WO2010032583A1 - Film protecteur de surface et stratifié - Google Patents

Film protecteur de surface et stratifié Download PDF

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Publication number
WO2010032583A1
WO2010032583A1 PCT/JP2009/064560 JP2009064560W WO2010032583A1 WO 2010032583 A1 WO2010032583 A1 WO 2010032583A1 JP 2009064560 W JP2009064560 W JP 2009064560W WO 2010032583 A1 WO2010032583 A1 WO 2010032583A1
Authority
WO
WIPO (PCT)
Prior art keywords
protective film
hard coat
coat layer
adhesive
elastic modulus
Prior art date
Application number
PCT/JP2009/064560
Other languages
English (en)
Japanese (ja)
Inventor
克彦 細越
光則 丸山
Original Assignee
株式会社 きもと
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社 きもと filed Critical 株式会社 きもと
Priority to CN2009801351619A priority Critical patent/CN102149778B/zh
Priority to JP2010529696A priority patent/JP6054591B2/ja
Publication of WO2010032583A1 publication Critical patent/WO2010032583A1/fr

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Classifications

    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
    • 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 surface protective film used for temporarily protecting the surface of a metal plate, a decorative plate, a plastic plate, a glass plate, etc. during processing, transportation, storage, etc., and a laminate on which the surface protective film is adhered. About the body.
  • such a surface protective film has good adhesiveness at the initial stage of application, but the adhesiveness with time after application tends to increase. For this reason, the used surface protection film cannot be easily peeled off from the object to be protected, requiring labor for the peeling operation. In some cases, a part of the adhesive layer of the surface protection film remains on the surface of the object to be protected. And the surface protective film stretches and breaks.
  • an object to be protected with a surface protective film is exposed to a high temperature state of about 100 to 150 ° C., for example, in a thermoforming process or a drying process after painting, or in a medium temperature state of about 40 to 60 ° C. for a long time.
  • a high temperature state of about 100 to 150 ° C.
  • a thermoforming process or a drying process after painting or in a medium temperature state of about 40 to 60 ° C. for a long time.
  • the present invention has excellent initial adhesiveness to the surface of an object to be protected such as a metal plate, a decorative plate, a plastic plate, and a glass plate, and when used in an application involving heat treatment, particularly high temperature heating, the adhesive strength even after the heat treatment.
  • the surface protection film that prevents the adhesive from remaining on the surface of the object to be protected and does not cause a peeling phenomenon such as floating, and the laminate on which the surface protection film is adhered The purpose is to provide a body.
  • the surface protective film of the present invention is a surface protective film having an adhesive layer on one surface of a substrate, and the adhesive layer has a difference between the storage elastic modulus at 150 ° C. and the storage elastic modulus at 20 ° C. (1).
  • the tan ⁇ maximum temperature is satisfied, and the tan ⁇ maximum temperature is ⁇ 5 ° C. or lower.
  • Equation 1 G ′ (150) ⁇ G ′ (20) ⁇ 0 (1)
  • G ′ (150) is a storage elastic modulus at 150 ° C.
  • G ′ (20) is a storage elastic modulus at 20 ° C.
  • tan ⁇ is a value obtained by dividing the loss elastic modulus by the storage elastic modulus.
  • the adhesive layer is characterized in that tan ⁇ at 100 ° C. to 150 ° C. is 0.1 or less.
  • the surface protective film of the present invention is obtained by laminating a surface having an adhesive layer of the surface protective film and a stainless steel plate (SUS304 steel plate defined in JIS G4305) and leaving it in an environment of 150 ° C. for 30 minutes.
  • the adhesive strength of the surface protective film to the stainless steel plate (180-degree peeling adhesive strength in JIS Z0237: 2000) is 0.1 N / 50 mm to 1 N / 50 mm.
  • G * G ′ + iG ′′ (2) [Wherein G ′ represents an elastic component of G, and G ′′ represents a viscous component of G. ]
  • the storage elastic modulus referred to in the present invention is related to the amount of energy stored when strain is applied to the viscoelastic body, and the loss elastic modulus is related to the loss due to heat of the energy.
  • the complex elastic modulus is a physical property value representing the relationship between stress and strain in a viscoelastic body. These are determined by measuring dynamic viscoelasticity.
  • the dynamic viscoelasticity referred to here is a viscoelastic behavior that appears when a regular vibration having a sinusoidal change is applied.
  • Tan ⁇ is a ratio of loss elastic modulus to storage elastic modulus, and is a value expressed by loss elastic modulus / storage elastic modulus.
  • the tan ⁇ maximum temperature is the temperature (° C.) at which tan ⁇ takes a maximum value.
  • the laminate of the present invention is characterized in that the surface having the pressure-sensitive adhesive layer of the surface protective film is stuck on the hard coat layer. Further, the hard coat layer has a contact angle with water of 110 degrees or less and a contact angle with kerosene of 50 degrees or less. The hard coat layer has a contact angle with water of 50 degrees or more and a wetting tension of 27 to 45 mN / m.
  • the present invention since it is a surface protective film having an adhesive layer exhibiting specific physical properties on one surface of a substrate, initial adhesiveness to the surface of an object to be protected such as a metal plate, a decorative plate, a plastic plate, or a glass plate
  • an object to be protected such as a metal plate, a decorative plate, a plastic plate, or a glass plate
  • the surface protection film which does not produce peeling phenomena, such as a float, can be provided.
  • a surface protective film that is excellent in initial tackiness even when stuck to a hard coat layer, particularly a hard coat layer having specific surface properties, and that hardly causes adhesive residue on the hard coat layer even after heat treatment. be able to.
  • the substrate used in the present invention is not particularly limited to transparent or opaque, and may be appropriately selected according to the use.
  • the material is transparent, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, Examples thereof include plastic films such as polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride, and norbornene compounds.
  • Opaque materials include opaque substrates such as paper and synthetic paper, the above plastic film made opaque by including pigments, and the above plastic film provided with a colored layer having a concealing property Etc.
  • the thickness of the base material varies depending on the use and cannot be generally specified. However, in consideration of ease of handling, the lower limit is generally 2 ⁇ m or more, preferably 10 ⁇ m or more, and the upper limit is 300 ⁇ m or less, preferably about 125 ⁇ m or less. Conceivable.
  • Such a substrate is subjected to easy adhesion treatment such as plasma treatment, corona discharge treatment, deep ultraviolet irradiation treatment, sand blast treatment, or undercoat easy adhesion treatment layer in order to improve adhesion with the adhesive layer described later. May be provided.
  • easy adhesion treatment such as plasma treatment, corona discharge treatment, deep ultraviolet irradiation treatment, sand blast treatment, or undercoat easy adhesion treatment layer in order to improve adhesion with the adhesive layer described later. May be provided.
  • the adhesive layer has the difference between the storage elastic modulus at 150 ° C. and the storage elastic modulus at 20 ° C. satisfying the above formula (1), and the tan ⁇ maximum temperature is ⁇ 5 ° C. or lower, preferably ⁇ 10 ° C. or lower, and further ⁇ 20 ° C. It is as follows.
  • the adhesive layer is such that the difference between the storage elastic modulus at 150 ° C. and the storage elastic modulus at 20 ° C. satisfies the above formula (1), so that the adhesive layer becomes too soft at high temperatures and Since it can be prevented from becoming too familiar, even when it is used for heat treatment, especially in applications involving high temperature heating of about 100 ° C to 150 ° C, there is little increase in adhesive strength even after heat treatment, and peeling from the object to be protected In this case, the adhesive residue on the surface of the object to be protected can hardly be left.
  • the adhesive layer has an initial tackiness by setting the tan ⁇ maximum temperature to -5 ° C or lower, so it has excellent initial adhesiveness, and peeling phenomenon such as floating even when exposed to a high temperature of about 100 ° C to 150 ° C. Can be made difficult to occur.
  • the adhesive layer preferably has a tan ⁇ at 100 ° C. to 150 ° C. of 0.1 or less.
  • tan ⁇ at 100 ° C. to 150 ° C. to 0.1 or less.
  • the adhesive layer preferably has an adhesive force with respect to the stainless steel plate after being left in an environment of 150 ° C. for 30 minutes between 0.1 N / 50 mm and 1 N / 50 mm.
  • the adhesive strength to the stainless steel plate after being left for 30 minutes in an environment of 150 ° C. is 0.1 N / 50 mm or more, peeling such as floating due to heat treatment in the drying process after thermoforming or painting The phenomenon can be made less likely to occur, and by setting it to 1 N / 50 mm or less, the peelability is good, and the workability and the handleability can be improved.
  • the adhesive constituting such an adhesive layer natural resin-based adhesives, synthetic resin-based adhesives and the like are used, and synthetic resin-based adhesives such as acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, etc. are preferably used. Among them, since it has weather resistance, hardly causes cohesive failure, can easily control the adhesive force, and can adjust the performance of removability and reattachability, a crosslinkable adhesive is preferable. A crosslinkable acrylic pressure-sensitive adhesive is particularly preferably used because of easy handling.
  • the crosslinking agent used for the adhesive layer is not particularly limited, and for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, an imine crosslinking agent, and a metal chelate can be used.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is 1 ⁇ m to 30 ⁇ m, preferably 2 ⁇ m to 10 ⁇ m in consideration of tackiness, adhesive strength, handling property, economy, etc. at the initial stage and after heating.
  • the adhesive layer in addition to adhesives and crosslinking agents, pigments, dyes, colorants, matting agents, antistatic agents, flame retardants, fungicides, rust inhibitors, antibacterial agents, ultraviolet absorbers, light stabilizers, You may add additives, such as a heat stabilizer, antioxidant, a plasticizer, a leveling agent, a flow regulator, an antifoamer, a dispersing agent, a fluorescent whitening agent, a storage stabilizer, a silane coupling agent. However, the addition amount of these additives is preferably in a range that does not hinder the effect of the adhesive layer.
  • the surface protective film of the present invention as described above is prepared by preparing an adhesive layer coating solution by dissolving or dispersing the above-mentioned adhesive agent, crosslinking agent, and additives added as necessary in a solvent.
  • the coating method of, for example, bar coater, die coater, blade coater, spin coater, roll coater, gravure coater, flow coater, spray, screen printing, etc., is applied onto the above-mentioned substrate, dried and cured by heating. It can be obtained by forming an adhesive layer. Further, from the viewpoint of handleability, it may be prepared by applying and drying on a substrate, and then providing a separator on the surface of the exposed adhesive layer and then curing by heating.
  • the surface protective film of the present invention can also be obtained by applying the above-mentioned adhesive layer coating solution onto a separator in the same manner as described above, drying it, bonding it to a substrate, and then curing it by heating.
  • Examples of the method of using the surface protective film of the present invention include, for example, protection during the production of optical members such as polarizing plates, during the printing process, during the production of electronic circuit boards, and during the production of electronic components such as ceramic capacitors. can give.
  • the surface protective film of the present invention is a surface protective film having an adhesive layer on one surface of a substrate, and the adhesive layer has a storage elastic modulus at 150 ° C. and a storage elastic modulus at 20 ° C. Since the difference satisfies the above formula (1) and the tan ⁇ maximum temperature is ⁇ 5 ° C. or less, it has excellent initial adhesiveness to the surface of a protected object such as a metal plate, a decorative plate, a plastic plate, a glass plate, and heat treatment.
  • the laminate of the present invention is obtained by sticking the surface having the adhesive layer of the surface protective film to the object to be stuck.
  • the hard coat layer used in various fields will be exemplified and described as the object to be attached.
  • the hard coat layer as an example can be obtained by preparing a curable composition (paint), applying it to a desired application target, and curing it.
  • the curable composition that can be used in this example contains a resin component.
  • the resin component includes one or both of a thermosetting resin and an ionizing radiation curable resin.
  • Thermosetting resins and ionizing radiation curable resins include, for example, polyester resins, acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, urethane resins, epoxy resins, and polycarbonates. Resin, melamine resin, phenol resin, silicone resin, fluorine resin and the like.
  • the resin component preferably contains at least an ionizing radiation curable resin from the viewpoint of excellent coating hardness (hard coat property) after curing.
  • an ionizing radiation curable resin a photopolymerizable prepolymer that is crosslinked and cured by irradiation with ionizing radiation (ultraviolet rays or electron beams) can be used.
  • the photopolymerizable prepolymer described later may be used alone, or two or more kinds may be used in combination.
  • the photopolymerizable prepolymer includes a cationic polymerization type and a radical polymerization type.
  • the cationic polymerization type photopolymerizable prepolymer include epoxy resins and vinyl ether resins.
  • the epoxy resin include bisphenol epoxy resin, novolac epoxy resin, alicyclic epoxy resin, and aliphatic epoxy resin.
  • the radical polymerization type photopolymerizable prepolymer an acrylic prepolymer (hard prepolymer) having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is hard coat property. In view of the above, it is particularly preferably used.
  • acrylic prepolymers examples include urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate, and silicone acrylate.
  • the urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol with polyisocyanate by reaction with (meth) acrylic acid.
  • polyester acrylate-based prepolymer include esterification of a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or a polyvalent carboxylic acid.
  • the epoxy acrylate prepolymer can be obtained, for example, by esterification by a reaction of an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac epoxy resin with (meth) acrylic acid.
  • the acrylic prepolymer can be appropriately selected according to the type and application of the member to be coated.
  • the acrylic prepolymer can be used alone, but it is preferable to add a photopolymerizable monomer in order to impart various performances such as improvement of cross-linking curability and adjustment of curing shrinkage.
  • photopolymerizable monomer examples include monofunctional acrylic monomers (for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate, etc.), bifunctional acrylic monomers (for example, 1,6-hexanediol diacrylate).
  • monofunctional acrylic monomers for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate, etc.
  • bifunctional acrylic monomers for example, 1,6-hexanediol diacrylate
  • Neopentyl glycol diacrylate diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, etc.
  • trifunctional or higher acrylic monomers eg dipentaerythritol hexaacrylate, trimethylpropane triacrylate, pentaerythritol tris
  • Acrylate includes not only acrylate but also methacrylate. These photopolymerizable monomers may be used alone or in combination of two or more.
  • the total content (in terms of solid content) of the photopolymerizable prepolymer and the photopolymerizable monomer in the curable composition is preferably 40 to 99% by weight, more preferably 60 to 95% by weight, based on the total resin component. More preferably, it is 80 to 90% by weight.
  • additives such as a photopolymerization initiator, a photopolymerization accelerator, and an ultraviolet sensitizer are blended in the curable composition. It is preferable to do.
  • the blending amount of these additives is usually selected in the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the total of the above-described photopolymerizable prepolymer and photopolymerizable monomer.
  • thermosetting resin may be contained in the resin component instead of or in addition to the ionizing radiation curable resin.
  • a thermopolymerizable monomer or prepolymer is used alone or in combination, and if desired, a thermopolymerization initiator, that is, a compound that generates active radical species by heating, or the like is contained.
  • thermosetting resin and ionizing radiation curable resin in addition to the thermosetting resin and ionizing radiation curable resin described above, other resins such as a thermoplastic resin may be included as long as the effects of the present invention are not impaired.
  • an additive component may be added to the curable composition as long as the effects of the present invention are not impaired.
  • the additive component include inorganic fine particles, resin fine particles, surface conditioners, lubricants, colorants, pigments, dyes, fluorescent brighteners, flame retardants, antibacterial agents, antifungal agents, ultraviolet absorbers, light stabilizers, heat Stabilizers, antioxidants, plasticizers, leveling agents, flow regulators, antifoaming agents, dispersants, storage stabilizers, crosslinking agents and the like can be mentioned.
  • inorganic fine particles or resin fine particles having a desired size a mat hard coat layer having a desired shape can be formed.
  • the mat hard coat layer when the adhesion of the adhesive layer is high with respect to the unevenness of the mat hard coat layer, the mat hard coat layer has a large surface area with the contacting adhesive layer, and therefore is subjected to heat treatment or the like. It tends to leave glue more than the clear hard coat layer. Also, when the adhesion of the adhesive layer is low with respect to the unevenness of the mat hard coat layer, the mat hard coat layer has a smaller surface area with the contacting adhesive layer, and therefore tends to be more likely to float than the clear hard coat layer. It is in. However, in the surface protective film of the present invention, since the adhesive layer has specific physical properties, even if it is attached to the mat hard coat layer, it is difficult for adhesive to remain even after heat treatment, and it is difficult for floating to occur. be able to.
  • the surface protective film of the present invention can be such that no adhesive residue is generated after the heat treatment.
  • the contact angle with respect to water is smaller than a specific value, and the contact angle with respect to the soot oil is adjusted to be smaller than a specific value.
  • the attached fingerprints are less noticeable (improving the degree of fingerprint visibility). Instead of imparting strong water and oil repellency to the coating surface, It is effective to impart excellent hydrophilicity and lipophilicity. And, by adjusting the surface properties of the hard coat layer so that each of the contact angle for water and the contact angle for oil is adjusted to be smaller than a specific value, it is possible to develop moderate hydrophilicity and lipophilicity. it can. If appropriate hydrophilicity and lipophilicity can be expressed on the surface of the hard coat layer, the contact area of the fingerprint component (consisting of an aqueous component and an oil component) with the coating surface will not be too small, and the fingerprint component will be coated. The surface can be appropriately wetted and spread. As a result, even when a fingerprint adheres to the surface of the hard coat layer, the attached fingerprint can be made inconspicuous (improvement in the difficulty of visually recognizing the fingerprint).
  • the contact angle with respect to water is adjusted to a predetermined angle or more, and the wetting tension is adjusted to a predetermined range, thereby improving the fingerprint visual difficulty and preventing the hard coat property from being lowered.
  • the wiping property of the fingerprint after the fingerprint is attached becomes good, and the fingerprint component after wiping can be made inconspicuous.
  • the contact angle of the hard coat layer with respect to water is adjusted to 110 ° or less. More preferably, it is adjusted to 100 ° or less. By adjusting the contact angle with water to 110 ° or less, the contact area with water does not become too small, and the attached fingerprint can be made inconspicuous (improvement of fingerprint visibility difficulty).
  • the contact angle of the hard coat layer with the oil is adjusted to 50 ° or less. More preferably, it is adjusted to 40 ° or less.
  • the contact angle with the cocoon oil is adjusted to 50 ° or less.
  • the contact angle of the hard coat layer with respect to water is preferably adjusted to 50 ° or more. More preferably, it is adjusted to 60 ° or more, more preferably 70 ° or more, and particularly preferably 80 ° or more.
  • the contact angle with water is adjusted to 50 ° or more.
  • the contact area with water does not become too large.
  • the aqueous component in the fingerprint is easily separated and the fingerprint wiping property is improved. That is, in this example, by adjusting the contact angle of the hard coat layer with respect to water within a predetermined range, in addition to the improvement in the difficulty of visually recognizing the fingerprint, the wiping property of the fingerprint is also improved.
  • the wetting tension of the hard coat layer is adjusted to 27 mN / m or more. More preferably, it is adjusted to 30 mN / m or more.
  • the wetting tension of the hard coat layer is preferably adjusted to 45 mN / m or less. More preferably, it is adjusted to 40 mN / m or less, more preferably 38 mN / m or less.
  • the value of the wetting tension is a value measured by a method in accordance with JIS-K6768 (1999).
  • a hard coat layer having such surface physical properties is obtained by blending a compound having a HLB value by the Griffin method within a specified range (nonionic compound) as an additive component to the curable composition of the hard coat layer described above. Can do.
  • examples of such compounds include nonionic compounds having an HLB value by the Griffin method of 2 or more, preferably 5 or more, more preferably 10 or more, for example 18 or less, preferably 15 or less.
  • a nonionic compound is a generic term for compounds that are soluble in water and do not exhibit ionic properties, but are composed of a combined bond of a hydrophobic group (lipophilic group) and a hydrophilic group.
  • Such compounds include at least hydrophilic groups (eg, polyalkylene oxide, hydroxyl group, carboxyl group, sulfonyl group, phosphate, amino group, isocyanate group, glycidyl group, alkoxysilyl group, ammonium salt, various metal salts, etc.).
  • a compound having at least one kind, and examples thereof include ethoxylated glycerin triacrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol diacrylate, polyether-modified acrylate, and polyhydroxy-modified acrylate.
  • polyethylene glycol diacrylate is preferably used from the viewpoints of solubility in a solvent and handleability.
  • fatty acid esters and polyethers can also be used as nonionic compounds.
  • fatty acid ester examples include fatty acid esters obtained by condensation of a monohydric alcohol or a dihydric or higher polyhydric alcohol and a fatty acid, such as propylene glycol monostearate, propylene glycol monolaurate, diethylene glycol monostearate, diethylene glycol. Examples thereof include monolaurate, glycerol monostearate, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, and the like. Moreover, polyoxyalkylene addition fatty acid ester is also mentioned as fatty acid ester.
  • ethylene oxide or propylene oxide is suitable as the alkylene oxide to be subjected to addition polymerization.
  • ethylene oxide and propylene oxide may be subjected to addition polymerization alone or may be copolymerized.
  • polyoxyalkylene-added fatty acid ester examples include polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerol monostearate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan monostearate, Polyoxyethylene (4) sorbitan tristearate, polyoxyethylene (5) sorbitan monooleate, polyoxyethylene (5) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxy Ethylene (4) sorbitan monolaurate, polyoxyethylene glycol 400 monooleate, polyoxyethylene glycol 400 monomonostearate Ether, polyethylene glycol 400 monolaurate, polyoxyethylene (4) sorbitan monolaurate and the like.
  • polyoxyethylene cholesteryl ether polyoxyethylene decyl tetradecyl ether, or the like may be used as a compound other than fatty acid ester or polyether.
  • the content of the compound having an HLB value in a predetermined range by the Griffin method is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the resin component. It is preferably 60 parts by weight or less, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less.
  • the hard coat layer preferably further has a pencil scratch value adjusted to H or higher. More preferably, it is adjusted to 2H or more.
  • the pencil scratch value is a value measured by a method according to JIS-K5600-5-4 (1999).
  • the hard coat layer preferably further has a refractive index adjusted to 1.45 to 1.65. More preferably, it is adjusted to 1.46 to 1.52.
  • a refractive index value within a predetermined range, the difference between the refractive index of the hard coat layer and the refractive index of the fingerprint component can be reduced.
  • the attached fingerprint becomes more inconspicuous (further improvement in the difficulty of visually recognizing the fingerprint), and the fingerprint component after wiping can be made inconspicuous.
  • the thickness of the hard coat layer is preferably about 0.1 ⁇ m or more and 30 ⁇ m or less.
  • the thickness of the hard coat layer is preferably about 0.1 ⁇ m or more and 30 ⁇ m or less.
  • the thickness of the hard coat layer may be a thin film having a thickness of about 10 ⁇ m or less, and further about 5 ⁇ m or less. Even if it is a thin film, necessary and sufficient performance is ensured.
  • the surface of the hard coat layer may be subjected to a surface treatment such as a plasma treatment, a corona discharge treatment, or a deep ultraviolet irradiation treatment.
  • a surface treatment such as a plasma treatment, a corona discharge treatment, or a deep ultraviolet irradiation treatment.
  • the hard coat layer having such surface properties is more susceptible to additive components and surface treatment than the above-described hard coat layer. It tends to be easy to do.
  • the adhesive layer since the adhesive layer has specific physical properties, even if it is attached to a hard coat layer having such specific surface physical properties, it is difficult for adhesive residue to remain after heat treatment. Can be.
  • the curable composition is usually realized in the form of a paint.
  • an organic solvent-based paint it may be appropriately selected depending on the type of resin component, but after dissolving or dispersing the above-described resin component (additional component further if necessary) with a diluting solvent such as an organic solvent, A curable composition can be manufactured by adding an additive as needed.
  • the base material As an object to be coated, it is a base material that is desired to have an effect of improving hard coat properties (abrasion resistance) and fingerprint visibility difficulty.
  • the aspect of the base material that can be used in this example is not particularly limited, and may have any thickness such as a film shape, a sheet shape, or a plate shape.
  • the surface of the substrate may have, for example, an uneven shape or a three-dimensional shape having a three-dimensional curved surface.
  • the material of the substrate is not particularly limited and may be a hard substrate such as a glass plate, but in this example, a flexible resin substrate is preferable.
  • the kind of resin which comprises a resin base material is not specifically limited.
  • a resin in the case of forming a resin substrate in the form of a film or a sheet for example, acrylic, polycarbonate, polyvinyl chloride, polyester, polypropylene, polyethylene, acetylcellulose, cycloolefin, and the like can be mentioned.
  • examples of the resin when the resin base material is formed in a plate shape include acrylic, polycarbonate, polyvinyl chloride, and the like.
  • an easy adhesion treatment may be performed on the surface of the base material for the purpose of improving the adhesion with the hard coat layer composed of a cured product of the curable composition.
  • Examples of the easy adhesion treatment include plasma treatment, corona discharge treatment, deep ultraviolet irradiation treatment, and formation of an undercoat easy adhesion layer.
  • Application (coating) of the curable composition to the object to be applied may be performed by a conventional method, for example, bar coating, die coating, blade coating, spin coating, roll coating, gravure coating, flow coating, dip coating, spray coating, screen. Examples include printing and brushing. It is applied so that the thickness of the coated film after application is preferably about 0.1 to 30 ⁇ m after drying and curing described below. When the curable composition is applied to the application target, the coated film is preferably dried at about 50 to 120 ° C.
  • Curing of the curable composition can be performed by irradiating the coated film after application with heat curing and / or ionizing radiation (light).
  • the radiation source is not particularly limited as long as the curable composition applied to the substrate can be cured in a short time.
  • examples of infrared ray sources include lamps, resistance heating plates, and lasers.
  • examples of the visible light source include sunlight, a lamp, a fluorescent lamp, and a laser.
  • Ultraviolet (ionizing radiation) radiation sources include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, metal halide lamps, and the like.
  • Ultraviolet rays in a wavelength region of 100 nm to 400 nm, preferably 200 nm to 400 nm, emitted from such an ultraviolet ray source are irradiated.
  • the electron beam (ionizing radiation) source include scanning and curtain electron beam accelerators. An electron beam having a wavelength region of 100 nm or less emitted from such an electron beam accelerator is irradiated.
  • the dose of ionizing radiation varies depending on the type of ionizing radiation.
  • the amount of light is preferably about 100 to 500 mJ / cm 2
  • it is preferably about 10 to 1000 krad.
  • the hard coat layer produced as described above is used in applications requiring improvement in hard coat properties (scratch resistance) and fingerprint visibility difficulty, particularly various displays (for example, plasma display panel PDP, cathode ray tube CRT, Hard coats for liquid crystal displays (LCDs, electroluminescence displays ELD, etc.); for showcases, watch and instrument cover glasses; for touch surfaces of touch panel electronic devices such as bank ATMs and ticket vending machines Is preferably used.
  • various displays for example, plasma display panel PDP, cathode ray tube CRT, Hard coats for liquid crystal displays (LCDs, electroluminescence displays ELD, etc.); for showcases, watch and instrument cover glasses; for touch surfaces of touch panel electronic devices such as bank ATMs and ticket vending machines Is preferably used.
  • Electronic devices include information processing apparatuses such as mobile phones having the above-mentioned various displays (including personal portable information terminals incorporating PDA (Personal Digital Assistants) functions) and personal computers. is there.
  • Examples 1 to 3 and Comparative Examples 1 to 4 As a base material, on one side of a 25 ⁇ m-thick polyethylene terephthalate film (Lumirror S28: Toray Industries, Inc.), a coating solution for adhesive layers (Examples 1 to 3 and Comparative Examples 1 to 4) having the formulation shown in Table 1 was applied as a bar coater. Each was coated by the method, and dried at 90 ° C. for 1.5 minutes to form a pressure-sensitive adhesive layer having a dry film thickness of 2.5 ⁇ m, which was then bonded to a separator (MRF: Mitsubishi Chemical Polyester Film Co., Ltd.) to improve handling. . Next, curing was performed in an environment of 60 ° C. for 48 hours to prepare surface protective films of Examples 1 to 4 and Comparative Examples 1 to 4.
  • MRF Mitsubishi Chemical Polyester Film Co., Ltd.
  • a viscoelasticity measuring device (Physica MCR301: Anton Paar), by measuring the dynamic viscoelasticity of the measurement sample, the storage elastic modulus at 150 ° C. and 20 ° C., the tan ⁇ maximum temperature, and the tan ⁇ at 100 ° C. to 150 ° C. Asked.
  • the measurement conditions were a strain of 0.1%, a frequency of 1 Hz, and a temperature range of ⁇ 30 ° C. to 160 ° C.
  • Adhesive strength after heating A test piece was prepared in the same manner as in (2), attached to a stainless steel plate, left in an environment of 23 ° C. and 50% RH for 30 minutes, and then left in an environment of 150 ° C. for 30 minutes. Further, after being left for 30 minutes in an environment of 23 ° C. and 50% RH, the adhesive strength was measured by peeling 180 degrees in the same manner as in (2).
  • the difference between the storage elastic modulus at 150 ° C. and the storage elastic modulus at 20 ° C. of the adhesive layer is greater than 0, satisfies the above formula (1), and the tan ⁇ maximum temperature is ⁇ It was 5 ° C or lower. For this reason, it has excellent initial adhesiveness, and there is little increase in adhesive force even after heat treatment at 150 ° C. for 30 minutes, there is no adhesive residue on the surface when peeling from the stainless steel plate, and it is difficult for floating to occur. It was.
  • the adhesive strength after heating (180-degree peeling adhesive strength according to JIS Z0237: 2000) was 0.1 N / 50 mm to 1 N / 50 mm, so that the peelability was good.
  • the tan ⁇ maximum temperature of the adhesive layer was ⁇ 5 ° C. or lower, but the tan ⁇ at 100 ° C. to 150 ° C. was greater than 0.1, and the storage elastic modulus at 150 ° C. Since the difference from the storage elastic modulus at 20 ° C. is less than 0 and does not satisfy the above formula (1), the float does not occur, but the initial adhesiveness is high, and the adhesive strength is also after heat treatment at 150 ° C. for 30 minutes. As a result, the adhesive remained on the surface when peeling from the stainless steel plate. Moreover, since the adhesive strength after heating (180 degree peeling adhesive strength in JIS Z0237: 2000) was 1 N / 50 mm or more, the peelability was poor.
  • Example 4 A hard coat film (KB film GN7B: having a clear hard coat layer made of an ionizing radiation curable resin on one surface of a substrate and a mat hard coat layer made of silica fine particles and an ionizing radiation curable resin on the other surface. Kimotosha) was prepared. Next, the surface which has the adhesion layer of the surface protection film of Example 1 was stuck on the clear hard-coat layer of the prepared hard coat film, and the laminated body of Example 4 was produced.
  • the clear hard coat layer had a contact angle with water of 62 degrees, a contact angle with cocoon oil of 31 degrees, and a wetting tension of 23 mN / m or less.
  • Example 5 The surface having the adhesive layer of the surface protective film of Example 1 was stuck on the matte hard coat layer of the hard coat film of Example 4 to produce the laminate of Example 5.
  • the mat hard coat layer has a contact angle with water of 79 degrees, a contact angle with cocoon oil of 34 degrees, and a wetting tension of 23 mN / m or less.
  • the arithmetic average roughness in JIS B0601: 2001 is 0.12 ⁇ 0.00. It was 04 ⁇ m.
  • Example 6 Prepare a hard coat film (KB film AFP: Kimoto Co., Ltd.) having a hard coat layer with a contact angle with water of 76 degrees, a contact angle with kerosene of 36 degrees, and a wetting tension of 32 mN / m on one side of the substrate. did. Next, the surface which has the adhesion layer of the surface protection film of Example 1 was stuck on the hard-coat layer of the prepared hard-coat film, and the laminated body of Example 6 was produced.
  • KB film AFP Kimoto Co., Ltd.
  • Adhesive strength after heating A test piece was prepared in the same manner as in (6), left in an environment of 23 ° C. and 50% RH for 30 minutes, then left in an environment of 150 ° C. for 30 minutes, and further 23 ° C. After leaving for 30 minutes in an environment of 50% RH, the adhesive strength was measured by peeling 180 degrees in the same manner as in (6).
  • Adhesive residue For the laminates of Examples 4 to 6 and Comparative Examples 5 to 7, a test piece was cut to the size of A-4 and allowed to stand in an environment of 23 ° C. and 50% RH for 30 minutes. Thereafter, the film was left for 90 minutes in an environment of 150 ° C., and further left for 30 minutes in an environment of 23 ° C. and 50% RH, and then the surface protective film was peeled off from the hard coat layer by hand. Evaluation is visually observed, and “XX” indicates that the adhesive remains on the entire surface of the hard coat layer, and “XX” indicates that the adhesive remains on the hard coat layer.
  • the laminates of the examples all had excellent initial tackiness with respect to the hard coat layer, and there was little increase in the adhesive strength even after heat treatment at 150 ° C. for 30 minutes, and no floating occurred. .
  • the laminate of Example 6 had specific physical properties when the surface protective film was peeled off from the hard coat layer after 150 ° C. and 90 minutes of heat treatment. Although the evaluation of the adhesive residue was inferior compared with the hard coat layer of the laminate, the adhesive residue could not be visually confirmed, and a fine adhesive residue could be confirmed with a magnifying glass.
  • the adhesive layer of the surface protective film had a difference between the storage elastic modulus at 150 ° C. and the storage elastic modulus at 20 ° C. smaller than 0 and did not satisfy the above formula (1).
  • the surface protective film was peeled off from the hard coat layer after the heat treatment at 150 ° C. for 90 minutes, adhesive residue clearly visible was generated in various places on the hard coat layer.
  • the surface protective film used in the laminate of the example is compared with the surface protective film used in the laminate of the comparative example, even when the object to be protected is various hard coat layers, It exhibits extremely excellent performance such as moderate initial tackiness, suppression of increase in adhesive strength after heat treatment, anti-floating property, and anti-glue property.

Landscapes

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

Abstract

L'invention porte sur un film protecteur de surface comprenant un substrat et une couche adhésive autocollante formée sur un côté de celui-ci, la couche adhésive autocollante étant telle que la différence entre le module de conservation à 150°C et celui à 20°C satisfait à une relation prescrite et que la température à laquelle la tan δ est maximale est inférieure ou égale à –5°C. Le film protecteur de surface exerce un excellent caractère poisseux initial sur la surface d'un objet devant être protégé, tel qu'une feuille de métal, une feuille stratifiée décorative, une feuille de matière plastique ou une feuille de verre, et présente peu d'augmentation de caractère poisseux même après traitement thermique, en particulier même lorsqu'il est utilisé dans un champ s'accompagnant d'un chauffage à haute température. Lorsque le film protecteur de surface est décollé d'un objet protégé par celui-ci, le film protecteur de surface laisse très peu de résidu d'adhésif autocollant sur la surface de l'objet résultant. En outre, le film protecteur de surface ne provoque pas de phénomène de délaminage tel qu'un arrachage.
PCT/JP2009/064560 2008-09-17 2009-08-20 Film protecteur de surface et stratifié WO2010032583A1 (fr)

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CN2009801351619A CN102149778B (zh) 2008-09-17 2009-08-20 表面保护膜及层合体
JP2010529696A JP6054591B2 (ja) 2008-09-17 2009-08-20 表面保護フィルム及び積層体

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WO2015163115A1 (fr) * 2014-04-22 2015-10-29 日東電工株式会社 Feuille adhésive
JP2019195997A (ja) * 2018-05-08 2019-11-14 住友化学株式会社 積層体およびその製造方法
JP2021070756A (ja) * 2019-10-31 2021-05-06 東洋インキＳｃホールディングス株式会社 加飾シート用保護フィルムおよび保護フィルム付加飾シート

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JP2015030797A (ja) * 2013-08-02 2015-02-16 日東電工株式会社 粘着テープ又はシート
KR101686644B1 (ko) * 2013-11-19 2016-12-14 주식회사 엘지화학 플라스틱 필름 적층체
JP6720481B2 (ja) * 2014-07-29 2020-07-08 大日本印刷株式会社 積層体、導電性積層体及びタッチパネル
TWI727167B (zh) * 2017-08-07 2021-05-11 日商拓自達電線股份有限公司 導電性接著劑
CN113795080A (zh) * 2021-08-18 2021-12-14 景旺电子科技(珠海)有限公司 印刷电路板的表面处理方法及印刷电路板

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WO2015163115A1 (fr) * 2014-04-22 2015-10-29 日東電工株式会社 Feuille adhésive
JP5890596B1 (ja) * 2014-04-22 2016-03-22 日東電工株式会社 粘着シート
JP2016135878A (ja) * 2014-04-22 2016-07-28 日東電工株式会社 粘着シート
JP2019123884A (ja) * 2014-04-22 2019-07-25 日東電工株式会社 粘着シート
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JP2019195997A (ja) * 2018-05-08 2019-11-14 住友化学株式会社 積層体およびその製造方法
JP2021070756A (ja) * 2019-10-31 2021-05-06 東洋インキＳｃホールディングス株式会社 加飾シート用保護フィルムおよび保護フィルム付加飾シート
JP7306226B2 (ja) 2019-10-31 2023-07-11 東洋インキＳｃホールディングス株式会社 加飾シート用保護フィルムおよび保護フィルム付加飾シート

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KR101627882B1 (ko) 2016-06-07
CN102149778B (zh) 2013-11-06
CN102149778A (zh) 2011-08-10
KR20110057210A (ko) 2011-05-31
TWI555814B (zh) 2016-11-01
JPWO2010032583A1 (ja) 2012-02-09
JP6054591B2 (ja) 2016-12-27

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