JP2018161783A - Resin shee with surface layer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin sheet with surface layer material suitable for suppressing generation of wrinkle at a roll shape.SOLUTION: A resin sheet 10 with surface layer material has a laminate structure containing a surface layer material 11, a surface layer material 12, and a resin layer 13, which is an adhesive layer for example, located between these surface layer materials 11 and 12, and has a roll shape in which the surface layer material 12 is positioned in an outer shape side than the surface layer material 11 in the laminate structure. Storage elastic modulus of the surface layer material 11 at 25°C is more than 1×10Pa. Storage elastic modulus of the surface layer material 12 at 25°C is 1×10Pa or more and smaller than storage elastic modulus of the surface layer material 11 at 25°C. Storage elastic modulus of the resin layer at 25°C is 5×10Pa or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin sheet with surface material on both sides.

  The resin material used in the form of a thin layer such as an adhesive layer may be provided in the form of a resin layer or a resin sheet with a surface layer material such as a separator on both sides. In addition, such a resin sheet with a surface layer material is formed as a long sheet body from the viewpoint of the handleability and workability of the sheet, and is in the form of a roll. There is a case. For example, the following Patent Documents 1 and 2 describe a technique related to a resin sheet with a surface layer material in the form of a roll.

JP 2011-201634 A JP-A-2015-160678

  In a resin sheet with a double-sided surface layer material in the form of a roll, wrinkles may conventionally occur in the surface layer material. In the laminated structure of the resin sheet in the form of a roll, the surface layer material located on the inner diameter side is curved with a smaller radius of curvature than the surface layer material located on the outer diameter side, and therefore tends to be subjected to compressive stress, and therefore Prone to wrinkles. The thicker the resin layer located between these two surface layer materials, the larger the difference in the radius of curvature between the inner diameter side surface material and the outer diameter side surface material in the laminated structure. Wrinkles tend to occur due to the tendency to undergo compressive stress. In addition, the softer the resin layer between the surface layer materials, the easier the wrinkles of the inner diameter side surface layer material occur. Generation | occurrence | production of the wrinkle in a surface layer material causes the thickness nonuniformity in the resin layer between surface layer materials, for example, and is unpreferable.

  The present invention has been conceived under the circumstances as described above, and an object thereof is to provide a resin sheet with a surface layer material suitable for suppressing the occurrence of wrinkles in the form of a roll. .

The resin sheet with a surface layer material provided by the present invention has a laminated structure including a first surface layer material, a second surface layer material, and a resin layer located between the first and second surface layer materials, and In the laminated structure, the second surface layer material takes the form of a roll positioned on the outer diameter side of the first surface layer material. The storage modulus at 25 ° C. of the first surface layer material (inner diameter side surface layer material) is larger than 1 × 10 ⁷ Pa or higher, preferably 1 × 10 ⁸ Pa or higher, more preferably 1 × 10 ⁹ Pa or higher. Is 2 × 10 ⁹ Pa or more. The storage elastic modulus at 25 ° C. of the second surface layer material (outer diameter side surface layer material) is smaller than the storage elastic modulus at 25 ° C. of the first surface layer material, and as long as it is 1 × 10 ⁷ Pa or more, preferably Is 5 × 10 ⁷ Pa or more, more preferably 1 × 10 ⁸ Pa or more. The resin layer is located between the first and second surface layer materials, and the storage elastic modulus at 25 ° C. is 5 × 10 ⁵ Pa or less, preferably 1 × 10 ⁵ Pa or less, more preferably 5 × 10 ⁴ Pa or less.

  In the resin sheet with the surface layer material, the first surface layer material located on the inner diameter side in the laminated structure is curved with a smaller radius of curvature than the second surface layer material located on the outer diameter side. As described above, the sheet has a configuration in which the second surface layer material on the outer diameter side has a smaller storage elastic modulus than that of the first surface layer material on the inner diameter side at 25 ° C. within normal temperature and the temperature range in the vicinity thereof. It has. The structure that the second surface layer material on the outer diameter side is softer than the first surface layer material on the inner diameter side is such that the first surface material has a smaller radius of curvature than the second surface material in the laminated structure of the resin sheet. It is suitable for relieving the compressive stress that the first surface layer material receives due to the curvature, and therefore suitable for suppressing the generation of wrinkles in the first surface layer material.

As described above, the resin sheet with a surface layer material of the present invention has a resin layer having a storage elastic modulus at 25 ° C. of 5 × 10 ⁵ Pa or less. The above structure in which the resin sheet with the surface layer material includes the first and second surface layer materials having a storage elastic modulus (25 ° C.) of 1 × 10 ⁷ Pa or more together with the resin layer that is soft to this extent is the present sheet. It is suitable for securing the net hardness of the entire sheet from the viewpoints of handleability and processability. In the roll-shaped double-sided surface-layered resin sheet, as the resin layer between the surface-layer materials is softer, wrinkles are more likely to occur in the inner-side surface layer material. The above-mentioned constitution suitable for ensuring the net hardness of the film, that is, the storage elastic modulus (25 ° C.) of 1 × 10 ⁷ Pa or more together with a soft resin layer having a storage elastic modulus (25 ° C.) of 5 × 10 ⁵ Pa or less. The above-mentioned configuration suitable for reducing the compressive stress received by the first surface layer material (inner diameter side surface layer material) and suppressing the generation of wrinkles in the first surface layer material. That is, the second surface layer material (outer diameter side surface layer material) has a smaller storage elastic modulus than the first surface layer material and is soft.

As described above, the resin sheet with a surface layer material is suitable for suppressing the generation of wrinkles in the form of a roll. The suppression of wrinkles in the resin sheet with a surface layer material is preferable, for example, to ensure the uniformity of the thickness of the resin layer positioned between the surface layer materials. Moreover, in this resin sheet with a surface layer material, although both the 1st and 2nd surface layer materials have the storage elastic modulus (25 degreeC) hardness of 1 * 10 < ⁷ > Pa or more, the 2nd surface layer material is smaller than a 1st surface layer material. The above configuration of having a storage elastic modulus and being soft (that is, the first surface layer material is harder and having a storage elastic modulus larger than that of the second surface layer material) ensures the net hardness of the entire sheet. In addition to being suitable for suppressing the generation of wrinkles in the first surface layer material, the one side surface required for performing the work of bonding the resin sheet with the first surface layer material after the peeling of the second surface layer material to the adherend Suitable for ensuring the hardness of the resin sheet with the surface layer material.

  In the resin sheet with a surface layer material, preferably, the resin layer is an adhesive layer. According to such a configuration, it is possible to provide a pressure-sensitive adhesive sheet with a double-sided surface layer material suitable for suppressing the generation of wrinkles in the form of a roll.

  In the resin sheet with a surface layer material, the thickness of the resin layer is preferably 100 μm or more, more preferably 150 μm or more, and more preferably 180 μm or more. Such a thick resin layer is suitable for use as an embedding material such as an embedding / adhesive material.

  In the resin sheet with a surface layer material, preferably, the first surface layer material and / or the second surface layer material is a separator. According to such a configuration, the surface layer material is easily peeled off from the resin layer when the resin layer is processed or used.

  In this resin sheet with a surface layer material, the ratio of the storage elastic modulus at 25 ° C. of the second surface layer material to the storage elastic modulus at 25 ° C. of the first surface layer material is preferably 0.6 or less, more preferably 0. 0.5 or less, more preferably 0.3 or less, more preferably 0.1 or less. Such a configuration relating to the storage elastic modulus of the first and second surface layer materials contributes to suppressing the generation of wrinkles in the resin sheet with the surface layer material in the form of a roll.

  In this resin sheet with a surface layer material, the value of the ratio of the product of the storage elastic modulus and thickness at 25 ° C. of the second surface layer material to the product of the storage elastic modulus and thickness at 25 ° C. of the first surface layer material is: Preferably, it is 0.7 or less, more preferably 0.6 or less, more preferably 0.3 or less, more preferably 0.2 or less, and more preferably 0.1 or less. The product of the storage elastic modulus and the thickness in the material layer is an index of the rigidity of the material layer. Such a configuration relating to the rigidity of the first and second surface material is a resin sheet with the surface material in the form of a roll. It helps to suppress the generation of wrinkles.

  In the resin sheet with a surface layer material in the form of a roll, the innermost diameter is preferably 15 cm or less, more preferably 10 cm or less, and more preferably 8 cm or less. Although the compressive stress received by the first surface layer material on the inner diameter side tends to be larger as the innermost diameter of the resin sheet with the surface layer material is smaller, the resin sheet with the surface layer material is the first surface layer material (inner diameter side surface layer material). A configuration suitable for relaxing the compressive stress received and suppressing the generation of wrinkles in the first surface layer material, that is, the second surface layer material (outer diameter side surface layer material) has a smaller storage elastic modulus than the first surface layer material. It has the structure of having and being soft as described above.

It is a partial expanded cross section schematic diagram of the resin sheet with a surface layer material which concerns on one Embodiment of this invention.

  FIG. 1 is a partially enlarged schematic cross-sectional view of a resin sheet 10 with a surface layer material according to an embodiment of the present invention. The resin sheet 10 with a surface layer material has a laminated structure including a surface layer material 11, a surface layer material 12, and a resin layer 13 positioned between the surface layer materials 11 and 12, and the surface layer material in the laminated structure. 12 takes the form of a roll located on the outer diameter side of the surface layer material 11. In this embodiment, the resin sheet 10 with a surface layer material is wound around the winding core C in an aspect or a direction in which the surface layer material 12 is positioned on the outer diameter side of the surface layer material 11 in the laminated structure.

  The surface layer material 11 in the resin sheet 10 with the surface layer material is an element for covering one surface of the resin layer 13 in the present embodiment, and is located on the inner diameter side of the surface layer material 12 in the sheet laminated structure. The surface layer material 12 in the resin sheet 10 with the surface layer material is an element for covering the other surface of the resin layer 13 in the present embodiment, and as described above, the outer diameter side of the surface layer material 11 in the sheet laminated structure. Located in. The surface layer material 11 and the surface layer material 12 can be peeled from the resin layer 13 when the resin layer 13 is processed or used. Such surface layer material 11 and / or surface layer material 12 is, for example, a separator. As the separator, for example, a resin film or paper material in which, for example, a corona treatment and a subsequent peeling treatment are performed on the surface of the resin layer 13 to be adhered can be used. Examples of the resin material for forming the resin film for the separator include polyolefin and polyester. Examples of the polyolefin include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolyprolene, polybutene, polymethylpentene, Ethylene-vinyl acetate copolymer (EVA), ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-butene copolymer, and ethylene-hexene copolymer Coalescence is mentioned. Examples of the polyester include polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT). The resin film for the separator may be an unstretched film, a uniaxially stretched film, or a biaxially stretched film. Examples of the release treatment agent for the release treatment include a silicone release treatment agent, a long-chain alkyl release treatment agent, a fluorine release treatment agent, and a molybdenum sulfide release treatment. Each of the surface layer materials 11 and 12 as described above may be made of one kind of material or two or more kinds of materials. The surface layer materials 11 and 12 may have a single layer structure or a multilayer structure. Moreover, the thickness of the surface layer materials 11 and 12 is respectively 25-200 micrometers, for example.

In the resin sheet 10 with the surface layer material, the storage elastic modulus at 25 ° C. of the surface layer material 11 is larger than 1 × 10 ⁷ Pa or more, preferably 1 × 10 ⁸ Pa or more, more preferably 1 × 10 ⁹ Pa or more. Preferably it is 2 × 10 ⁹ Pa or more. The storage elastic modulus at 25 ° C. of the surface layer material 12 is smaller than the storage elastic modulus at 25 ° C. of the surface layer material 11 and is 1 × 10 ⁷ Pa or more, preferably 5 × 10 ⁷ Pa or more, more preferably. Is 1 × 10 ⁸ Pa or more. The value of the ratio of the storage elastic modulus at 25 ° C. of the surface layer material 12 to the storage elastic modulus at 25 ° C. of the surface layer material 11 is preferably not more than 0.6, more preferably not more than 0.5, and more preferably 0.3. Below, more preferably 0.1 or less. The ratio of the product of the storage elastic modulus and thickness at 25 ° C. of the surface layer material 12 to the product of the storage elastic modulus and thickness at 25 ° C. of the surface layer material 11 is preferably 0.7 or less. Preferably it is 0.6 or less, more preferably 0.3 or less, more preferably 0.2 or less, more preferably 0.1 or less. The storage elastic modulus can be determined based on a dynamic viscoelasticity measurement performed using a dynamic viscoelasticity measuring device (trade name “RSA III”, manufactured by TA Instruments). In this measurement, the size of the sample piece as the measurement object is 30 mm long × 10 mm wide, the distance between the chucks for holding the sample piece is 20 mm, the measurement mode is the tension mode, and the measurement temperature range is from −30 ° C. The temperature is 100 ° C., the frequency is 1 Hz, the strain is 0.1%, and the heating rate is 5 ° C./min.

The resin layer 13 in the resin sheet 10 with the surface layer material is located between the surface layer materials 11 and 12 as described above, and the storage elastic modulus at 25 ° C. is 5 × 10 ⁵ Pa or less, preferably 1 ×. 10 ⁵ Pa or less, more preferably 5 × 10 ⁴ Pa or less. Examples of the resin material for forming the resin layer 13 include acrylic resins, urethane resins, silicone resins, ethylene propylene resins, styrene resins, and imide resins. In addition to the resin material, the resin layer 13 may contain, for example, a tackifier, an antioxidant, and a colorant such as a pigment or a dye. Such a resin layer 13 may be made of one kind of material, may be made of two or more kinds of materials, may have a single layer structure, or may have a multilayer structure. Good.

  The resin layer 13 in the resin sheet with surface layer material 10 may be an adhesive layer. When the resin layer 13 is an adhesive layer, the resin sheet 10 with a surface layer material provides an adhesive sheet. When the resin layer 13 is an adhesive layer, examples of the adhesive for forming the resin layer 13 include an acrylic polymer as an acrylic adhesive, a polyurethane as a urethane adhesive, and a rubber adhesive. And silicone-based pressure-sensitive adhesives.

  The acrylic polymer as the acrylic pressure-sensitive adhesive contains, for example, a monomer unit derived from an acrylic ester and / or a methacrylic ester as a main monomer unit having the largest mass ratio. Hereinafter, “(meth) acryl” means “acryl” and / or “methacryl”. Examples of the (meth) acrylic acid ester for forming the monomer unit of the acrylic polymer include, for example, hydrocarbon groups such as (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, and (meth) acrylic acid aryl ester. Examples thereof include (meth) acrylic acid esters. Examples of (meth) acrylic acid alkyl esters include (meth) acrylic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Pentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, Examples include octadecyl ester and eicosyl ester. Examples of (meth) acrylic acid cycloalkyl ester include cyclopentyl ester and cyclohexyl ester of (meth) acrylic acid. Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylate and benzyl (meth) acrylate. As the (meth) acrylic acid ester as the main monomer for the acrylic polymer, one kind of (meth) acrylic acid ester may be used, or two or more kinds of (meth) acrylic acid esters may be used. .

  The acrylic polymer may contain a monomer unit derived from another monomer copolymerizable with the (meth) acrylic acid ester in order to modify the cohesive strength and heat resistance. Examples of such monomer components include carboxy group-containing monomers, acid anhydride monomers, hydroxy group-containing monomers, and glycidyl group-containing monomers. Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride. Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, ( Examples include 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate. Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. As the other monomer for the acrylic polymer, one type of monomer may be used, or two or more types of monomers may be used.

  The acrylic polymer may contain a monomer unit derived from a polyfunctional monomer copolymerizable with a monomer component such as (meth) acrylic acid ester in order to form a crosslinked structure in the polymer skeleton. Examples of such polyfunctional monomers include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyglycidyl (meth) acrylate, polyester (meth) acrylate, and urethane ( And (meth) acrylate. As the polyfunctional monomer for the acrylic polymer, one kind of polyfunctional monomer may be used, or two or more kinds of polyfunctional monomers may be used.

  The acrylic polymer can be obtained by polymerizing raw material monomers for forming the acrylic polymer. Examples of the polymerization technique include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization.

  The pressure-sensitive adhesive for forming the resin layer 13 as the pressure-sensitive adhesive layer may contain, for example, an external crosslinking agent in order to increase the number average molecular weight of the acrylic polymer as the base polymer. Examples of the external crosslinking agent for reacting with an acrylic polymer to form a crosslinked structure include a polyisocyanate compound, an epoxy compound, an aziridine compound, and a melamine crosslinking agent.

  The resin layer 13 may be a radiation curable pressure-sensitive adhesive layer that is cured by being irradiated with radiation such as ultraviolet rays. Examples of the radiation-curable pressure-sensitive adhesive for forming such a pressure-sensitive adhesive layer include, for example, the above-mentioned acrylic polymer as an acrylic pressure-sensitive adhesive and radiation having a functional group such as a radiation-polymerizable carbon-carbon double bond. An additive type radiation curable pressure-sensitive adhesive containing a polymerizable monomer component or oligomer component may be mentioned. Examples of the radiation polymerizable monomer component include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra. Examples include (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4-butanediol di (meth) acrylate. Examples of radiation-polymerizable oligomer components include various oligomers such as urethane, polyether, polyester, polycarbonate, and polybutadiene.

  Examples of the radiation curable pressure-sensitive adhesive for forming the resin layer 13 as the pressure-sensitive adhesive layer include an internal radiation-curable pressure-sensitive adhesive. The internal radiation-curable pressure-sensitive adhesive is, for example, an acrylic polymer having a functional group such as a radiation-polymerizable carbon-carbon double bond at the end of the main chain or in the main chain. Contained as. Such an internal radiation-curable pressure-sensitive adhesive is suitable for suppressing an unintended change in the adhesive property due to the movement of a low molecular weight component in the formed pressure-sensitive adhesive layer. In the pressure-sensitive adhesive, the above-mentioned acrylic polymer can be adopted as the acrylic polymer that forms the basic skeleton of the base polymer. As a method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer, for example, a raw material monomer including a monomer having a predetermined functional group (first functional group) is copolymerized to form an acrylic polymer. After obtaining, a compound having a predetermined functional group (second functional group) that can react and bond with the first functional group and a radiation-polymerizable carbon-carbon double bond is converted to carbon-carbon. Examples thereof include a method in which an addition reaction or a condensation reaction is performed on an acrylic polymer while maintaining the radiation polymerization property of a double bond. Examples of the combination of the first functional group and the second functional group include, for example, carboxy group and epoxy group, epoxy group and carboxy group, carboxy group and aziridyl group, aziridyl group and carboxy group, hydroxy group and isocyanate group, and isocyanate group. And a hydroxy group. Examples of the isocyanate compound having both a radiation-polymerizable carbon-carbon double bond and an isocyanate group as the second functional group include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, and m-isopropenyl-α, α-dimethyl. Benzyl isocyanate is mentioned.

  The radiation curable pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer 12 preferably contains a photopolymerization initiator. Examples of photopolymerization initiators include α-ketol compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, camphors. Examples include quinones, halogenated ketones, acyl phosphinoxides, and acyl phosphonates.

  The above polyurethane as a urethane-based pressure-sensitive adhesive is a polymer having a number of urethane bonds in the molecular chain. For example, polyfunctional isocyanate, polyhydric alcohol, and active hydrogen such as water and amine used as necessary. It is a polymer with a group-containing compound. Examples of the polyfunctional isocyanate include hexamethylene diisocyanate (HDI), 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), diphenylmethane diisocyanate (MDI), and tolylene diisocyanate. (TDI), xylylene diisocyanate (XDI), and hydrogenated MDI. Examples of the polyhydric alcohol include aliphatic or alicyclic polyhydric alcohols and aromatic polyhydric alcohols. Examples of the aliphatic or alicyclic polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanediol. Examples of the aromatic polyhydric alcohol include bisphenol A and resorcinol. Such polyurethanes can be synthesized, for example, by solution polymerization, emulsion polymerization, or bulk polymerization in a so-called prepolymer method of two-step synthesis or a so-called one-shot method of one-step synthesis.

  Examples of the rubber-based pressure-sensitive adhesive include synthetic rubbers such as diene synthetic rubber and non-diene synthetic rubber, and natural rubber. Examples of the diene-based synthetic rubber include isoprene rubber, butadiene rubber, styrene / butadiene rubber, and chloroprene rubber. Examples of the non-diene rubber include butyl rubber, ethylene propylene rubber, urethane rubber, and silicone rubber.

  The thickness of the resin layer 13 in the resin sheet with a surface layer material 10 is preferably 100 μm or more, more preferably 150 μm or more, and more preferably 180 μm or more.

  In this embodiment, when the resin sheet 10 with the surface layer material is wound around the winding core C, the diameter of the winding core C, that is, the innermost inner diameter R of the resin sheet 10 with the surface layer material is preferably 15 cm or less, more preferably It is 10 cm or less, more preferably 8 cm or less. Examples of the constituent material of the winding core C include plastic materials and paper materials. Examples of the plastic material for the winding core C include acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer.

  The resin sheet 10 with a surface layer material having the above-described configuration is manufactured through the following process, for example. First, the resin composition for forming the resin layer 13 is applied on one surface layer material (the surface layer material 11 or the surface layer material 12) to form a resin composition layer. Examples of the coating method include fountain coating, roll coating, screen coating, and gravure coating. Next, the resin composition layer is heated and dried as necessary, and a crosslinking reaction is caused in the resin composition as necessary to form the resin layer 13. The heating temperature is, for example, 80 to 150 ° C., and the heating time is, for example, 0.5 to 5 minutes. Then, after the other surface layer material (the surface layer material 12 or the surface layer material 11) is bonded to the exposed surface of the resin layer 13 formed on one surface layer material, the pair of surface layer materials 11, 12 and the resin layer 13 A laminated sheet containing is wound around the core. The tension | tensile_strength (winding tension | tensile_strength) applied to a lamination sheet in winding is 50-300N, for example, Preferably it is 100-200N. Moreover, the speed | rate (winding speed) in winding is 1-100 m / min, for example, Preferably it is 20-40 m / min.

  For example, the resin sheet 10 with a surface layer material manufactured as described above can be configured as a supply material such as a sheet-like pressure-sensitive adhesive or an embedding and pressure-sensitive adhesive material. Examples of the embedding and adhesion material include an adhesion material for embedding the ball grid array and bonding the package to a predetermined substrate in the process of manufacturing the semiconductor package with the ball grid array.

  As described above, the resin sheet 10 with a surface layer material has a storage modulus smaller than that of the surface layer material 11 on the inner diameter side, at the outer diameter side surface layer material 12 at 25 ° C. within the temperature range of normal temperature and the vicinity thereof. It has the structure. The configuration in which the outer diameter side surface layer material 12 is softer than the inner diameter side surface material 11 is such that the surface material 11 is curved with a smaller radius of curvature than the surface material 12 in the laminated structure of the resin sheet 10 with the surface material. Therefore, it is suitable for alleviating the compressive stress that the surface layer material 11 receives due to this, and therefore suitable for suppressing the generation of wrinkles in the surface layer material 11.

As described above, the resin sheet 10 with a surface layer material includes the resin layer 13 having a storage elastic modulus at 25 ° C. of 5 × 10 ⁵ Pa or less. The above structure in which the resin sheet 10 with the surface layer material includes the surface layer materials 11 and 12 having a storage elastic modulus (25 ° C.) of 1 × 10 ⁷ Pa or more together with the soft resin layer 13 to this extent is easy to handle the sheet. It is suitable for securing the net hardness of the entire sheet from the viewpoints of processability and processability. The resin sheet 10 with a surface layer material is suitable for ensuring the net hardness of the entire sheet, that is, the storage elastic modulus together with the soft resin layer 13 having a storage elastic modulus (25 ° C.) of 5 × 10 ⁵ Pa or less. (25 ° C.) In the configuration including the first and surface layer materials 12 of 1 × 10 ⁷ Pa or more, the compressive stress received by the surface layer material 11 (inner diameter side surface layer material) is alleviated and the generation of wrinkles in the surface layer material 11 is suppressed. Further, the above-described configuration suitable for the above-described configuration, that is, the configuration in which the surface layer material 12 (outer diameter side surface layer material) has a smaller storage elastic modulus than the surface layer material 11 and is soft is further provided.

As described above, the resin sheet 10 with a surface layer material is suitable for suppressing the generation of wrinkles in the form of a roll. Such wrinkle suppression is preferable, for example, to ensure the uniformity of the thickness of the resin layer 13 positioned between the surface layer materials 11 and 12. Moreover, in the resin sheet 10 with a surface layer material, although the surface layer materials 11 and 12 both have a storage elastic modulus (25 ° C.) of 1 × 10 ⁷ Pa or more, the surface layer material 12 has a smaller storage elastic modulus than the surface layer material 11. The above-mentioned configuration of having and soft (that is, the surface layer material 11 has a larger storage elastic modulus than the surface layer material 12 and is hard) has the wrinkle of the surface layer material 11 while ensuring the net hardness of the entire sheet. In addition to being suitable for suppressing the occurrence, the hardness of the resin sheet 10 with a single-sided surface layer material required for performing the work of bonding the resin sheet 10 with the surface layer material 11 after the surface layer material 12 is peeled off to the adherend. It is suitable for securing the thickness.

In the resin sheet 10 with a surface layer material, the storage elastic modulus at 25 ° C. of the surface layer material 11 is preferably 1 × 10 ⁸ Pa or more, more preferably 1 × 10 ⁹ Pa or more, more preferably 2 ×, as described above. 10 ⁹ Pa or more. As described above, the storage elastic modulus of the surface layer material 12 at 25 ° C. is smaller than the storage elastic modulus of the surface layer material 11 at 25 ° C., and is preferably 5 × 10 ⁷ Pa or more, more preferably 1 × 10. ⁸ Pa or more. These structures are received by the surface layer material 11 because the surface layer material 11 (inner diameter side surface layer material) is curved with a smaller radius of curvature than the surface layer material 12 in the laminated structure of the resin sheet 10 with the surface layer material. It is preferable for relaxing the compressive stress, and is therefore preferable for suppressing generation of wrinkles in the surface layer material 11.

  As described above, the thickness of the resin layer 13 of the resin sheet with a surface layer material 10 is preferably 100 μm or more, more preferably 150 μm or more, and more preferably 180 μm or more. Thus, the thick resin layer 13 is preferable when used as an embedding material such as an embedding and adhesive material.

  As described above, the surface layer material 11 and / or the surface layer material 12 of the resin sheet with surface layer material 10 is a separator. According to such a configuration, the surface layer material 11 and / or the surface layer material 12 can be easily peeled from the resin layer 13 when the resin layer 13 is processed or used.

  The value of the ratio of the storage elastic modulus at 25 ° C. of the surface layer material 12 to the storage elastic modulus at 25 ° C. of the surface layer material 11 in the resin sheet 10 with the surface layer material is preferably 0.6 or less, more preferably as described above. Is 0.5 or less, more preferably 0.3 or less, and more preferably 0.1 or less. Such a configuration relating to the storage elastic modulus of the surface layer materials 11 and 12 contributes to suppressing the generation of wrinkles in the resin sheet 10 with the surface layer material in the form of a roll. The ratio of the product of the storage elastic modulus and thickness at 25 ° C. of the surface layer material 12 to the product of the storage elastic modulus and thickness at 25 ° C. of the surface layer material 11 is preferably 0 as described above. 0.7 or less, more preferably 0.6 or less, more preferably 0.3 or less, more preferably 0.2 or less, more preferably 0.1 or less. The product of the storage elastic modulus and the thickness of the material layer is an index of the rigidity of the material layer. Such a configuration relating to the rigidity of the surface layer materials 11 and 12 is the same as that of the resin sheet 10 with the surface layer material in the form of a roll. Helps reduce wrinkles.

  As described above, the innermost diameter R of the resin sheet 10 with a surface layer material in the form of a roll is preferably 15 cm or less, more preferably 10 cm or less, and more preferably 8 cm or less. Although the compressive stress received by the surface layer material 11 on the inner diameter side tends to increase as the outermost inner diameter R of the resin sheet 10 with surface layer material decreases, the resin sheet 10 with surface layer material relaxes the compressive stress received by the surface layer material 11. A structure suitable for suppressing the generation of wrinkles in the surface material 11, that is, a structure in which the surface material 12 has a smaller storage elastic modulus than the surface material 11 and is soft as described above. It is.

[Example 1]

<Preparation of adhesive solution>
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 100 mol of 2-ethylhexyl acrylate (2EHA), 20 mol of 2-hydroxyethyl acrylate (HEA), and 100 parts by mass of these monomer components A mixture containing 0.2 part by mass of benzoyl peroxide as a polymerization initiator and toluene as a polymerization solvent was stirred at 60 ° C. for 6 hours in a nitrogen atmosphere (polymerization reaction). Subsequently, the mixture was stirred at 78 ° C. for 2 hours under a nitrogen atmosphere (aging). To the reaction solution containing the acrylic polymer thus obtained, 16 mol of 2-methacryloyloxyethyl isocyanate (MOI) was added and stirred at 50 ° C. for 8 hours in an air atmosphere (addition reaction). Thereby, a polymer solution containing an acrylic polymer to which MOI was added was obtained. The weight average molecular weight (Mw) of the acrylic polymer in the polymer solution was about 1.0 × 10 ⁶ . Then, 0.1 parts by mass of a polyisocyanate compound (trade name “Coronate L”, manufactured by Tosoh Corporation) and 0.5 parts by mass with respect to 100 parts by mass of the acrylic polymer to which MOI is added. The photopolymerization initiator (trade name “Irgacure 369”, manufactured by BASF) was added and mixed to obtain an adhesive solution (adhesive solution S).

<Production of laminated sheet>
The pressure-sensitive adhesive solution S obtained as described above is applied onto the silicone-treated surface of the PET separator as the first surface layer material to form a coating film, and this coating film is heated and dried at 120 ° C. for 2 minutes. And a 200 μm thick resin layer (adhesive layer) was formed. Next, the LDPE separator as the second surface layer material was bonded to the resin layer on the first surface layer material, and the laminate sheet was produced through storage at 23 ° C. for 72 hours. The PET separator used in this example was subjected to corona treatment on one side of a polyethylene terephthalate separator (trade name “Lumirror S10 # 50”, thickness 0.05 mm, manufactured by Toray Industries, Inc.), and then applied to the corona treatment surface. On the other hand, it was produced by applying a silicone treatment with a silicone release agent (trade name “KS-3601”, manufactured by Shin-Etsu Silicone). The LDPE separator used in this example was subjected to corona treatment on one side of a 55 μm thick film formed by low-density polyethylene (trade name “Petrocene LW01”, manufactured by Tosoh Corporation) by a T-die extrusion method. The corona-treated surface was prepared by applying a silicone treatment with a silicone release agent (trade name “X-62-7622”, manufactured by Shin-Etsu Silicone).

<Wound>
The laminated sheet obtained as described above has a cylindrical separator (outer diameter is 3 inches, made of acrylonitrile-butadiene-styrene copolymer), and a PET separator (first surface layer material) is provided on the inner diameter side surface layer material. It was wrapped so that In this winding, the winding tension was 120 N, the winding speed was 20 m / min, and the winding length was 10 m. As described above, the resin sheet with a surface layer material of Example 1 was produced.

[Example 2]
A roll-shaped resin sheet with a surface material of Example 2 was produced in the same manner as the resin sheet with a surface material of Example 1 except that an EVA separator was used instead of the LDPE separator as the second surface material. The EVA separator used in the present example is a 0.115 mm thick film formed by T-die extrusion from an ethylene-vinyl acetate copolymer (trade name “Evaflex P1007”, manufactured by Mitsui DuPont Polychemical Co., Ltd.). After the corona treatment was performed on one surface of the film, the corona treatment surface was subjected to silicone treatment with a silicone release agent (trade name “X-62-7622”, manufactured by Shin-Etsu Silicone).

Example 3
Other than using a PET separator having a thickness of 0.125 mm instead of the above-described PET separator having a thickness of 0.05 mm as the first surface layer material, and using a PO separator instead of the LDPE separator as the second surface layer material Produced the roll-shaped resin sheet with the surface layer material of Example 3 in the same manner as the resin sheet with the surface layer material of Example 1. The PET separator used in this example was subjected to corona treatment on one side of a polyethylene terephthalate separator (trade name “Lumirror S10 # 125”, thickness 0.125 mm, manufactured by Toray Industries, Inc.), and then applied to the corona treatment surface. On the other hand, it was produced by applying a silicone treatment with a silicone release agent (trade name “KS-3601”, manufactured by Shin-Etsu Silicone). The PO separator used in this example is a polypropylene random copolymer (trade name “Wintech WFX4M”, manufactured by Nippon Polypro Co., Ltd.) and an amorphous polypropylene (trade name “Tough Selenium H5002”, manufactured by Sumitomo Chemical Co., Ltd.). ) After corona treatment was applied to one side of a 0.08 mm thick film formed by T-die extrusion from a resin material obtained by mixing 40 parts by mass with a dry blend method, It is produced by applying a silicone treatment with a silicone release agent (trade name “X-62-7622”, manufactured by Shin-Etsu Silicone).

Example 4
In the same manner as in the resin sheet with a surface layer material of Example 1, except that a PET separator having a thickness of 0.038 mm was used instead of the PET separator having a thickness of 0.05 mm as the first surface layer material, A roll-shaped resin sheet with a surface layer material was produced. The PET separator used in this example was subjected to corona treatment on one side of a polyethylene terephthalate separator (trade name “Lumirror S10 # 38”, thickness 0.125 mm, manufactured by Toray Industries, Inc.), and then applied to the corona-treated surface. On the other hand, it was produced by applying a silicone treatment with a silicone release agent (trade name “KS-3601”, manufactured by Shin-Etsu Silicone).

Example 5
Except that the PET separator having a thickness of 0.038 mm was used instead of the above-described PET separator having a thickness of 0.05 mm as the first surface layer material, and that the thickness of the resin layer was changed to 300 μm instead of 200 μm, A roll-shaped resin sheet with a surface layer material of Example 5 was produced in the same manner as the resin sheet with a surface layer material of Example 1. The PET separator used in this example was prepared in the same manner as the PET separator used in Example 4.

[Examples 6 to 8]
Except that the thickness of the resin layer was changed to 100 μm (Example 6), 300 μm (Example 7), or 500 μm (Example 8) instead of 200 μm, it was the same as the resin sheet with a surface layer material of Example 1. The roll-shaped resin sheet with each surface layer material of Examples 6-8 was produced.

Example 9
Conducted in the same manner as the resin sheet with a surface material of Example 1 except that the thickness of the resin layer was changed to 300 μm instead of 200 μm, and an rPP separator was used instead of the LDPE separator as the second surface material. The roll-shaped resin sheet with a surface layer material of Example 9 was produced. The rPP separator used in this example is a corona on one side of a 0.055 mm thick film formed by a T-die extrusion method from a polypropylene random copolymer (trade name “Wintech WFX4M”, manufactured by Nippon Polypro Co., Ltd.). After the treatment, the corona-treated surface was prepared by silicone treatment with a silicone release agent (trade name “X-62-7622”, manufactured by Shin-Etsu Silicone).

Example 10
A roll-shaped resin sheet with a surface material of Example 10 was produced in the same manner as the resin sheet with a surface material of Example 1 except that an OPP separator was used instead of the LDPE separator as the second surface material. The OPP separator used in this example was subjected to corona treatment on one side of a biaxially stretched polypropylene film (trade name “Trephan 2500H”, thickness 0.06 mm, manufactured by Toray Industries, Inc.), and then applied to the corona-treated surface. On the other hand, it was produced by applying a silicone treatment with a silicone release agent (trade name “X-62-7622”, manufactured by Shin-Etsu Silicone).

Example 11
A roll-shaped resin sheet with a surface material of Example 10 was produced in the same manner as the resin sheet with a surface material of Example 1 except that a CPP separator was used instead of the LDPE separator as the second surface material. The CPP separator used in the present example was subjected to corona treatment on one side of a 0.1 mm-thick film formed from polypropylene (trade name “Noblen FLX80E4”, manufactured by Sumitomo Chemical Co., Ltd.) by a T-die extrusion method. The corona-treated surface was prepared by applying a silicone treatment with a silicone release agent (trade name “X-62-7622”, manufactured by Shin-Etsu Silicone).

[Comparative Example 1]
Other than using a PET separator having a thickness of 0.038 mm instead of the above-described PET separator having a thickness of 0.05 mm as the first surface layer material, and using a PET separator instead of the LDPE separator as the second surface layer material Produced a roll-shaped resin sheet with a surface layer material of Example 9 in the same manner as the resin sheet with a surface layer material of Example 1. The PET separator as the first surface layer material used in this comparative example was produced in the same manner as the PET separator used in Example 4. The PET separator as the second surface layer material used in this comparative example was subjected to corona treatment on one side of a polyethylene terephthalate separator (trade name “Lumirror S10 # 100”, thickness 0.1 mm, manufactured by Toray Industries, Inc.). The corona-treated surface was prepared by applying a silicone treatment with a silicone release agent (trade name “KS-3601”, manufactured by Shin-Etsu Silicone).

[Storage modulus of adhesive layer]
Based on the dynamic viscoelasticity measurement performed using a dynamic viscoelasticity measuring device (trade name “RSA III”, manufactured by TA Instruments) for each separator and each resin layer in the above Examples and Comparative Examples, 25 ° C. The storage elastic modulus was determined. A test piece to be subjected to dynamic viscoelasticity measurement was prepared by cutting out from a separator or a resin layer in a size of 30 mm in length × 10 mm in width (the resin layer was prepared in an uncured state). In this measurement, the distance between chucks of the sample piece holding chuck is 20 mm, the measurement mode is the tension mode, the measurement temperature range is −30 ° C. to 100 ° C., the frequency is 1 Hz, the strain is 0.1%, The heating rate was 5 ° C./min. The obtained storage elastic modulus (25 ° C.) is listed in Table 1. For each separator and each resin layer, the product of the storage elastic modulus at 25 ° C. and the thickness (index of rigidity) is also listed in Table 1. For each resin sheet with a surface layer material, the value of the ratio of the storage elastic modulus (G2) at 25 ° C. of the second surface layer material to the storage elastic modulus (G1) at 25 ° C. of the first surface layer material is also listed in Table 1. In addition, for each resin sheet with a surface layer material, the product (G1 × T1) of the storage elastic modulus (G1) and the thickness (T1) at 25 ° C. in the first surface layer material at 25 ° C. in the second surface layer material The value of the ratio of the product (G2 × T2) of the storage elastic modulus (G2) and the thickness (T2) is also listed in Table 1.

[Occurrence of wrinkles]
Each resin sheet with a surface layer material in Examples and Comparative Examples was examined for wrinkles. Specifically, the case where wrinkles did not occur was evaluated as excellent (◎), and the case where wrinkles occurred more than one week after the production of the resin sheet with the surface layer material (when wound) is good. The case where wrinkles occurred immediately after winding was evaluated as defective (x). The evaluation results are listed in Table 1.

[Evaluation]
In the resin sheet with a surface layer material of Examples 1 to 11 having the configuration of the present invention, generation of wrinkles was suppressed as compared with the resin sheet with a surface material of Comparative Example 1.

10 Resin sheet with surface material 11 Surface material (first surface material)
12 Surface material (2nd surface material)
13 Resin layer C Winding core R Inner diameter

Claims (7)

Having a laminated structure including a first surface layer material, a second surface layer material, and a resin layer located between the first and second surface layer materials;
The first surface layer material has a storage elastic modulus at 25 ° C. larger than 1 × 10 ⁷ Pa,
The second surface layer material has a storage elastic modulus at 25 ° C. of 1 × 10 ⁷ Pa or more and smaller than the storage elastic modulus of the first surface layer material,
The resin layer has a storage elastic modulus at 25 ° C. of 5 × 10 ⁵ Pa or less,
The resin sheet with a surface layer material in which the second surface layer material is in the form of a roll positioned on the outer diameter side of the first surface layer material in the laminated structure.   The resin sheet with a surface layer material according to claim 1, wherein the resin layer is an adhesive layer.   The resin sheet with a surface layer material according to claim 1, wherein the resin layer has a thickness of 100 μm or more.   The resin sheet with a surface layer material according to any one of claims 1 to 3, wherein the first surface layer material and / or the second surface layer material is a separator.   The resin with a surface layer material according to any one of claims 1 to 4, wherein a value of a ratio of the storage elastic modulus of the second surface layer material to the storage elastic modulus of the first surface layer material is 0.6 or less. Sheet.   The value of the ratio of the product of the storage elastic modulus and thickness of the second surface layer material to the product of the storage elastic modulus and thickness of the first surface layer material is 0.7 or less. A resin sheet with a surface layer material according to any one of the above.   The resin sheet with a surface layer material according to any one of claims 1 to 6, wherein the roll has an innermost diameter of 15 cm or less.

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