the metal mold | die 30 of this invention is illustrated to Fig.6 (a)-(e). As the concave shape 31 of the preferable mold 30, a rectangular shape (FIG. 6A), a triangular shape (FIG. 6B), a circular shape (FIG. 6C), or a combination of these deformed and mixed (FIG. 6D ), (E)) and the like, but other shapes can also be used. The concave shape 31 in the mold 30 may be continuous in the longitudinal direction or may be discrete in the longitudinal direction. In the mold 30, the interval and arrangement method of the concave shapes 31 are not particularly limited, and the shape and depth may be changed in the middle, or may be regular or random arrangement.

  Thereby, the laminated body 20 which has the protrusions 23, such as a discrete dot shape and a continuous stripe shape, and the laminated body 20 which has the protrusions 23 containing both of these can be manufactured suitably.

  The mold surface 32 in contact with the laminate 20 is not particularly limited, but it is preferable to perform surface treatment such as fluororesin processing or plasma treatment in order to improve the releasability when peeling the laminate 20 from the mold 30. .

  As the material of the mold, various materials such as glass, silicon, stainless steel (SUS), nickel (Ni) can be used, and are not particularly limited. Among them, stainless steel (SUS), nickel (Ni), etc. A metal material rich in durability is preferred.

  As a surface treatment method of the mold 30, a method of chemically bonding a surface treatment agent to the mold surface (chemical adsorption method), a method of physically adsorbing the surface treatment agent to the mold surface (physical adsorption method), etc. Is mentioned. Among these, it is preferable to perform the surface treatment by a chemical adsorption method from the viewpoint of repeated durability of the surface treatment effect and prevention of contamination on the surface of the laminate.

  The manufacturing method of the mold 30 having the concave shape 31 on the surface is a method of directly cutting, laser processing or electron beam processing on the metal surface, or direct cutting, laser processing or electron beam processing on the plating film formed on the metal surface. The method of construction, the method of applying electroforming to these, etc. are mentioned. In addition, after applying the resist on the substrate, the resist is formed by a predetermined patterning method using a photolithography method, and then the substrate is subjected to an etching process, or the inverted pattern is applied by electroforming to the substrate from which the resist has been removed. The method of obtaining is mentioned. A concave pattern can be obtained by applying anisotropic etching. As the substrate, a silicon substrate or the like can be applied in addition to the metal plate.

  The laminated body having the protrusions of the present invention makes use of the structural characteristics obtained by the protrusions, for example, sensor sheet circuits, electronic paper and light guide plates, organic EL display devices, antenna circuits, RF-ID circuits, TFT circuit formations. It is suitably used for medical cell culture sheets and the like.

[Characteristic evaluation method]
A. Regarding the cross-sectional shape Cross-sectional observation of the protrusion after molding is performed by cutting the protrusion at the position where the protrusion height is maximum. Cross-sectional observation is preferably performed using a scanning electron microscope, and a microtome can be used for cutting out the observation sample from the laminate 20. In order to prevent the observation surface from collapsing due to cross-section cutting, it is preferable to cut the blade by tilting it by about 5 ° with respect to the projection 23 on the surface perpendicular to the stacking direction. In cutting out the cross section, the inclination of the blade at the time of cutting is not particularly specified, but it is cut at an angle depending on the type of resin and the shape of the protrusion 23, or after being immersed in liquid nitrogen and frozen or cut separately. It is preferable to suppress the collapse of the shape by a method such as embedding with a resin and then cutting.

B. Regarding the glass transition temperature Tg1 of the resin constituting the first resin layer. Using a sample different from the sample used for the evaluation of the cross-sectional shape, the glass transition temperature Tg1 of the resin constituting the first resin layer 21 is cut out at the base of the laminate 20, and the first resin layer 21 The cross section of was measured using the nanoindentation method. Here, the nano-indentation method is a method in which a sharp indenter is pushed into a resin layer, a dynamic vibration is applied to the indenter, and the dynamic viscoelastic properties of the resin layer are measured. Even when different resins are included, the value of Tg1 can be obtained for the entire mixture of the two or more resins. In the present invention, the indentation amount is 1 μm, the driving frequency is 1 Hz, the strain amplitude is 5 nm, the rate of temperature rise is 2 ° C./min, using a nanoindentation device “TI Premier DxSol” manufactured by Hysitoron and a Berkovich diamond indenter. The temperature dependence of the viscoelastic properties of each resin layer cross section was measured under the measurement conditions of minutes. From this measurement result, the temperature at which the tan δ of the resin constituting the first resin layer 21 was maximized was defined as Tg1.

C. Regarding the thickness t ′ of the first resin layer 21 and the second resin layer 22 at the base portion The thickness t ′ of the first resin layer 21 and the second resin layer 22 is obtained by cutting a cross section at the base portion of the laminate 20 and It measured using the scanning electron microscope VE-8800 by Corporation | KK. From the measurement results, the thickness from the surface at the base of the laminate 20 to the interface between the first resin layer 21 and the second resin layer 22 is t1 ′, and the thickness of the first resin layer 21 and the second resin layer 22 is The thickness from the interface to the base was defined as t2 ′.

D. Strength / Rigidity The laminate after molding was cut into 10 mm × 10 mm, and the compression modulus was measured under conditions according to JIS K7181: 2011 using an Instron 5582 type compression tester. The number of tests was n = 5, and the average value was the compression modulus. At this time, the test speed was 0.01 mm / min, and a 100N load cell was used.

Example 1
(1) Laminate On a PET film as a base material layer, a modified epoxy resin having a thermosetting property (trade name: Aron Mighty AS-60, manufactured by Toagosei Co., Ltd.) is used as a second resin layer using a die coater. Then, a polyurethane film having a thickness of 18 μm having thermoplasticity as a first resin layer on the modified epoxy resin of the second resin layer (trade name: Esmer URS, 4) and using the apparatus shown in FIG. 4, thermocompression bonding is performed at a press plate temperature of 100 ° C., a press pressure of 0.5 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. And the laminated body comprised with the polyurethane film, the semi-hardened modified | denatured epoxy resin, and PET film which is a base material layer was obtained.

(2) Mold On the surface of the stainless steel plate, a material mainly composed of Ni was coated with a thickness of about 100 μm. Then, the following shape was given to the mold surface by cutting.
Pattern: Lattice-like concave section: trapezoidal groove (upper base: 20 μm, lower base: 25 μm, depth: 50 μm)
Pitch between adjacent patterns: 150 μm
Size: 20 mm x 20 mm.

(3) Molding apparatus and conditions The apparatus as shown in FIG. 4 was applied. The press unit is a mechanism that is pressed by a hydraulic pump, and two press plates are attached inside in a vertical direction, and are connected to a heating device and a cooling device, respectively. The mold is placed on the upper surface of the lower press plate. Moreover, the peeling means for peeling the film after shaping | molding from a metal mold | die is installed in the press unit.

  Next, molding was performed by the method shown in FIG. 4 under conditions of a mold temperature of 125 ° C., a press pressure of 3 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. to obtain a laminate having protrusions.

(4) Results When the surface shape of the obtained laminate was observed using an Olympus 3D laser microscope OLS4100, the inverted shape of the concave shape of the mold was transferred to the surface of the laminate, resulting in a trapezoidal shape. It was confirmed that a grid pattern with an upper base of 20 μm, a lower base of 25 μm, and a height of 50 μm was formed with a pitch of 150 μm.

  Moreover, about the cross-sectional shape of protrusion, the cross section was cut out in the lattice point part with the highest protrusion height, and it observed using the Keyence Corporation scanning electron microscope VE-8800. The measured values of the obtained protrusions are shown in Tables 1 and 2, and the cross-sectional shape is shown in FIG. In the cross section of the protrusion obtained as shown in FIG. 7, the second resin layer penetrates into the first resin layer of the protrusion, the thickness t1 ′ of the first resin layer at the base is 10 μm, and the base The thickness t2 ′ of the second resin layer was 7 μm, (t1 ′ + t2 ′) was 17 μm, and the thickness t2 of the second resin layer at the protrusion was 54 μm.

  Moreover, the compression elastic modulus of the obtained laminated body was 2591 MPa.

(Example 2)
(1) Laminate On a PET film as a base material layer, a thermosetting liquid epoxy resin (trade name: precision epoxy resin ECR-9250K, manufactured by Sumitomo Bakelite Co., Ltd.) as a second resin layer is a die coater. And an acrylic resin film having a thickness of 25 μm having thermoplasticity as a first resin layer on the epoxy resin of the second resin layer (trade name: acrylprene, (Mitsubishi Rayon Co., Ltd.) are bonded together, and using the apparatus shown in FIG. 4, thermocompression bonding is performed at a press plate temperature of 110 ° C., a press pressure of 0.5 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. And the laminated body comprised with the acrylic resin film, the semi-hardened liquid epoxy resin, and the PET film which is a base material layer was obtained.

(2) Mold On the surface of the stainless steel plate, a material mainly composed of Ni was coated with a thickness of about 100 μm. Then, the following shape was given to the mold surface by cutting.
Pattern: Lattice-like cross section concave shape: Trapezoidal groove (upper base: 20 μm, lower base: 20 μm, depth: 20 μm)
Pitch between adjacent patterns: 156 μm
Size: 20 mm x 20 mm.

(3) Molding apparatus and conditions The apparatus as shown in FIG. 4 was applied. The press unit is a mechanism that is pressed by a hydraulic pump, and two press plates are attached inside in a vertical direction, and are connected to a heating device and a cooling device, respectively. The mold is placed on the upper surface of the lower press plate. Moreover, the peeling means for peeling the film after shaping | molding from a metal mold | die is installed in the press unit.

  Next, molding was performed by the method shown in FIG. 4 under conditions of a mold temperature of 125 ° C., a press pressure of 3 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. to obtain a laminate having protrusions.

(4) Results When the surface shape of the obtained laminate was observed using an Olympus 3D laser microscope OLS4100, the inverted shape of the concave shape of the mold was transferred to the surface of the laminate, resulting in a trapezoidal shape. It was confirmed that a grid pattern with an upper base of 20 μm, a lower base of 20 μm, and a height of 20 μm was formed with a pitch of 156 μm.

  Moreover, about the cross-sectional shape of protrusion, the cross section was cut out in the lattice point part with the highest protrusion height, and it observed using the Keyence Corporation scanning electron microscope VE-8800. Tables 1 and 2 show measured values of the obtained protrusions. In the cross section of the obtained protrusion, the second resin layer penetrates into the inside of the first resin layer of the protrusion, the thickness t1 ′ of the first resin layer at the base is 3 μm, and the second resin layer at the base is The thickness t2 ′ was 2 μm, (t1 ′ + t2 ′) was 5 μm, and the thickness t2 of the second resin layer at the protrusion was 17 μm.

  Moreover, the compression elastic modulus of the obtained laminate was 2075 MPa.

(Example 3)
(1) Laminate On a PET film as a base material layer, a modified epoxy resin having a thermosetting property (trade name: Aron Mighty AS-60, manufactured by Toagosei Co., Ltd.) is used as a second resin layer using a die coater. The acrylic resin film having a thickness of 25 μm and having thermoplasticity as the first resin layer on the epoxy resin of the second resin layer (trade name: Acryprene, Mitsubishi) 4) and using the apparatus shown in FIG. 4, thermocompression bonding was performed at a press plate temperature of 100 ° C., a press pressure of 0.5 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. A laminate composed of an acrylic resin film, a semi-cured modified epoxy resin, and a PET film as a base material layer was obtained.

(2) Mold On the surface of the stainless steel plate, a material mainly composed of Ni was coated with a thickness of about 100 μm. Then, the following shape was given to the mold surface by cutting.
Pattern: Lattice-like cross section concave shape: Trapezoidal groove (upper base: 20 μm, lower base: 20 μm, depth: 20 μm)
Pitch between adjacent patterns: 156 μm
Size: 20 mm x 20 mm.

(3) Molding apparatus and conditions The apparatus as shown in FIG. 4 was applied. The press unit is a mechanism that is pressed by a hydraulic pump, and two press plates are attached inside in a vertical direction, and are connected to a heating device and a cooling device, respectively. The mold is placed on the upper surface of the lower press plate. Moreover, the peeling means for peeling the film after shaping | molding from a metal mold | die is installed in the press unit.

  Next, molding was performed by the method shown in FIG. 4 under conditions of a mold temperature of 125 ° C., a press pressure of 3 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. to obtain a laminate having protrusions.

(4) Results When the surface shape of the obtained laminate was observed using an Olympus 3D laser microscope OLS4100, the inverted shape of the concave shape of the mold was transferred to the surface of the laminate, resulting in a trapezoidal shape. It was confirmed that a grid pattern with an upper base of 20 μm, a lower base of 20 μm, and a height of 20 μm was formed with a pitch of 156 μm.

  Moreover, about the cross-sectional shape of protrusion, the cross section was cut out in the lattice point part with the highest protrusion height, and it observed using the Keyence Corporation scanning electron microscope VE-8800. Tables 1 and 2 show measured values of the obtained protrusions. In the cross section of the obtained protrusion, the second resin layer penetrates into the inside of the first resin layer of the protrusion, the thickness t1 ′ of the first resin layer at the base is 8 μm, and the second resin layer at the base is The thickness t2 ′ was 2 μm, (t1 ′ + t2 ′) was 10 μm, and the thickness t2 of the second resin layer at the protrusion was 19 μm.

  Further, the compression elastic modulus of the obtained laminate was 1721 MPa.

(Comparative Example 1)
(1) Laminate A 40 μm thick polyurethane film (trade name: Esmer URS, manufactured by Nihon Matai Co., Ltd.) having thermoplasticity as a first resin layer is bonded to a PET film as a base layer, and the base layer and A laminate composed of the first resin layer was obtained.

(2) Mold A mold similar to that used in Example 1 was used.

(3) Molding apparatus and conditions In the same manner as in Example 1, molding was performed under the conditions of a mold temperature of 125 ° C., a press pressure of 3 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. by the method shown in FIG. A laminate having protrusions was obtained.

(4) Results When the surface shape of the obtained laminate was observed using an Olympus 3D laser microscope OLS4100, the surface of the laminate was trapezoidal (upper 22 μm, lower 25 μm, height 45 μm). ), A grid pattern having a pitch of 150 μm was formed, and the mold shape could not be transferred sufficiently.

  Further, after peeling off the base material layer and the first resin layer of the obtained laminate, a cross section was cut out at a lattice point portion where the height of the protrusion was the highest, and a scanning electron microscope VE-8800 manufactured by Keyence Corporation was used. The cross-sectional shape was observed. Tables 1 and 2 show measured values of the obtained protrusions. The protrusions were formed only by the deformation of the first resin layer, and the mold shape could not be transferred sufficiently.

(Comparative Example 2)
(1) Laminate A 25 μm-thick acrylic resin film (trade name: Acryprene, manufactured by Mitsubishi Rayon Co., Ltd.) having thermoplasticity as a first resin layer is bonded onto a PET film as a base material layer, A laminate composed of the first resin layer was obtained.

(2) Mold A mold similar to that used in Example 2 was used.

(3) Molding apparatus and conditions The conditions were changed from those in Example 2, and molding was performed by the method shown in FIG. 4 under conditions of a mold temperature of 145 ° C., a press pressure of 5 MPa, a press pressure holding time of 60 seconds, and a press pressure release temperature of 50 ° C. Thus, a laminate having protrusions was obtained.

(4) Results When the surface shape of the obtained laminate was observed using an Olympus 3D laser microscope OLS4100, the surface of the laminate was trapezoidal (upper 20 μm, lower 20 μm, 20 μm high). It was confirmed that a grid pattern with a pitch of 156 μm was formed.

  Further, after peeling off the base material layer and the first resin layer of the obtained laminate, a cross section was cut out at a lattice point portion where the height of the protrusion was the highest, and a scanning electron microscope VE-8800 manufactured by Keyence Corporation was used. The cross-sectional shape was observed. Tables 1 and 2 show measured values of the obtained protrusions. The protrusion was formed only by the deformation of the first resin layer, and the mold shape was sufficiently transferred.

  At this time, the compression elastic modulus was 1322 MPa, which was smaller by 753 MPa than the compression elastic modulus of the laminate obtained in Example 2.

  The laminate obtained by the method for producing a laminate having protrusions of the present invention can be used for various applications by appropriately selecting the material constituting the protrusions. As an example of the application, when a conductive material is used as a material for forming the protrusion, a conductive film, an electromagnetic wave shielding film, an electric circuit, and the like can be given. In addition, when a light diffusing material, a light absorbing material, a light emitting material, or the like is used, a sheet material and a display member having light controllability can be obtained. In addition, it can be applied to biochips, semiconductor integrated materials, design members, optical circuits, optical connector members, microneedles, and the like.

10: Laminate 20: Laminate 21: First resin layer 22: Second resin layer 23: Protrusion 24: Base layer 30: Mold 31: Concave shape 32: Mold surface 50: Film-like laminate 51 : Unwinding roll 52: unwinding unit 53: mold 54: press unit 55: peeling means 56: take-up roll 57, 58: press plate 59, 60: buffer means 61: heating means 62: curing means 70: film shape Laminate 71: Unwinding roll 72: Heating roll 73: Mold 74: Nip roll 75: Curing means 76: Cooling roll 77: Release roll 78: Winding roll t: Height of protrusion t1: First resin layer at the protrusion Thickness t2 of the second resin layer at the protrusion t1 ′: thickness of the first resin layer at the base t2 ′: thickness of the second resin layer at the base w: width of the protrusion w2: second resin at the protrusion Layer width

Claims (4)

  It has at least a first resin layer and a second resin layer, the resin constituting the first resin layer is a thermoplastic resin, and the resin constituting the second resin layer is thermosetting. Or it is resin which has photocurability, has a processus | protrusion on the said 1st resin layer surface, the thickness of the 2nd resin layer in this process is t2, the thickness of the 1st resin layer in a base part is t1 ', A laminate having protrusions, wherein (t1 ′ + t2 ′) ≦ t2 when the thickness of the second resin layer is t2 ′.   The laminate having a protrusion according to claim 1, wherein 2.0 ≦ (t2 / w2), where w2 is a width of the second resin layer in the protrusion.   The cross-sectional area ratio A2 / A satisfies 0.25 or more, where A is the cross-sectional area of the protrusion and A2 is the cross-sectional area of the second resin layer in the protrusion. A laminate having a plurality of protrusions.   At least one of a mold having a concave shape at least on the surface or a laminate having the first resin layer and the second resin layer, the glass transition temperature Tg1 [° C.] of the resin constituting the first resin layer The first heating step of heating as described above, and the pressure transfer step of pressing the mold from the first resin layer side of the laminate and transferring the projections having the inverted shape of the concave shape to the laminate. And the second heating step or the light irradiation step, the cooling step for cooling the laminate and the mold to less than Tg1 [° C.], and the peeling step for peeling the die and the laminate. A process for producing a laminate having protrusions, wherein protrusions are formed on the surface of the first resin layer of the body.