WO2013141215A1 - Film to be applied to window - Google Patents

Film to be applied to window Download PDF

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Publication number
WO2013141215A1
WO2013141215A1 PCT/JP2013/057697 JP2013057697W WO2013141215A1 WO 2013141215 A1 WO2013141215 A1 WO 2013141215A1 JP 2013057697 W JP2013057697 W JP 2013057697W WO 2013141215 A1 WO2013141215 A1 WO 2013141215A1
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Prior art keywords
film
adhesive layer
pressure
window
sensitive adhesive
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PCT/JP2013/057697
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French (fr)
Japanese (ja)
Inventor
弘司 難波
Original Assignee
株式会社 きもと
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Publication of WO2013141215A1 publication Critical patent/WO2013141215A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a window pasting film having a support, an adhesive layer, and a separator in this order.
  • Patent Document 1 discloses a scattering prevention pressure-sensitive adhesive sheet having a hard coat layer on the surface opposite to the pressure-sensitive adhesive layer of the base film, and prevents the hard coat layer from being lifted off when the pressure-sensitive adhesive sheet is punched. Therefore, it is described that the storage elastic modulus (0 ° C.) of the pressure-sensitive adhesive is within a predetermined range.
  • the window pasting film is usually provided with an adhesive layer on the support, and then the adhesive layer and the separator are bonded together, wound up in a roll shape, and stored.
  • an object of this invention is to provide the film for window sticking which can reduce
  • the present inventors have found the following. First, it is found that the crater of the adhesive layer is generated in the adhesive layer located closer to the winding core when it is wound and stored in a roll shape, but is not generated in the adhesive layer closer to the roll surface layer. It was. The difference depending on the location of crater generation is thought to be due to the difference in pressure applied to the adhesive layer between the roll core side and the surface layer side, and the pressure applied to the adhesive layer and crater generation in the roll state As a result, it was found that when pressure is applied to the adhesive layer, the adhesive layer is deformed to generate craters. And it discovered that by making the hardness of an adhesion layer into a specific hardness, it was possible to resist the pressure in the roll state and prevent the occurrence of craters without reducing the function as the adhesion layer.
  • the window pasting film of the present invention has a support, an adhesive layer, and a separator in this order, and the storage elastic modulus at 20 ° C. of the adhesive layer is 4.5 ⁇ 10 4 Pa or more. Is.
  • the film for window pasting of this invention Preferably, the storage elastic modulus in 20 degreeC of the said adhesion layer is 2.0 * 10 ⁇ 5 > Pa or less, It is characterized by the above-mentioned.
  • the window pasting film of the present invention is preferably characterized in that it has a functional layer on the surface opposite to the surface having the adhesive layer of the support.
  • the window pasting film of the present invention reduces the occurrence of craters in the adhesive layer and can exhibit a good appearance when wound and stored in a roll shape. .
  • the film for window pasting of this invention has a support body, an adhesion layer, and a separator in this order, and the storage elastic modulus in 20 degreeC of the said adhesion layer is 4.5x10 ⁇ 4 > Pa or more, It is characterized by the above-mentioned. is there.
  • the storage elastic modulus in 20 degreeC of the said adhesion layer is 4.5x10 ⁇ 4 > Pa or more, It is characterized by the above-mentioned. is there.
  • embodiments of each component will be described.
  • the support used in the window pasting film of the present invention includes a plastic film.
  • the plastic film include polyester, polycarbonate, acrylic, triacetyl cellulose, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyamide, polyimide, vinylidene chloride-vinyl chloride copolymer, and the like.
  • Such a support may contain various commonly used ultraviolet absorbers, antioxidants, anti-aging agents, slip agents, etc., or may have a layer containing these separately. .
  • the thickness of the support varies depending on the application used, it cannot be generally stated, but is preferably 10 ⁇ m to 350 ⁇ m, more preferably 30 ⁇ m to 188 ⁇ m.
  • the adhesive layer is laminated on one surface of the support and has a hardness that does not deform with a predetermined pressure.
  • Predetermined pressure is the pressure applied to the core in the state of being wound and stored in a roll, and it varies depending on the diameter of the roll and the diameter of the core, but specifically about 10 kg to 30 kg relative to the roll width. This is a pressure generated when a winding tension of 1 is applied.
  • the adhesive layer has a storage elastic modulus at 20 ° C. of 4.5 ⁇ 10 4 Pa or more, preferably 4.9 ⁇ 10 4 Pa or more, more preferably 5.3 ⁇ 10 4 Pa or more.
  • the storage elastic modulus at 20 ° C. of the adhesive layer is preferably 2.0 ⁇ 10 5 Pa or less, more preferably 1.8 ⁇ 10 5 or less, and further preferably 1.6 ⁇ 10 5 or less.
  • the storage elastic modulus at 20 ° C. of the adhesive layer is 2.0 ⁇ 10 5 Pa or less, sufficient adhesive force is easily obtained.
  • the storage elastic modulus (20 degreeC) of the adhesion layer mentioned above can be prepared by adjusting the adhesive which comprises an adhesion layer, its molecular weight, and an additive. Moreover, when forming an adhesion layer by application
  • materials will be described.
  • the pressure-sensitive adhesive a natural resin-based pressure-sensitive adhesive, a synthetic resin-based pressure-sensitive adhesive, or the like is used, and a synthetic resin-based pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or a urethane-based pressure-sensitive adhesive is preferably used. Among these, a crosslinkable acrylic pressure-sensitive adhesive that has weather resistance and is easy to handle is preferably used.
  • the storage elastic modulus of the pressure-sensitive adhesive itself tends to increase when the molecular weight of the pressure-sensitive adhesive is large, and decreases when the molecular weight is small.
  • the lower limit of the weight average molecular weight of the pressure-sensitive adhesive is preferably 300,000 or more, more preferably 400,000 or more, further preferably 500,000 or more
  • the upper limit is preferably 900,000 or less, more preferably 800,000 or less, and more preferably 700,000 or less. preferable.
  • the storage elastic modulus at 20 ° C. of the adhesive layer can be easily adjusted to 4.5 ⁇ 10 4 Pa or more.
  • the storage elastic modulus of the adhesive itself when the storage elastic modulus of the adhesive itself is low, the storage elastic modulus can be increased by using a crosslinking agent. Furthermore, the storage elastic modulus can be increased by using a crosslinking accelerator in addition to the crosslinking agent.
  • an isocyanate crosslinking agent an epoxy crosslinking agent, an imine crosslinking agent, a metal chelate, or the like can be used.
  • a suitable ratio of the pressure-sensitive adhesive and the crosslinking agent is such that the lower limit of the crosslinking agent is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and 0.4 parts by weight or more with respect to 100 parts by weight of the pressure-sensitive adhesive.
  • the upper limit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 1 part by weight or less.
  • the crosslinking agent component By setting the crosslinking agent component to 0.01 parts by weight or more, the storage elastic modulus at 20 ° C. of the adhesive layer can be adjusted to 4.5 ⁇ 10 4 Pa or more. On the other hand, when the amount is 10 parts by weight or less, the adhesive strength is excellent.
  • the crosslinking accelerator a tin-based crosslinking accelerator, an aluminum-based crosslinking accelerator, or the like can be used.
  • the suitable ratio of the crosslinking agent and the crosslinking accelerator is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and more preferably 5 parts by weight or more at the lower limit of the crosslinking accelerator component with respect to 100 parts by weight of the crosslinking agent component.
  • the upper limit is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 10 parts by weight or less.
  • the amount of the pressure-sensitive adhesive layer can be adjusted to 4.5 ⁇ 10 4 Pa or more.
  • the amount is 50 parts by weight or less, the increase in the viscosity of the liquid containing the pressure-sensitive adhesive, the crosslinking agent, and the crosslinking accelerator is reduced, and coating becomes easy.
  • the thickness of the adhesive layer is not particularly limited, it is preferably 2 ⁇ m to 60 ⁇ m and more preferably 5 ⁇ m to 40 ⁇ m in consideration of the sticking property to the adherend of the film for window pasting, peelability and the like. If it is 5 ⁇ m or less, the tackiness is unstable, and if it is 40 ⁇ m or more, the pressure-sensitive adhesive protrudes from the side of the film, resulting in inconvenience in handling.
  • crosslinking agents and crosslinking accelerators in addition to adhesives, crosslinking agents and crosslinking accelerators, retarders, pigments, dyes, colorants, matting agents, antistatic agents, flame retardants, fungicides, rust inhibitors, antibacterial agents, UV absorption Additives such as additives, light stabilizers, heat stabilizers, antioxidants, plasticizers, leveling agents, flow regulators, antifoaming agents, dispersants, optical brighteners, storage stabilizers, silane coupling agents, etc. May be. However, the addition amount of these additives is preferably in a range that does not hinder the effect of the adhesive layer.
  • the pressure-sensitive adhesive layer is generally a coating solution obtained by dissolving or dispersing the above pressure-sensitive adhesive, a crosslinking agent and / or crosslinking accelerator added as necessary, and other additives in a solvent as necessary. Is formed by coating and drying on a support by a known coating method. In addition, if the adhesive layer is heated at 60 to 130 ° C. for 12 to 48 hours as necessary after coating and drying, the storage elastic modulus at 20 ° C. of the adhesive layer can be adjusted to 4.5 ⁇ 10 4 Pa or more.
  • the film for window pasting of the present invention has a configuration in which an adhesive layer is laminated on one surface of a support and the adhesive layer and a separator are bonded together.
  • Polyester, polyethylene, polypropylene, paper, etc. can be used as the separator base material to be bonded to the adhesive layer.
  • a separator using such a substrate is difficult to peel from the adhesive layer, it is preferable to provide a release treatment layer on the surface in contact with the adhesive layer.
  • a resin having good release properties such as fluorine and silicone, or a release agent such as silicone oil is mixed with the resin, and dissolved or dispersed in a solvent to form a coating solution.
  • the liquid can be formed by coating and drying by a known coating method.
  • an adhesive layer is formed on one surface of a support, and the surface on which the adhesive layer is formed and the surface on which the release treatment layer of the separator is formed are laminated. To do.
  • a structure having a functional layer on the surface opposite to the surface on which the adhesive layer is laminated of the support used for the window pasting film of the present invention is preferable.
  • the functional layer examples include a cured film for an anti-scratch film, a photocatalytic layer containing a photocatalytic material for a self-cleaning film such as a photocatalytic film, an ultraviolet absorbing layer for an ultraviolet absorbing film, and an infrared ray for an infrared absorbing film. If it is an absorption layer or a decorative film, there is an image receiving layer, if it is a colored film, there is a colored layer, and if it is a fogging-preventing film, there is an antifogging layer. These can use a well-known thing according to a use application.
  • a cured film will be described as an example of the functional layer.
  • the resin constituting the cured film it is preferable to use a curable resin such as a thermosetting resin having good transparency and an ionizing radiation curable resin.
  • thermosetting resins and ionizing radiation curable resins include polyester resins, acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, urethane resins, epoxy resins, It is composed of polycarbonate resin, melamine resin, phenol resin, silicone resin, fluorine resin and the like.
  • thermoplastic resin may be mixed with these curable resins. By adding a thermoplastic resin, the hardness of the cured film can be adjusted.
  • thermoplastic resin examples include acrylic resins, polyester resins, cellulose resins, vinyl resins, polyethylene resins, polystyrene resins, and polypropylene resins. These resins can be used alone or in combination.
  • an ultraviolet absorber, an infrared absorber, or the like can be added, whereby an ultraviolet absorbing function or an infrared absorbing function can be imparted in addition to the scratch preventing function.
  • the formed sheet sample was hollowed out into a cylindrical shape having a diameter of 25 mm, and a test piece having a diameter of 25 mm and a thickness of 600 ⁇ m consisting of only an adhesive layer was prepared. And the storage elastic modulus at 20 degrees C of the adhesion layer was measured for the test piece at the frequency of 1 Hz by the torsional shear method using the viscoelasticity measuring apparatus (PhysicaMCR301: Anton Paar).
  • the film for window pasting of Examples 1 and 2 has a storage elastic modulus at 20 ° C. of 4.5 ⁇ 10 4 Pa or more of the adhesive layer, and the number of craters generated in the adhesive layer is less than 1 / m 2 . Appearance was good. Moreover, sufficient adhesive force was acquired because the storage elastic modulus in 20 degreeC of an adhesion layer is 2.0 * 10 ⁇ 5 > Pa or less.
  • the film for window pasting of Comparative Examples 1 and 2 has a storage elastic modulus of 4.5 ⁇ 10 4 Pa or less at 20 ° C. of the adhesive layer, and the number of craters generated in the adhesive layer is 1 / m 2. As a result, the appearance was poor.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A film which is to be applied to a window and which bears a substrate, a pressure-sensitive adhesive layer and a separator in this order, wherein the pressure-sensitive adhesive layer exhibits a storage modulus of 4.5×104 to 2.0×105 Pa at 20°C. The film may further bear a functional layer such as a hard coat on the reverse surface of the substrate, namely, on the surface thereof that is reverse to the surface on which the pressure-sensitive adhesive layer is present. The pressure-sensitive adhesive layer of the film suffers little cratering, namely, forms few dents or depressions even when the film is stored in the form of a roll. Therefore, the film can attain good surface appearance when applied to a window.

Description

窓貼り用フィルムWindow pasting film
　本発明は、支持体、粘着層、セパレータをこの順に有する窓貼り用フィルムに関する。 The present invention relates to a window pasting film having a support, an adhesive layer, and a separator in this order.
　近年、建物の窓ガラス面に貼合する窓貼り用フィルムが多く利用されている。これらは、紫外線や赤外線の進入を防ぐ、ガラスに着色や装飾を施す、ガラスが割れたときの飛散を防止する、侵入者がガラスを割ることができないようにする、などの目的で貼られている。 In recent years, many films for pasting windows that are bonded to the window glass of buildings have been used. These are affixed for the purpose of preventing the entry of ultraviolet rays and infrared rays, coloring and decorating the glass, preventing scattering when the glass breaks, and preventing intruders from breaking the glass. Yes.
　このような窓貼り用フィルムは、基本的に、基材フィルムの上に粘着層が形成された粘着シートの構造を有している（特許文献１）。特許文献１には、基材フィルムの粘着層と反対の面にハードコート層を備えた飛散防止用粘着シートが開示され、この粘着シートを抜き加工する際に、ハードコート層の浮き剥がれを防止するため粘着剤の貯蔵弾性率（０℃）を所定の範囲にすることが記載されている。 Such a window pasting film basically has an adhesive sheet structure in which an adhesive layer is formed on a base film (Patent Document 1). Patent Document 1 discloses a scattering prevention pressure-sensitive adhesive sheet having a hard coat layer on the surface opposite to the pressure-sensitive adhesive layer of the base film, and prevents the hard coat layer from being lifted off when the pressure-sensitive adhesive sheet is punched. Therefore, it is described that the storage elastic modulus (0 ° C.) of the pressure-sensitive adhesive is within a predetermined range.
特開２０１１－１６８６５２号公報（請求項１）JP 2011-168652 A (Claim 1)
　ところで窓貼り用フィルムは、窓ガラスへの貼合作業を容易にするため、通常、支持体に粘着層を設けた後、その粘着層とセパレータとを貼り合せ、ロール状に巻き取り、保管される。窓ガラスに貼合する際に、セパレータを粘着層から剥がしながら、粘着層を窓ガラスに密着させ貼合している。 By the way, in order to facilitate the pasting operation to the window glass, the window pasting film is usually provided with an adhesive layer on the support, and then the adhesive layer and the separator are bonded together, wound up in a roll shape, and stored. The When bonding to the window glass, the pressure-sensitive adhesive layer is adhered to the window glass and bonded while peeling the separator from the pressure-sensitive adhesive layer.
　このようなロール状に巻き取られた窓貼り用フィルムでは、粘着層の塗膜にクレーターと呼ばれる、へこみや、くぼみが発生し、外観不良となる問題を生じている。
　そこで本発明は、粘着層のクレーターの発生を低減し、良好な外観を呈することができる窓貼り用フィルムを提供することを目的とする。 In such a window pasting film wound up in a roll shape, a dent or a dent called a crater is generated in the coating film of the adhesive layer, resulting in a problem of poor appearance.
Then, an object of this invention is to provide the film for window sticking which can reduce | generate the generation | occurrence | production of the crater of an adhesion layer, and can exhibit a favorable external appearance.
　本発明者らは上記課題を解決すべく鋭意研究した結果、次のことを見出した。まず粘着層のクレーターは、ロール状に巻き取り保管している際に、巻き芯に近いほうに位置する粘着層には発生するが、ロール表層に近いほうの粘着層には発生しないことが判った。このようなクレーター発生の場所による違いは、ロールの巻き芯側と表層側とで粘着層にかかる圧力に差があることに起因すると考え、ロール状の状態において粘着層にかかる圧力とクレーターの発生の関係を検討したところ、粘着層に圧力がかかると、粘着層が変形することによって、クレーターが発生することが判った。そして粘着層の硬さを特定の硬さとすることにより、粘着層としての機能を低下させることなく、ロール状態の圧力に抗しクレーターの発生を防止しうることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found the following. First, it is found that the crater of the adhesive layer is generated in the adhesive layer located closer to the winding core when it is wound and stored in a roll shape, but is not generated in the adhesive layer closer to the roll surface layer. It was. The difference depending on the location of crater generation is thought to be due to the difference in pressure applied to the adhesive layer between the roll core side and the surface layer side, and the pressure applied to the adhesive layer and crater generation in the roll state As a result, it was found that when pressure is applied to the adhesive layer, the adhesive layer is deformed to generate craters. And it discovered that by making the hardness of an adhesion layer into a specific hardness, it was possible to resist the pressure in the roll state and prevent the occurrence of craters without reducing the function as the adhesion layer.
　すなわち、本発明の窓貼り用フィルムは、支持体、粘着層、セパレータをこの順に有し、前記粘着層の２０℃における貯蔵弾性率が４．５×１０４Ｐａ以上であることを特徴とするものである。 That is, the window pasting film of the present invention has a support, an adhesive layer, and a separator in this order, and the storage elastic modulus at 20 ° C. of the adhesive layer is 4.5 × 10 4 Pa or more. Is.
　また、本発明の窓貼り用フィルムは、好ましくは、前記粘着層の２０℃における貯蔵弾性率が２．０×１０５Ｐａ以下であることを特徴とするものである。 Moreover, the film for window pasting of this invention, Preferably, the storage elastic modulus in 20 degreeC of the said adhesion layer is 2.0 * 10 < 5 > Pa or less, It is characterized by the above-mentioned.
　また、本発明の窓貼り用フィルムは、好ましくは、前記支持体の粘着層を有する面の反対面に機能層を有することを特徴とするものである。 The window pasting film of the present invention is preferably characterized in that it has a functional layer on the surface opposite to the surface having the adhesive layer of the support.
　本発明の窓貼り用フィルムは、特定の貯蔵弾性率の粘着層を用いることにより、ロール状に巻き取り保管した際に、粘着層でのクレーターの発生が低減し良好な外観を呈することができる。 By using an adhesive layer having a specific storage modulus, the window pasting film of the present invention reduces the occurrence of craters in the adhesive layer and can exhibit a good appearance when wound and stored in a roll shape. .
　本発明の窓貼り用フィルムは、支持体、粘着層、セパレータをこの順に有し、前記粘着層の２０℃における貯蔵弾性率が４．５×１０４Ｐａ以上であることを特徴とするものである。以下、各構成要素の実施の形態について説明する。 The film for window pasting of this invention has a support body, an adhesion layer, and a separator in this order, and the storage elastic modulus in 20 degreeC of the said adhesion layer is 4.5x10 < 4 > Pa or more, It is characterized by the above-mentioned. is there. Hereinafter, embodiments of each component will be described.
　本発明の窓貼り用フィルムに用いる支持体としては、プラスチックフィルムがあげられる。プラスチックフィルムとしては、ポリエステル、ポリカーボネート、アクリル、トリアセチルセルロース、ポリプロピレン、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリアミド、ポリイミド、塩化ビニリデン－塩化ビニル共重合体等があげられる。また、このような支持体は、通常用いられる各種紫外線吸収剤、酸化防止剤、老化防止剤、スリップ剤等が含有されたものでも良く、別途これらを含有する層を有するものであっても良い。 The support used in the window pasting film of the present invention includes a plastic film. Examples of the plastic film include polyester, polycarbonate, acrylic, triacetyl cellulose, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyamide, polyimide, vinylidene chloride-vinyl chloride copolymer, and the like. Such a support may contain various commonly used ultraviolet absorbers, antioxidants, anti-aging agents, slip agents, etc., or may have a layer containing these separately. .
　支持体の厚みは使用する用途によって異なるので一概にいえないが、１０μｍ～３５０μｍが好ましく、３０μｍ～１８８μｍがより好ましい。 Although the thickness of the support varies depending on the application used, it cannot be generally stated, but is preferably 10 μm to 350 μm, more preferably 30 μm to 188 μm.
　粘着層は、支持体の一方の面に積層されており、所定の圧力に対し変形しない硬さを備えている。所定の圧力とは、ロール状に巻き取り保管した状態で巻き芯側にかかる圧力であり、ロールの径や巻き芯の径によっても異なるが、具体的にはロール巾に対して１０ｋｇ～３０ｋｇ程度の巻き取り張力が付加された場合に生じる圧力である。 The adhesive layer is laminated on one surface of the support and has a hardness that does not deform with a predetermined pressure. Predetermined pressure is the pressure applied to the core in the state of being wound and stored in a roll, and it varies depending on the diameter of the roll and the diameter of the core, but specifically about 10 kg to 30 kg relative to the roll width. This is a pressure generated when a winding tension of 1 is applied.
　このような硬さとするため、粘着層は、２０℃における貯蔵弾性率が４．５×１０４Ｐａ以上、好ましくは４．９×１０４Ｐａ以上、より好ましくは５．３×１０４Ｐａ以上とする。支持体にこのような粘着層を設けることにより、その粘着層とセパレータとを貼り合せ、ロール状に巻き取り保管した際に、粘着層でのクレーターの発生が低減し良好な外観を呈することができる。 In order to obtain such hardness, the adhesive layer has a storage elastic modulus at 20 ° C. of 4.5 × 10 4 Pa or more, preferably 4.9 × 10 4 Pa or more, more preferably 5.3 × 10 4 Pa or more. And By providing such a pressure-sensitive adhesive layer on the support, the adhesive layer and the separator are bonded together, and when wound and stored in a roll, the occurrence of craters in the pressure-sensitive adhesive layer is reduced and a good appearance may be exhibited. it can.
　また、粘着層の２０℃における貯蔵弾性率は２．０×１０５Ｐａ以下が好ましく、１．８×１０５以下がより好ましく、１．６×１０５以下がさらに好ましい。粘着層の２０℃における貯蔵弾性率が２．０×１０５Ｐａ以下であることにより、十分な粘着力が得られ易くなる。 Moreover, the storage elastic modulus at 20 ° C. of the adhesive layer is preferably 2.0 × 10 5 Pa or less, more preferably 1.8 × 10 5 or less, and further preferably 1.6 × 10 5 or less. When the storage elastic modulus at 20 ° C. of the adhesive layer is 2.0 × 10 5 Pa or less, sufficient adhesive force is easily obtained.
　上述した粘着層の貯蔵弾性率（２０℃）は、粘着層を構成する粘着剤とその分子量及び添加剤を調整することにより調製することができる。また粘着層を塗布、乾燥によって形成する際に、加熱工程を追加することによっても調整することができる。まず材料について説明する。
　粘着剤としては天然樹脂系粘着剤、合成樹脂系粘着剤等が使用され、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤等の合成樹脂系粘着剤が好ましく使用される。なかでも、耐候性を有し取り扱いの容易な架橋性のアクリル系粘着剤が好ましく用いられる。 The storage elastic modulus (20 degreeC) of the adhesion layer mentioned above can be prepared by adjusting the adhesive which comprises an adhesion layer, its molecular weight, and an additive. Moreover, when forming an adhesion layer by application | coating and drying, it can also adjust by adding a heating process. First, materials will be described.
As the pressure-sensitive adhesive, a natural resin-based pressure-sensitive adhesive, a synthetic resin-based pressure-sensitive adhesive, or the like is used, and a synthetic resin-based pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or a urethane-based pressure-sensitive adhesive is preferably used. Among these, a crosslinkable acrylic pressure-sensitive adhesive that has weather resistance and is easy to handle is preferably used.
　粘着剤自体の貯蔵弾性率は、粘着剤の分子量が大きいと高くなり、分子量が小さいと低くなる傾向がある。粘着剤の重量平均分子量は、下限は３０万以上が好ましく、４０万以上がより好ましく、５０万以上がさらに好ましく、上限は９０万以下が好ましく、８０万以下がより好ましく、７０万以下がさらに好ましい。粘着剤の重量平均分子量の下限を３０万以上とし、上限を９０万以下することで、粘着層の２０℃における貯蔵弾性率を４．５×１０４Ｐａ以上に調整しやすくできる。 The storage elastic modulus of the pressure-sensitive adhesive itself tends to increase when the molecular weight of the pressure-sensitive adhesive is large, and decreases when the molecular weight is small. The lower limit of the weight average molecular weight of the pressure-sensitive adhesive is preferably 300,000 or more, more preferably 400,000 or more, further preferably 500,000 or more, the upper limit is preferably 900,000 or less, more preferably 800,000 or less, and more preferably 700,000 or less. preferable. By setting the lower limit of the weight average molecular weight of the adhesive to 300,000 or more and the upper limit to 900,000 or less, the storage elastic modulus at 20 ° C. of the adhesive layer can be easily adjusted to 4.5 × 10 4 Pa or more.
　また粘着剤自体の貯蔵弾性率が低い場合には、架橋剤を用いることにより、貯蔵弾性率を高くできる。さらに架橋剤に加えて架橋促進剤を用いることにより、貯蔵弾性率を高くできる。 In addition, when the storage elastic modulus of the adhesive itself is low, the storage elastic modulus can be increased by using a crosslinking agent. Furthermore, the storage elastic modulus can be increased by using a crosslinking accelerator in addition to the crosslinking agent.
　架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、イミン系架橋剤、金属キレート等を用いることができる。粘着剤と架橋剤の好適な割合は、粘着剤１００重量部に対して架橋剤は、下限で０．０１重量部以上が好ましく、０．１重量部以上がより好ましく、０．４重量部以上がさらに好ましく、また上限で１０重量部以下が好ましく、５重量部以下がより好ましく、１重量部以下がさらに好ましい。架橋剤成分を０．０１重量部以上にすることで、粘着層の２０℃における貯蔵弾性率を４．５×１０４Ｐａ以上に調整できる。一方１０重量部以下にすることで接着力に優れたものとなる。 As the crosslinking agent, an isocyanate crosslinking agent, an epoxy crosslinking agent, an imine crosslinking agent, a metal chelate, or the like can be used. A suitable ratio of the pressure-sensitive adhesive and the crosslinking agent is such that the lower limit of the crosslinking agent is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and 0.4 parts by weight or more with respect to 100 parts by weight of the pressure-sensitive adhesive. The upper limit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 1 part by weight or less. By setting the crosslinking agent component to 0.01 parts by weight or more, the storage elastic modulus at 20 ° C. of the adhesive layer can be adjusted to 4.5 × 10 4 Pa or more. On the other hand, when the amount is 10 parts by weight or less, the adhesive strength is excellent.
　架橋促進剤としては、スズ系架橋促進剤、アルミニウム系架橋促進剤等を用いることができる。架橋剤と架橋促進剤の好適な割合は、架橋剤成分１００重量部に対して架橋促進剤成分は、下限で０．１重量部以上が好ましく、１重量部以上がより好ましく、５重量部以上がさらに好ましく、また上限で５０重量部以下が好ましく、４０重量部以下がより好ましく、１０重量部以下がさらに好ましい。架橋促進剤成分を０．１重量部以上にすることで粘着剤と架橋剤の架橋反応が速くなり、粘着層の２０℃における貯蔵弾性率が４．５×１０４Ｐａ以上に調整できる。一方５０重量部以下にすることで、粘着剤、架橋剤と架橋促進剤を配合した液の粘度上昇が少なくなり塗工が容易になる。 As the crosslinking accelerator, a tin-based crosslinking accelerator, an aluminum-based crosslinking accelerator, or the like can be used. The suitable ratio of the crosslinking agent and the crosslinking accelerator is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and more preferably 5 parts by weight or more at the lower limit of the crosslinking accelerator component with respect to 100 parts by weight of the crosslinking agent component. The upper limit is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 10 parts by weight or less. By setting the crosslinking accelerator component to 0.1 parts by weight or more, the crosslinking reaction between the pressure-sensitive adhesive and the crosslinking agent is accelerated, and the storage elastic modulus at 20 ° C. of the pressure-sensitive adhesive layer can be adjusted to 4.5 × 10 4 Pa or more. On the other hand, when the amount is 50 parts by weight or less, the increase in the viscosity of the liquid containing the pressure-sensitive adhesive, the crosslinking agent, and the crosslinking accelerator is reduced, and coating becomes easy.
　粘着層の厚みは特に限定されないが、窓貼り用フィルムの被着体への貼付性、剥離性等を考慮すると、２μｍ～６０μｍが好ましく、５μｍ～４０μｍがより好ましい。５μｍ以下では粘着性が不安定であり、４０μｍ以上では粘着剤がフィルムのわきからはみ出し、取扱い上不都合が生じる。 Although the thickness of the adhesive layer is not particularly limited, it is preferably 2 μm to 60 μm and more preferably 5 μm to 40 μm in consideration of the sticking property to the adherend of the film for window pasting, peelability and the like. If it is 5 μm or less, the tackiness is unstable, and if it is 40 μm or more, the pressure-sensitive adhesive protrudes from the side of the film, resulting in inconvenience in handling.
　粘着層には、粘着剤、架橋剤および架橋促進剤の他、遅延剤、顔料、染料、着色剤、マット剤、帯電防止剤、難燃剤、防カビ剤、防錆剤、抗菌剤、紫外線吸収剤、光安定剤、熱安定剤、酸化防止剤、可塑剤、レベリング剤、流動調整剤、消泡剤、分散剤、蛍光増白剤、貯蔵安定剤、シランカップリング剤等の添加剤を添加してもよい。ただし、これら添加剤の添加量は粘着層の効果を阻害しない範囲であることが望ましい。 In the adhesive layer, in addition to adhesives, crosslinking agents and crosslinking accelerators, retarders, pigments, dyes, colorants, matting agents, antistatic agents, flame retardants, fungicides, rust inhibitors, antibacterial agents, UV absorption Additives such as additives, light stabilizers, heat stabilizers, antioxidants, plasticizers, leveling agents, flow regulators, antifoaming agents, dispersants, optical brighteners, storage stabilizers, silane coupling agents, etc. May be. However, the addition amount of these additives is preferably in a range that does not hinder the effect of the adhesive layer.
　粘着層は、一般には、上記粘着剤、必要に応じて添加される架橋剤および／又は架橋促進剤、その他の添加剤を必要に応じて溶剤に溶解または分散して塗布液とし、この塗布液を公知の塗布方法によって、支持体に塗布、乾燥することによって形成される。また、塗布、乾燥した後に、必要に応じて６０～１３０℃で１２～４８時間加熱すると、粘着層の２０℃における貯蔵弾性率が４．５×１０４Ｐａ以上に調整できる。 The pressure-sensitive adhesive layer is generally a coating solution obtained by dissolving or dispersing the above pressure-sensitive adhesive, a crosslinking agent and / or crosslinking accelerator added as necessary, and other additives in a solvent as necessary. Is formed by coating and drying on a support by a known coating method. In addition, if the adhesive layer is heated at 60 to 130 ° C. for 12 to 48 hours as necessary after coating and drying, the storage elastic modulus at 20 ° C. of the adhesive layer can be adjusted to 4.5 × 10 4 Pa or more.
　本発明の窓貼り用フィルムは、支持体の一方の面に粘着層が積層され、粘着層とセパレータを貼り合わせた構成となっている。 The film for window pasting of the present invention has a configuration in which an adhesive layer is laminated on one surface of a support and the adhesive layer and a separator are bonded together.
　粘着層に貼り合わせるセパレータの基材には、ポリエステル、ポリエチレン、ポリプロピレン、紙等があげられる。このような基材を用いたセパレータが粘着層から剥離しにくい場合には、粘着層と接する面に離型処理層を設けることが好ましい。離型処理層を設ける方法としては、フッ素系、シリコーン系等の離型性の良い樹脂や、シリコーンオイルなどの離型剤を樹脂に混ぜ、溶剤に溶解または分散して塗布液とし、この塗布液を公知の塗布方法によって塗布、乾燥することにより形成することができる。 セ パ レ ー タ Polyester, polyethylene, polypropylene, paper, etc. can be used as the separator base material to be bonded to the adhesive layer. When a separator using such a substrate is difficult to peel from the adhesive layer, it is preferable to provide a release treatment layer on the surface in contact with the adhesive layer. As a method for providing a release treatment layer, a resin having good release properties such as fluorine and silicone, or a release agent such as silicone oil is mixed with the resin, and dissolved or dispersed in a solvent to form a coating solution. The liquid can be formed by coating and drying by a known coating method.
　本発明の窓貼り用フィルムの製造方法は、支持体の一方の面に粘着層を形成し、この粘着層を形成した面と前記セパレータの離型処理層を形成した面とを対向させてラミネートする。 In the method for producing a window pasting film of the present invention, an adhesive layer is formed on one surface of a support, and the surface on which the adhesive layer is formed and the surface on which the release treatment layer of the separator is formed are laminated. To do.
　本発明の窓貼り用フィルムに用いる支持体の、粘着層が積層される面と反対の面には、機能層を有する構成が好ましい。 A structure having a functional layer on the surface opposite to the surface on which the adhesive layer is laminated of the support used for the window pasting film of the present invention is preferable.
　機能層としては、たとえば傷つき防止フィルムであれば硬化膜、光触媒フィルム等のセルフクリーニングフィルムであれば光触媒性材料を含む光触媒層、紫外線吸収フィルムであれば紫外線吸収層、赤外線吸収フィルムであれば赤外線吸収層、装飾用フィルムであれば画像受容層、着色フィルムであれば着色層、くもり防止フィルムであれば防曇層がある。これらは、使用用途に合わせ公知のものを使用できる。 Examples of the functional layer include a cured film for an anti-scratch film, a photocatalytic layer containing a photocatalytic material for a self-cleaning film such as a photocatalytic film, an ultraviolet absorbing layer for an ultraviolet absorbing film, and an infrared ray for an infrared absorbing film. If it is an absorption layer or a decorative film, there is an image receiving layer, if it is a colored film, there is a colored layer, and if it is a fogging-preventing film, there is an antifogging layer. These can use a well-known thing according to a use application.
　機能層の一例として硬化膜について説明する。硬化膜を構成する樹脂としては、透明性の良い熱硬化性樹脂、電離放射線硬化性樹脂などの硬化性樹脂を用いることが好ましい。 A cured film will be described as an example of the functional layer. As the resin constituting the cured film, it is preferable to use a curable resin such as a thermosetting resin having good transparency and an ionizing radiation curable resin.
　熱硬化性樹脂および電離放射線硬化性樹脂としては、例えばポリエステル系樹脂、アクリル系樹脂、アクリルウレタン系樹脂、ポリエステルアクリレート系樹脂、ポリウレタンアクリレート系樹脂、エポキシアクリレート系樹脂、ウレタン系樹脂、エポキシ系樹脂、ポリカーボネート系樹脂、メラミン系樹脂、フェノール系樹脂、シリコーン系樹脂、フッ素系樹脂などで構成される。 Examples of thermosetting resins and ionizing radiation curable resins include polyester resins, acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, urethane resins, epoxy resins, It is composed of polycarbonate resin, melamine resin, phenol resin, silicone resin, fluorine resin and the like.
　また、これら硬化性樹脂に熱可塑性樹脂を混合しても良い。熱可塑性樹脂を加えることにより、硬化膜の硬度を調整することができる。 Further, a thermoplastic resin may be mixed with these curable resins. By adding a thermoplastic resin, the hardness of the cured film can be adjusted.
　また、熱可塑性樹脂としてはアクリル系樹脂、ポリエステル系樹脂、セルロース系樹脂、ビニル系樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、ポリプロピレン系樹脂などがあげられる。これらの樹脂の中から、単独または混合して使用できる。
　このような硬化膜には、紫外線吸収剤や赤外線吸収剤などを添加することもでき、それによって、傷つき防止機能に加えて紫外線吸収機能や赤外線吸収機能を付与することができる。 Examples of the thermoplastic resin include acrylic resins, polyester resins, cellulose resins, vinyl resins, polyethylene resins, polystyrene resins, and polypropylene resins. These resins can be used alone or in combination.
To such a cured film, an ultraviolet absorber, an infrared absorber, or the like can be added, whereby an ultraviolet absorbing function or an infrared absorbing function can be imparted in addition to the scratch preventing function.
　以下、実施例により本発明を更に説明する。なお、「部」、「％」は特に示さない限り、重量基準とする。 Hereinafter, the present invention will be further described with reference to examples. “Parts” and “%” are based on weight unless otherwise specified.
１．窓貼り用フィルムの作製
　支持体として、厚み５０μｍのポリエチレンテレフタレートフィルム（三菱化学ポリエステルフィルム社製、製品名：Ｔ６００Ｅ）の一方の面に、表１の処方の粘着層塗布液（実施例１～２、比較例１～２）をダイコーター法によりそれぞれ塗布し、１００℃、２分間乾燥することにより乾燥膜厚２０μｍの粘着層を形成した。次いで、粘着層を形成した面とセパレータ（三菱化学ポリエステルフィルム社製、製品名：ＭＲＦ）の離型処理面とを貼り合せ、ロール状（巻き芯の直径：１５２ｍｍ、ロールの直径：３９１ｍｍ、ロールの幅：９６０ｍｍ）に巻き取り、実施例１～２および比較例１～２の窓貼り用フィルムを作製した。 1. Preparation of film for window pasting Adhesive layer coating liquids of the formulations shown in Table 1 (Examples 1 and 2) on one side of a 50 μm thick polyethylene terephthalate film (product name: T600E, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) as a support. Comparative Examples 1 and 2) were each applied by a die coater method and dried at 100 ° C. for 2 minutes to form an adhesive layer having a dry film thickness of 20 μm. Next, the surface on which the adhesive layer is formed and the release treatment surface of the separator (product name: MRF, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) are bonded together to form a roll (winding core diameter: 152 mm, roll diameter: 391 mm, roll The film for window pasting of Examples 1-2 and Comparative Examples 1-2 was produced.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
２．評価
　表１の実施例および比較例で得られた窓貼り用フィルムについて、（１）粘着層の２０℃における貯蔵弾性率を測定した。また、（２）粘着層でのクレーターの発生について評価を行った。結果を表２に示す。 2. Evaluation About the film for window pasting obtained by the Example and comparative example of Table 1, (1) The storage elastic modulus in 20 degreeC of the adhesion layer was measured. Moreover, (2) Generation | occurrence | production about the crater in an adhesion layer was evaluated. The results are shown in Table 2.
（１）粘着層の２０℃における貯蔵弾性率
　貯蔵弾性率のサンプル作成と測定は、次のとおり行なった。粘着層の塗布液を、セパレータ（三菱化学ポリエステルフィルム社製、製品名：ＭＲＦ）の離型処理面に塗布し乾燥を行い、膜厚２０μｍの粘着層を形成した。ついで、粘着層をセパレータの離型処理面よりはく離し、はく離した粘着層を３０枚重ね合わせて、粘着層のみからなる厚さ６００μｍのシートサンプルを形成した。さらに、形成したシートサンプルを直径２５ｍｍの円柱状にくりぬき、粘着層のみからなる直径２５ｍｍ×厚さ６００μｍの試験片を作成した。そして、試験片を粘弾性測定装置（ＰｈｙｃｉｃａMCR301：Ａｎｔｏｎ　Ｐａａｒ社）を使用してねじり剪断法により周波数１Ｈｚにて、粘着層の２０℃における貯蔵弾性率を測定した。 (1) Storage elastic modulus of adhesive layer at 20 ° C. Samples of storage elastic modulus were prepared and measured as follows. The pressure-sensitive adhesive layer coating solution was applied to a release treatment surface of a separator (Mitsubishi Chemical Polyester Film, product name: MRF) and dried to form a pressure-sensitive adhesive layer having a thickness of 20 μm. Next, the pressure-sensitive adhesive layer was peeled off from the release treatment surface of the separator, and 30 peeled pressure-sensitive adhesive layers were overlapped to form a sheet sample having a thickness of 600 μm consisting of only the pressure-sensitive adhesive layer. Further, the formed sheet sample was hollowed out into a cylindrical shape having a diameter of 25 mm, and a test piece having a diameter of 25 mm and a thickness of 600 μm consisting of only an adhesive layer was prepared. And the storage elastic modulus at 20 degrees C of the adhesion layer was measured for the test piece at the frequency of 1 Hz by the torsional shear method using the viscoelasticity measuring apparatus (PhysicaMCR301: Anton Paar).
（２）粘着層でのクレーターの発生
　粘着層でのクレーターの発生を次のように評価した。ロール状の窓貼り用フィルムの巻き芯側に位置していた１０ｍ長のフィルムについて、１平方メートル当たりの直径１ｍｍ以上のクレーターの数を、欠点検出器（長瀬産業株式会社製、機種名：ＳＣＡＮＴＥＣ７０００）を用いて検出した。 (2) Generation of Crater in Adhesive Layer The generation of crater in the adhesive layer was evaluated as follows. About the 10m long film located on the roll core side of the roll-shaped window pasting film, the number of craters with a diameter of 1mm or more per square meter is detected by a defect detector (model name: SCANTEC 7000, manufactured by Nagase Sangyo Co., Ltd.) It detected using.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
３．考察
　表２から以下のことが理解できる。
　実施例１、２の窓貼り用フィルムは、粘着層の２０℃における貯蔵弾性率が４．５×１０４Ｐａ以上であり、粘着層でのクレーターの発生の数が１個／ｍ２未満で外観は良好であった。また、粘着層の２０℃における貯蔵弾性率が２．０×１０５Ｐａ以下であることにより、十分な粘着力が得られた。 3. Discussion From Table 2, the following can be understood.
The film for window pasting of Examples 1 and 2 has a storage elastic modulus at 20 ° C. of 4.5 × 10 4 Pa or more of the adhesive layer, and the number of craters generated in the adhesive layer is less than 1 / m 2 . Appearance was good. Moreover, sufficient adhesive force was acquired because the storage elastic modulus in 20 degreeC of an adhesion layer is 2.0 * 10 < 5 > Pa or less.
　一方、比較例１、２の窓貼り用フィルムは、粘着層の２０℃における貯蔵弾性率が４．５×１０４Ｐａ以下であり、粘着層でのクレーターの発生の数が１個／ｍ２以上となり外観は不良であった。

  On the other hand, the film for window pasting of Comparative Examples 1 and 2 has a storage elastic modulus of 4.5 × 10 4 Pa or less at 20 ° C. of the adhesive layer, and the number of craters generated in the adhesive layer is 1 / m 2. As a result, the appearance was poor.

Claims (6)

  1. 　支持体、粘着層、セパレータをこの順に有する窓貼り用フィルムであって、前記粘着層の２０℃における貯蔵弾性率が４．５×１０４Ｐａ以上であることを特徴とする窓貼り用フィルム。 A window pasting film having a support, an adhesive layer, and a separator in this order, wherein the adhesive elastic layer has a storage elastic modulus at 20 ° C. of 4.5 × 10 4 Pa or more.
  2. 　前記粘着層の２０℃における貯蔵弾性率が２．０×１０５Ｐａ以下であることを特徴とする請求項１記載の窓貼り用フィルム。 The film for window pasting according to claim 1, wherein a storage elastic modulus of the adhesive layer at 20 ° C. is 2.0 × 10 5 Pa or less.
  3. 　前記粘着層は、重量平均分子量が３０万以上、９０万以下の架橋性のアクリル系粘着剤を含むことを特徴とする請求項１または２に記載の窓貼り用フィルム。 3. The window pasting film according to claim 1, wherein the adhesive layer contains a crosslinkable acrylic adhesive having a weight average molecular weight of 300,000 or more and 900,000 or less.
  4. 　前記粘着層は、粘着剤と、粘着剤１００重量部に対し、０．０１重量部以上の架橋剤と０．１重量部以上の架橋促進剤を含むことを特徴とする請求項１ないし３いずれか一項に記載の窓貼り用フィルム。 The said adhesive layer contains 0.01 weight part or more crosslinking agent and 0.1 weight part or more crosslinking accelerator with respect to an adhesive and 100 weight part of adhesives, Any 1 thru | or 3 characterized by the above-mentioned. The film for window sticking of Claim 1.
  5. 　前記支持体の前記粘着層を有する面の反対面に機能層を有することを特徴とする請求項１記載の窓貼り用フィルム。 The window pasting film according to claim 1, further comprising a functional layer on a surface opposite to the surface having the adhesive layer of the support.
  6. 　請求項１ないし５のいずれか一項に記載の窓貼り用フィルムであって、ロール状に巻かれた形態の窓貼り用フィルム。

          It is a film for window sticking as described in any one of Claims 1 thru | or 5, Comprising: The film for window sticking of the form wound by roll shape.

PCT/JP2013/057697 2012-03-23 2013-03-18 Film to be applied to window WO2013141215A1 (en)

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