WO2013153990A1 - Film de protection de surface autoadhésif - Google Patents

Film de protection de surface autoadhésif Download PDF

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Publication number
WO2013153990A1
WO2013153990A1 PCT/JP2013/060087 JP2013060087W WO2013153990A1 WO 2013153990 A1 WO2013153990 A1 WO 2013153990A1 JP 2013060087 W JP2013060087 W JP 2013060087W WO 2013153990 A1 WO2013153990 A1 WO 2013153990A1
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Prior art keywords
mass
adhesive
film
adhesive layer
resin
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PCT/JP2013/060087
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English (en)
Japanese (ja)
Inventor
茂知 山本
大木　祐和
多賀　敦
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020147025456A priority Critical patent/KR102020085B1/ko
Priority to KR1020197014658A priority patent/KR102089231B1/ko
Priority to CN201380019463.6A priority patent/CN104220548A/zh
Publication of WO2013153990A1 publication Critical patent/WO2013153990A1/fr

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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
    • C09J7/387—Block-copolymers
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • 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
    • C09J2453/00—Presence of block copolymer

Definitions

  • the present invention relates to an adhesive film.
  • the adhesive film of the present invention is a member such as a prism sheet used for optical applications, a synthetic resin plate (for example, for building materials), a stainless plate (for example, for building materials), an aluminum plate, a decorative plywood, a steel plate, and a glass plate.
  • a synthetic resin plate for example, for building materials
  • a stainless plate for example, for building materials
  • an aluminum plate for example, a decorative plywood, a steel plate, and a glass plate.
  • Home appliances, precision machinery to protect the surface of automobile bodies during manufacturing, to protect articles from being scratched when stacked, stored, transported, transported in the manufacturing process, and articles Can be suitably used for protecting from scratches during secondary processing (for example, bending or pressing).
  • the above-mentioned coverings have been diversified, and there are many not only those with a smooth coating surface but also surface irregularities.
  • Examples of the covering having surface irregularities include a prism type lens portion of a prism sheet used for an optical member.
  • the adhesive layer has a high adhesive force so that the adhesive force can be obtained even if the contact area is small. Can be considered.
  • the base material layer is made of a fluorine-based resin, a silicone-based resin (see, for example, Patent Document 1), an ultra high molecular weight polydimethylsiloxane (for example, see Patent Document 2, etc.), a saturated fatty acid bisamide (for example,
  • a fluorine-based resin for example, a silicone-based resin
  • an ultra high molecular weight polydimethylsiloxane for example, see Patent Document 2, etc.
  • a saturated fatty acid bisamide for example,
  • the problem to be solved by the present invention shows a strong adhesive force to the covering, and can be used for various coverings, while storing the adhesive film in a roll state, and then paying out the film, It is an object of the present invention to provide a self-adhesive surface protective film that is less prone to problems such as partial stretching or deformation of the film and that is excellent in processability of the film.
  • the present inventors have found that the above-mentioned problems can be solved by setting the type and blending ratio of the resin used in the adhesive layer within a predetermined range, and the present invention has been achieved.
  • the present invention is obtained by laminating a pressure-sensitive adhesive layer on one side of a base material layer made of polypropylene resin and a release layer on the opposite side by co-extrusion, and the resin constituting the pressure-sensitive adhesive layer is a styrene-based elastomer, At least a polyethylene resin, and the styrene elastomer is a hydrogenated block copolymer having a styrene polymer block and a butadiene polymer block, or a random mixture of a styrene polymer block, styrene and butadiene.
  • a hydrogenated block copolymer having a copolymer block wherein the polyethylene-based resin is an ethylene homopolymer and / or an ethylene- ⁇ -olefin copolymer, and the styrene-based elastomer in the adhesive layer
  • the content is 35% by mass or more and 99% by mass or less, the content of the polyethylene resin is 1% by mass or more, 6
  • the self-adhesive surface protective film wherein the sum of the ethylene component and the polyethylene resin in the styrene elastomer is 35% by mass or more and less than 70% by mass in the adhesive layer component.
  • the adhesive film has a strong adhesive force to the covering and can be used for various coverings.
  • a self-adhesive surface protective film that is less prone to stretching and deforming and that has excellent processability of the film.
  • the flexural modulus of the ethylene resin used for the adhesive layer is preferably 10 MPa or more and less than 90 MPa.
  • the MFR (190 ° C., 2.16 kgf) of the polyethylene resin in the adhesive layer is preferably 0.5 to 8 g / 10 min.
  • the MFR (230 ° C., 2.16 kgf) of the styrene elastomer in the adhesive layer is preferably 0.5 to 8 g / 10 min.
  • the MFR (230 ° C., 2.16 kgf) of the polypropylene resin in the base material layer is 1.0 to 15 g / 10 min.
  • the pressure-sensitive adhesive film according to the present invention exhibits a strong adhesive force to the covering and can be used for various coverings. However, when the pressure-sensitive adhesive film is stored in a roll state and then fed out, the film is partially The film has the advantage that the film is not easily stretched or deformed, and is excellent in processability of the film.
  • the pressure-sensitive adhesive film of the present invention requires a base material layer mainly composed of a polypropylene resin.
  • the polypropylene resin used here include crystalline polypropylene, random copolymer of propylene and a small amount of ⁇ -olefin, or block copolymer. More specifically, as a crystalline polypropylene resin, an n-heptane-insoluble isotactic propylene homopolymer used in ordinary extrusion molding or the like, or propylene containing 60% by mass or more of propylene and another ⁇ -olefin is used. Mention may be made of copolymers. This propylene homopolymer or a copolymer of propylene and another ⁇ -olefin can be used alone or in combination.
  • the base material layer preferably contains 60% by mass or more of propylene units, more preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • propylene unit is less than 60% by mass, the film loses its sensation and may be difficult to handle.
  • propylene unit amount is less than 60% by mass or a polyethylene resin is used, the film becomes flexible and easily stretched, and there is a problem that the film partially stretches or deforms when the film is fed out. It becomes easy to get up.
  • n-heptane insolubility is indicative of the crystallinity of polypropylene and at the same time indicates safety.
  • n-heptane insolubility (at 25 ° C., 60 ° C. according to Ministry of Health and Welfare Notification No. 20 in February 1982). It is a preferred embodiment to use one that is compatible with an elution amount of 150 ppm or less (30 ppm or less when the operating temperature exceeds 100 ° C.)).
  • the ⁇ -olefin copolymer component constituting the copolymer of propylene and other ⁇ -olefins includes ⁇ -olefins having 2 to 8 carbon atoms, such as ethylene or 1-butene, 1-pentene, 1-hexene. C4- or higher ⁇ -olefins such as 4-methyl-1-pentene.
  • the copolymer is preferably a random or block copolymer obtained by polymerizing one or more of the above-mentioned ⁇ -olefins with propylene.
  • copolymers of propylene and other ⁇ -olefins can be used alone or in admixture of two or more.
  • the melt flow rate (MFR: 230 ° C., 2.16 kgf) of the polypropylene resin used is preferably in the range of 1.0 to 15 g / 10 minutes, more preferably in the range of 2.0 to 10.0 g / 10 minutes.
  • the waste film produced when the film obtained in the present invention is processed can be re-granulated as a recovered raw material and added to the base material layer.
  • the production cost can be reduced.
  • the pressure-sensitive adhesive layer according to the present invention needs to contain a styrene elastomer in order to develop a high pressure-sensitive adhesive force. Moreover, in order to express the adhesive force and the drawing property of the film from the roll state, the adhesive layer needs to contain a polyethylene resin. By adding a polyethylene-based resin, it is possible to reduce the peeling force from the pressure-sensitive adhesive side to the release surface. Moreover, tackifying resin other than polyethylene resin, a softening agent, polystyrene, etc. can also be mixed with an adhesion layer as needed for control of adhesive force.
  • the amount of the styrene-based elastomer in the adhesive layer is 35% by mass or more and 99% by mass or less with respect to 100% by mass of the adhesive layer component in order to express high adhesive force and roll-out property from the roll state. It is necessary. If it is less than 35% by mass, the adhesive strength is lowered and it is difficult to obtain the required adhesive strength.
  • the amount of styrenic elastomer in the adhesive layer is preferably in the range of 38% by mass to 95% by mass. More preferably, it is the range of 40 mass% or more and 90 mass% or less.
  • styrene elastomers include hydrogenated AB-A block polymers such as styrene-butadiene-styrene copolymers, hydrogenated AB block polymers such as styrene-butadiene copolymers, and styrene- Examples thereof include a hydrogenated product of a styrene random copolymer such as butadiene rubber. These hydrogenated bodies may be partially hydrogenated bodies or fully hydrogenated bodies.
  • the styrene component in the styrene-based elastomer is desirably 5% by mass or more and 40% by mass or less. If it is less than 5% by mass, granulation at the time of producing the resin becomes difficult, and if it exceeds 40% by mass, the adhesive strength is lowered, and it may be difficult to obtain the required adhesive strength.
  • the styrene component in the styrene-based elastomer is preferably in the range of 8% by mass to 35% by mass, and more preferably in the range of 10% by mass to 30% by mass.
  • the ethylene component in the styrene elastomer is desirably 15% by mass or more and 70% by mass or less.
  • the ethylene component in the styrene-based elastomer has an effect of increasing the compatibility with the polyethylene-based resin, and also has an effect of increasing the feeding property of the film from the roll state. Therefore, it is considered that when the amount of ethylene component is large, the effect of improving the feedability is likely to increase.
  • the ethylene component in a styrene-type elastomer has contributed greatly also to expression of adhesive force, and when the amount of ethylene components exceeds 70 mass%, there exists a possibility that the adhesive force of an adhesion layer may become high too much.
  • a butylene component is present in the styrene-based elastomer.
  • the butylene component is 50% by mass or more, when a polyethylene resin is added, the adhesive force tends to be difficult to decrease, which is preferable.
  • the melt flow rate (MFR: 230 ° C., 2.16 kgf) of the styrene elastomer to be used is preferably in the range of 0.5 to 8 g / 10 minutes, and 2.0 to 7.0 g / 10 minutes in terms of film forming properties. The range of is more preferable.
  • the amount of the polyethylene-based resin in the adhesive layer needs to be 1% by mass or more and 65% by mass or less in order to develop high adhesive force and roll out property from the roll state.
  • the amount of the polyethylene resin in the adhesive layer is preferably in the range of 3% by mass to 60% by mass.
  • polyethylene resin examples include low density polyethylene, a copolymer of ethylene and ⁇ -olefin, and the like.
  • low-density polyethylene in particular, linear low-density polyethylene called LLDPE and ultra-low-density polyethylene called VLDPE are preferable because they can improve the film feeding property while maintaining adhesive strength.
  • LLDPE linear low-density polyethylene
  • VLDPE ultra-low-density polyethylene
  • ⁇ -olefin examples include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.
  • the sum of the ethylene component and the ethylene resin in the styrene elastomer is in the range of 35% by mass or more and less than 70% by mass in the adhesive layer component.
  • the adhesive strength is lowered and sufficient adhesive strength cannot be obtained.
  • the sum of the ethylene component and the ethylene-based resin is less than 35% by mass in the adhesive layer component, the peeling force of the film adhesive layer on the release layer is increased.
  • the sum of the ethylene component and the ethylene-based resin is 40% by mass or more and less than 70% by mass in the adhesive layer component.
  • the sum of the ethylene component and the ethylene-based resin is 45% by mass or more and 65% by mass or less in the adhesive layer component.
  • the sum of the ethylene component and the ethylene-based resin is 45% by mass or more and 63% by mass or less in the adhesive layer component.
  • the flexural modulus of the polyethylene resin is 10 MPa or more and less than 90 MPa.
  • the flexural modulus of the polyethylene resin is preferably in the range of 15 MPa to 80 MPa, more preferably in the range of 20 MPa to 70 MPa.
  • the ethylene component in the polyethylene resin is preferably 70% by mass or more.
  • the ethylene component of the polyethylene resin is more preferably 75% by mass or more, and still more preferably 80% by mass or more.
  • the ethylene content of the polyethylene resin is preferably 98% by mass or less, more preferably 96% by mass or less, still more preferably 95% by mass or less, and particularly preferably 94% by mass or less.
  • the polyethylene resin in which the ethylene component in the polyethylene resin is 70% by mass or more include CX3007 and VL100 manufactured by Sumitomo Chemical Co., Ltd.
  • the density of the polyethylene resin is 850kg / m 3 ⁇ 920kg / m 3, more preferably a 860kg / m 3 ⁇ 910kg / m 3, in particular at 870kg / m 3 ⁇ 908kg / m 3
  • it is 880 kg / m 3 to 906 kg / m 3 .
  • the melt flow rate (MFR: 190 ° C., 2.16 kgf) of the polyethylene-based resin used is preferably in the range of 0.5 g / 10 min to 8 g / 10 min, and 0.8 g / 10 min to 7.0 g / 10 min.
  • the range of is more preferable. By making it the said range, it becomes easy to perform the film-forming which made the thickness of each layer uniform.
  • the adhesive layer may contain a polyolefin resin other than the polyethylene resin, and the type thereof is not particularly limited, and examples thereof include crystalline polypropylene, copolymerization of propylene and a small amount of ⁇ -olefin, and the like. Since these resins generally tend to decrease the adhesive strength even if they are blended in a small amount, it is preferable to blend them in a proportion of 1% by mass or more and 20% by mass or less.
  • tackifying resins include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, terpene resins, coumarone-indene resins, styrene resins, rosin resins, and the like.
  • the molecular weight of the tackifying resin is not particularly limited and can be set appropriately, but if the molecular weight is small, there is a risk of causing material transfer from the adhesive layer to the coated body or heavy peeling, while the molecular weight is large. If it becomes, there exists a tendency for the improvement effect of adhesive force to become scarce. Accordingly, the number average molecular weight of the tackifying resin is preferably about 1,000 to 100,000. The number average molecular weight can be measured by gel permeation chromatography (standard substance: polystyrene) or the like.
  • the compounding amount of the tackifying resin in the adhesive layer is preferably in the range of 5% by mass to 20% by mass with respect to 100% by mass of the adhesive layer component. If the compounding amount of the tackifying resin exceeds 20% by mass, the molecular weight of the tackifying resin is low, so the melt viscosity becomes extremely low, and a polypropylene resin is mainly used when coextrusion film formation using a T die or the like is performed. Not only is it difficult to laminate the base material layer as a component, but also the adhesive layer becomes sticky, and the roll-out property of the film from the roll state tends to be difficult to improve.
  • the blending amount of the tackifying resin is preferably 6% by mass or more and 20% by mass or less. More preferably, it is the range of 6 mass% or more and 15 mass% or less.
  • the amount of the polystyrene resin blended is preferably 3% by mass or more and 12% by mass or less, more preferably 5% by mass or more and 10% by mass or less.
  • the softening agent examples include low molecular weight diene polymers, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene and derivatives thereof, and polybutene.
  • the molecular weight of the softening agent is not particularly limited and can be set appropriately.However, if the molecular weight is small, there is a risk of causing material transfer from the adhesive layer to the coated body or heavy peeling, while the molecular weight is large. There is a tendency that the effect of improving the adhesion is poor. Accordingly, the number average molecular weight of the softener is preferably about 1,000 to 100,000. The number average molecular weight can be measured by the same method as in the case of the tackifier resin.
  • the tackifying resin and softening agent used in the adhesive layer are liquids or powders depending on the type, and there are things that contaminate the extruder during extrusion.
  • Such a problem can be improved by using a tackifier resin or a softener in a master batch with a polyethylene resin or a polyolefin resin. Therefore, it is preferable to use the tackifier resin and the softening agent in a master batch with a polyethylene resin or a polyolefin resin.
  • the pressure-sensitive adhesive force of the pressure-sensitive adhesive film (pressure-sensitive adhesive layer) of the present invention is preferably in the range of 200 cN / 25 mm to 1000 cN / 25 mm with respect to the acrylic plate at 23 ° C. in consideration of use in various coverings.
  • the adhesive strength is less than 200 cN / 25 mm, turning or the like occurs when protecting depending on the covering, and the function as a protective film cannot be carried.
  • the adhesive strength exceeds 1000 cN / 25 mm, there is a possibility that the film cannot be smoothly peeled when the film is peeled from the covering.
  • the range is 2 cN / 25 mm to 20 cN / 25 mm with respect to the prism sheet at 23 ° C. in consideration of use.
  • the adhesive strength is less than 2 cN / 25 mm, turning or the like occurs when protecting, and the function as a protective film cannot be carried.
  • the adhesive strength exceeds 20 cN / 25 mm, there is a possibility that the film cannot be smoothly peeled when the film is peeled off.
  • the adhesive strength can be appropriately set by changing the resin composition, thickness, etc. of the adhesive layer.
  • the pressure-sensitive adhesive layer according to the present invention may contain known additives as necessary.
  • a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improvement agent and the like may be contained.
  • these components have a relatively low molecular weight, and may bleed out to the surface of the adhesive layer to reduce the adhesive strength of the adhesive layer. Therefore, when using an additive, it is preferable that the amount of low molecular weight substances on the surface of the adhesive layer is less than 1 mg / m 2 .
  • the measurement of the low molecular weight substance on the surface of the adhesive layer was performed according to the following procedure. After washing the surface of the adhesive layer with an organic solvent that does not erode the resin constituting the adhesive layer such as ethanol, the organic solvent was removed from the cleaning liquid with an evaporator, and the residue was weighed and the numerical value obtained by washing was washed. It was obtained by dividing by the surface area of the adhesive layer surface. If the residue is present in an amount of 1 mg / m 2 or more, there will be foreign matter between the adhesive layer surface and the surface of the cover, reducing the contact area with the cover and reducing the van der Waals force. Adhesive strength decreases, which is not preferable. When adding additives, select additives such as polymer type, or study the amount and method of addition, so that there is no migration or transfer of low molecular weight substances (foreign substances) to the adhesive layer. It is necessary to.
  • the pressure-sensitive adhesive film of the present invention has a release layer on the surface opposite to the pressure-sensitive adhesive layer laminated on one side of the base material layer. Thereby, even if it sticks adhesive films, it can suppress that blocking of adhesive films arises.
  • a release layer especially when the adhesive film is stored in a roll state, and when the film is subsequently fed out, it is difficult to cause problems such as partial stretching or deformation of the film, and excellent in workability. It can be.
  • it is effective to form surface irregularities on the release layer to reduce the contact area with the adhesive layer.
  • the release layer preferably has a polypropylene resin as a main component (about 50% by mass or more).
  • a polypropylene resin include a propylene-ethylene block copolymer.
  • ⁇ -olefin (co) polymers having 4 or more carbon atoms such as low density polyethylene and 4-methylpentene-1 (co) polymer are preferably used.
  • Other examples include linear low density polyethylene, high density polyethylene, copolymers of ethylene and a small amount of ⁇ -olefin, copolymers of ethylene and vinyl acetate, polystyrene, polyester resins, polyamide resins, and the like. It is done.
  • 4-methylpentene-1 (co) polymer not only the surface of the release layer is roughened but also the surface free energy on the film surface is lowered, thereby further improving the peelability. Can be expected.
  • the three-dimensional average surface roughness SRa of the release layer surface is preferably 0.10 ⁇ m or more and 0.50 ⁇ m or less. By doing so, blocking resistance and the protection performance of a covering can be improved.
  • the surface roughness of the release layer is lower than 0.10 ⁇ m, the film feedability when the film is in roll form may be deteriorated.
  • the surface roughness of the release layer is higher than 0.50 ⁇ m, the surface irregularities of the release layer may be transferred to the surface of the adhesive layer, and the adhesive force may be significantly reduced.
  • the surface unevenness of the release layer is more preferably a surface having an average surface roughness SRa of 0.25 ⁇ m or more and 0.45 ⁇ m or less.
  • the three-dimensional average surface roughness SRa of the release layer surface means the average roughness at the center plane when the surface roughness curve is approximated by a sine curve, and can be measured by a surface roughness measuring device or the like.
  • the self-adhesive surface protective film of this invention is comprised from each layer of the base material layer containing the said resin component, the adhesion layer, and a mold release layer.
  • the thickness of the self-adhesive surface protective film of the present invention is preferably 10 ⁇ m or more and 150 ⁇ m or less, more preferably 15 ⁇ m or more and 120 ⁇ m or less, and further preferably 20 ⁇ m or more and 100 ⁇ m or less. If the total thickness of the film is too thin, it may be inferior in handling, and if it is too thick, the rigidity becomes high and handling properties are inferior, and the film may be disadvantageous in terms of cost.
  • the thickness of the base material layer of the present invention is preferably 5 ⁇ m or more and less than 100 ⁇ m, more preferably 10 ⁇ m or more and 75 ⁇ m or less, and further preferably 15 ⁇ m or more and 55 ⁇ m or less.
  • the thickness of the base material layer is less than 5 ⁇ m, there is a problem that the waist feeling is weak, wrinkles etc. are easily formed when pasted to a covering as a protective film, and sufficient adhesive strength cannot be obtained. If it is above, the film is disadvantageous in terms of cost.
  • the thickness of the adhesive layer of the present invention is preferably 1 ⁇ m or more and less than 30 ⁇ m.
  • the thickness of the adhesive layer is preferably 2 ⁇ m or more and 20 ⁇ m or less, more preferably 3 ⁇ m or more and 15 ⁇ m or less, and particularly preferably 4 ⁇ m or more and 8 ⁇ m or less.
  • the thickness of the release layer of the present invention is preferably 1 ⁇ m or more and less than 30 ⁇ m.
  • the thickness of the release layer is preferably 2 ⁇ m or more and 20 ⁇ m or less, and more preferably 3 ⁇ m or more and 15 ⁇ m or less.
  • the peel strength of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film of the present application with respect to the release surface is preferably in the range of 250 cN / 40 mm or less at 23 ° C. from the viewpoint of the film payout property when the pressure-sensitive adhesive film is in roll form. If the peeling force exceeds 250 cN / 40 mm, problems such as partial stretching or deformation of the film occur when the film is fed out when the adhesive film is rolled. More preferably, it is 200 cN / 40 mm or less. In addition, the lower limit of the peeling force with respect to the mold release surface of the pressure-sensitive adhesive film is about 1 cN / 40 mm, more preferably about 5 cN / 40 mm, as a practical value.
  • the self-adhesive surface protective film of the present invention is composed of a substrate layer containing the above resin component, an adhesive layer, and a release layer, and the resin constituting each layer is, for example, a single-screw or biaxial extruder. It is obtained by being fed into a feed block type or multi-manifold type T-die while being melted and laminated and extruded with three layers (base material layer, adhesive layer, release layer) or more.
  • the temperature of the extruder of each layer may be appropriately adjusted in consideration of the molding temperature of the components used in each layer in order to bring each layer into a molten state. For example, it may be adjusted in the range of 200 ° C. to 260 ° C. Also good.
  • the temperature of the T die may be the same as the above temperature.
  • the take-up speed from the T die to the casting roll may be a speed at which each layer has a suitable thickness, for example, 10 m / min to 200 m / min, preferably 10 m / min to 100 m / min.
  • the adhesive film of the present invention is preferably in the form of a roll in terms of handling.
  • the upper limit of the width and the winding length of the film roll is not particularly limited, but from the viewpoint of ease of handling, the width is generally 1.5 m or less, and the winding length is preferably 5000 m or less when the film thickness is 40 ⁇ m.
  • a winding core a plastic core and metal cores, such as 3 inches, 6 inches, and 8 inches, can usually be used.
  • the adhesive film of the present invention is a member such as a prism sheet used for optical applications, a synthetic resin plate (for example, for building materials), a stainless plate (for example, for building materials), an aluminum plate, a decorative plywood, a steel plate, and a glass plate.
  • a synthetic resin plate for example, for building materials
  • a stainless plate for example, for building materials
  • an aluminum plate for example, a decorative plywood, a steel plate, and a glass plate.
  • Home appliances, precision machinery to protect the surface of automobile bodies during production, to protect against damage when stacking, storing, transporting, transporting in the manufacturing process, and goods Can be used for protecting from scratches during secondary processing (for example, bending or pressing).
  • the present invention will be further described with reference to examples.
  • the present invention is not limited to the following examples without departing from the gist thereof.
  • the evaluation method of the physical property in a following example and a comparative example is as follows.
  • the covering and the test piece are 5 mm.
  • the pressure was reciprocated once at a speed of / sec.
  • the resistance value when peeled by 180 degrees was defined as the adhesive strength [cN / 25 mm].
  • 180 degree peeling means holding the peeling angle between the acrylic plate and the film at the time of measuring the resistance value at the time of peeling at 180 degrees.
  • a polyester sheet having a thickness of 190 ⁇ m and a size of 25 mm ⁇ 170 mm is prepared as a grip margin for the measurement sample, and the width of the paste margin is 15 mm at the end of the measurement sample on which the test piece and the acrylic plate are pressure-bonded.
  • the polyester sheet was affixed with cellophane tape and used as a grip allowance for measurement.
  • a schematic diagram of the measurement sample is shown in FIG. The measurement was carried out for three samples prepared from the films produced in the examples and comparative examples, and the average value was taken as the adhesive strength of the samples. In the case of the prism sheet, the measurement was performed in the same manner.
  • a test piece having a length of 150 mm in the winding direction at the time of film production and a length of 40 mm in the direction perpendicular thereto is cut out and pasted to the adhesive surface and the acrylic plate through a double-sided adhesive tape.
  • a rubber roll having a mass of 2000 g (with a roller surface spring hardness of 80 Hs and a 6 mm thick rubber layer, 45 mm width and 95 mm diameter (including rubber layer)) ), The mold release surface and the test piece were reciprocated once at a speed of 5 mm / second and pressure bonded.
  • Example 1 (Preparation of base material layer) 100% by mass of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, 230 ° C. MFR: 7.5 g / 10 min) was melt-extruded at 240 ° C. with a 90 mm ⁇ single screw extruder to obtain a base material layer.
  • a homopolypropylene resin manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, 230 ° C. MFR: 7.5 g / 10 min
  • Styrene elastomer hydrogenated block copolymer of styrene and butadiene, manufactured by Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene component ratio 12% by mass, ethylene component ratio 18% by mass, 230 ° C. MFR: 4.5 g / 10 min) 40% by mass, ethylene- ⁇ -olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd .: CX3007, 190 ° C.
  • Lamination extrusion is performed in a 245 ° C three-layer T die (feed block type, lip width 850 mm, lip gap 1 mm) with the base material layer, adhesive layer, and release layer melted in each extruder. It was.
  • the extruded film is taken to a casting roll at a temperature of 30 ° C. at a rate of 20 m / min, cooled and solidified, and the substrate layer thickness is 28 ⁇ m, the adhesive layer thickness is 6 ⁇ m, the release layer thickness is 6 ⁇ m, the film width is 600 mm, and the film length.
  • a three-kind three-layer unstretched film having a length of 1100 m was obtained.
  • this film was slit at a speed of 50 m / min while applying a contact pressure of 50 N to the film width by a rubber roll with a take-up tension of 40 N, whereby an unstretched film having a film width of 550 mm and a film length of 500 m was obtained. Obtained.
  • Example 2 The base material layer and the release layer were the same as in Example 1, but the adhesive layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
  • Styrene elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene component ratio 12% by mass, ethylene component ratio 18% by mass, 230 ° C. MFR: 4.5 g / 10 min) 60% by mass and ethylene- ⁇ olefin copolymer 40% by mass (Sumitomo Chemical Co., Ltd .: CX3007, 190 ° C. MFR: 3.7 g / 10 min, elastic modulus: 26 MPa) was melt-extruded at 210 ° C. with a 45 mm ⁇ single screw extruder to obtain an adhesive layer.
  • Example 3 The base material layer and the release layer were the same as in Example 1, but the adhesive layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
  • Styrene elastomer hydrogenated block copolymer of styrene and butadiene, manufactured by Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene component ratio 12% by mass, ethylene component ratio 18% by mass, 230 ° C.
  • MFR 4.5 g / 10 min
  • 40% by mass and ethylene- ⁇ -olefin copolymer (Sumitomo Chemical Co., Ltd .: VL100, 190 ° C.
  • MFR 0.8 g / 10 min
  • elastic modulus 64 MPa
  • petroleum resin Arakawa Chemical: Alcon (registered) (Trademark) P125
  • 10% by mass was melt-extruded at 210 ° C. with a 40 mm ⁇ single-screw extruder to obtain an adhesive layer.
  • Example 4 The base material layer and the release layer were the same as in Example 1, but the adhesive layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
  • Styrene elastomer manufactured by Asahi Kasei Chemicals: Tuftec (registered trademark) H1041, styrene component ratio 30% by mass, ethylene component ratio 49% by mass, 230 ° C.
  • MFR 5.0 g / 10 min
  • 85% by mass and ethylene- ⁇ olefin copolymer (Sumitomo Chemical Co., Ltd .: CX3007, 190 ° C.
  • MFR 0.8 g / 10 min, elastic modulus: 26 MPa) 5 mass% and petroleum resin (Arakawa Chemical: Alcon (registered trademark) P125) 10 mass% are 40 mm ⁇ single screw extruder. Was subjected to melt extrusion at 210 ° C. to form an adhesive layer.
  • Example 5 The substrate layer and the release layer were the same as in Example 1, except that the adhesive layer was changed to the following contents, the substrate layer thickness was 26 ⁇ m, the adhesive layer thickness was 8 ⁇ m, and the release layer thickness was 6 ⁇ m.
  • a three-kind three-layer unstretched film was obtained by the same production method as in No. 1.
  • Styrene elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene component ratio 12% by mass, ethylene component ratio 18% by mass, 230 ° C. MFR: 4.5 g / 10 min) 60% by mass and ethylene- ⁇ olefin copolymer 40% by mass (Sumitomo Chemical Co., Ltd .: CX3007, 190 ° C. MFR: 3.7 g / 10 min, elastic modulus: 26 MPa) was melt-extruded at 210 ° C. with a 45 mm ⁇ single screw extruder to obtain an adhesive layer.
  • Example 6 The substrate layer and the release layer were the same as in Example 1, except that the adhesive layer was changed to the following contents, the substrate layer thickness was 30 ⁇ m, the adhesive layer thickness was 4 ⁇ m, and the release layer thickness was 6 ⁇ m.
  • a three-kind three-layer unstretched film was obtained by the same production method as in No. 1.
  • Styrene elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene component ratio 12% by mass, ethylene component ratio 18% by mass, 230 ° C. MFR: 4.5 g / 10 min) 40% by mass and ethylene- ⁇ olefin copolymer (Sumitomo Chemical Co., Ltd .: CX3007, 190 ° C. MFR: 3.7 g / 10 min, elastic modulus: 26 MPa) 55% by mass and petroleum resin (Arakawa Chemical: Alcon (registered trademark) P125) 5% by mass are 45 mm ⁇ single-screw extruder. Was subjected to melt extrusion at 210 ° C. to form an adhesive layer.
  • Example 4 The base material layer and the release layer were the same as in Example 1, but the adhesive layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
  • Styrenic elastomer manufactured by Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene component ratio 12% by mass, ethylene component ratio 18% by mass, 230 ° C. MFR: 4.5 g / 10 min
  • 40% by mass and homopolypropylene manufactured by Sumitomo Chemical Co., Ltd.
  • FLX80E4 190 ° C.
  • the films obtained in Examples 1 to 6 had practically sufficient adhesive strength when used as a protective film, and had good peelability when the film was drawn from a roll. It was.
  • the films obtained in Comparative Examples 1 and 2 were not necessarily good in peelability when the film was drawn from the roll.
  • the films obtained in Comparative Examples 3 and 4 could not be said to have sufficient adhesion to the covering.
  • all the films obtained in the comparative examples were inferior in quality and low in practicality.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne un film de protection de surface autoadhésif comprenant des couches adhésives qui sont stratifiées sur les deux surfaces d'une couche de substrat de résine de polypropylène par coextrusion d'une couche de libération sur les surfaces faisant face aux couches adhésives, la résine formant les couches adhésives comprenant au moins une résine de polyéthylène et un élastomère de type styrène choisi, par exemple, parmi des agents d'hydrogénation de copolymères séquencés comportant des séquences polymères styrène et des séquences polymères butadiène, la quantité d'élastomère de type styrène comprise dans les couches adhésives étant située dans la plage allant de 35 à 99 % en masse inclus, la quantité de résine de polyéthylène comprise dans les couches adhésives étant située dans la plage allant de 1 à 65 % en masse inclus, et la somme de la résine de polyéthylène et des constituants d'éthylène dans l'élastomère de type styrène étant située dans la plage allant de 35 à 70 % en masse des constituants des couches adhésives.
PCT/JP2013/060087 2012-04-10 2013-04-02 Film de protection de surface autoadhésif WO2013153990A1 (fr)

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KR1020147025456A KR102020085B1 (ko) 2012-04-10 2013-04-02 자기 점착성 표면 보호 필름
KR1020197014658A KR102089231B1 (ko) 2012-04-10 2013-04-02 자기 점착성 표면 보호 필름
CN201380019463.6A CN104220548A (zh) 2012-04-10 2013-04-02 自粘合性表面保护薄膜

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JP2017534483A (ja) * 2014-09-22 2017-11-24 ダウ グローバル テクノロジーズ エルエルシー 密着特性を有するホイルラップ
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CN106103089B (zh) * 2014-02-28 2018-10-16 东丽薄膜先端加工股份有限公司 加热工序用表面保护膜
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CN104789143B (zh) * 2015-03-24 2017-08-29 昆山金华安电子科技有限公司 一种导光板光面专用聚丙烯保护膜
CN105500859A (zh) * 2015-06-26 2016-04-20 宝丽菲姆保护膜（苏州）有限公司 一种高粘自粘保护膜及其制备方法
JP6090543B1 (ja) 2015-08-21 2017-03-08 東レフィルム加工株式会社 表面保護フィルム
CN106221596A (zh) * 2016-07-22 2016-12-14 辽博科技（上海）有限公司 一种光学级自粘性保护膜及其在电子光学组件的应用
CN106281085A (zh) * 2016-08-18 2017-01-04 宁波卓胜新材料有限公司 一种汽车零配件用自粘气保护胶带及其制备方法
CN107142032B (zh) * 2017-05-03 2020-12-08 张家港康得新光电材料有限公司 自粘保护膜
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JP6569723B2 (ja) 2019-09-04
JP2018087332A (ja) 2018-06-07
CN110157350A (zh) 2019-08-23
CN104220548A (zh) 2014-12-17
KR102020085B1 (ko) 2019-09-09
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CN110283545A (zh) 2019-09-27
JP6286856B2 (ja) 2018-03-07

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