CN103889715B - Polyolefin mesentery - Google Patents

Polyolefin mesentery Download PDF

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Publication number
CN103889715B
CN103889715B CN201280052780.3A CN201280052780A CN103889715B CN 103889715 B CN103889715 B CN 103889715B CN 201280052780 A CN201280052780 A CN 201280052780A CN 103889715 B CN103889715 B CN 103889715B
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China
Prior art keywords
release layer
weight
film
layer
alpha
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CN201280052780.3A
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CN103889715A (en
Inventor
山本茂知
大木祐和
多贺敦
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Toyobo Co Ltd
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Toyobo Co Ltd
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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability

Landscapes

  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Problem of the present invention is the self adhesion surface protection film obtaining a kind of film flexibility (adaptability) of operation excellence; it shows strong bonding force to coating body and can be used in various coating body, even and if when being also difficult to when extracting film afterwards out to extend with causing membrane portions or the problem such as distortion with roller volume state keeping bonding film.The present invention relates to a kind of polyolefin mesentery, it is characterized in that, it is by the one side laminate adhesive layer of coextrusion at the substrate layer formed by polypropylene-based resin, and form at the stacked release layer of opposing face, the resin forming release layer at least comprises the block copolymer of propylene and ethene, with alpha-olefin (being total to) polymer that carbon number is more than 4, carbon number is that the use level of alpha-olefin (being total to) polymer of more than 4 is more than 5 % by weight and lower than 35 % by weight in the resinous principle forming release layer, the surface roughness (SRa) of release layer is more than 0.20 μm and less than 0.50 μm.

Description

Polyolefin mesentery
Technical field
The present invention relates to a kind of polyolefin mesentery.Polyolefin mesentery of the present invention may be used for the parts such as the prismatic lens used in optical applications, synthetic resin board (such as construction material is used), corrosion resistant plate (such as construction material is used), aluminium sheet, fancy plywood, steel plate, glass plate, family's electrical article, precision optical machinery etc.In addition, said polyolefins mesentery can be suitable for for protection manufacture time body of a motor car surface, be used for protection article pile up, keeping, transport or manufacturing process in carry time escape injury and be used for protection article escape injury in secondary operations (such as bending machining or press process) time.
Background technology
Just use the bonding film for the purpose of the surface of protective covering body when the processing of construction material, electric product, electronic product, automobile etc., keeping, transport all the time; such bonding film must have good cohesive, and can easily peel off and can not make each surface of adhesive contamination after a procedure.
In recent years, for above-mentioned coating body, along with the variation of its kind, can not only see by the level and smooth coating body of clad can, and many coating bodies with concave-convex surface can also be seen.As the coating body with concave-convex surface, the prism-type lens section etc. of the prismatic lens such as used in optics can be listed.In order to embody sufficient bonding force when the coating body with concave-convex surface such to prismatic lens uses, and consider the bonding force etc. improving adhesive layer, even if contact area is little also can obtain bonding force to make.
In order to improve the bonding force of adhesive layer, although resin can be used as to show the styrene series elastomer, olefin-based elastomer etc. of high adhesion as principal component, if but improve the bonding force of adhesive layer, then when occurring producing adhesion when extracting film afterwards out with roller volume state keeping film, extend to membrane portions or the problem such as distortion.
As the countermeasure of the problems referred to above, attempting by use in release layer carbon number be more than 4 alpha olefin copolymer improve adhesion (such as with reference to patent document 1 etc.) when extracting film out.But, at the general temperature extruding polypropylene-based resin, use T mould etc. by coextrusion masking, the stacked carbon number containing more than 50 % by weight is the release layer of the alpha olefin copolymer of more than 4 at the one side of the substrate layer formed by polypropylene-based resin if want, then the unfavorable condition that the masking that there is release layer is deteriorated.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-No. 42757 publications
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is the self adhesion surface protection film providing a kind of film flexibility (adaptability) of operation excellence; it shows strong bonding force to coating body and can be used in various coating body, even and if when being also difficult to when extracting film afterwards out to extend with causing membrane portions or the problem such as distortion with roller volume state keeping bonding film.That is, the object of the present invention is to provide a kind of polyolefin mesentery, it has good fissility and masking and can not produce shaggy transfer printing and can not suppress cohesive.
For solving the means of problem
The present inventor etc. conduct in-depth research, and found that and can solve above-mentioned problem by the scope match ratio of the resin used in release layer, surface roughness being set to regulation, thus complete the present invention.Namely, the present invention relates to a kind of polyolefin mesentery, it is characterized in that, it is by the one side laminate adhesive layer of coextrusion at the substrate layer formed by polypropylene-based resin, and form at the stacked release layer of opposing face, the resin forming release layer at least comprises the block copolymer of propylene and ethene, with alpha-olefin (being total to) polymer that carbon number is more than 4, carbon number is that the use level of alpha-olefin (being total to) polymer of more than 4 is more than 5 % by weight and lower than 35 % by weight in the resinous principle forming release layer, the surface roughness (SRa) of release layer is more than 0.20 μm and less than 0.50 μm.
In this case, preferably make above-mentioned carbon number be more than 4 alpha olefin copolymer be 4-methyl-1-pentene system (being total to) polymer.
In addition, in this case, the MFR of above-mentioned polypropylene-based resin (230 DEG C, 2.16Kgf) is preferably made to be 1.0 ~ 15g/10 minute.
And then, in this case, preferably make at least to use styrene series elastomer in above-mentioned adhesive layer and the MFR of this styrene series elastomer (230 DEG C, 2.16Kgf) is 0.5 ~ 20g/10 minute.
Invention effect
Polyolefin mesentery of the present invention has the following advantages: show strong bonding force to coating body and can be used in various coating body, even and if when being also difficult to when extracting film afterwards out to extend with causing membrane portions or the problem such as distortion with roller volume state keeping bonding film, make the flexibility (adaptability) of operation of film excellent.That is, according to the present invention, can provide a kind of polyolefin mesentery, it has good fissility and masking and can not produce shaggy transfer printing and can not suppress cohesive.
Accompanying drawing explanation
Fig. 1 is the schematic diagram measuring sample.
Detailed description of the invention
Below, the embodiment of polyolefin mesentery (bonding film) of the present invention is described.
(substrate layer)
Polyolefin mesentery needs of the present invention take polypropylene-based resin as the substrate layer of principal component, as polypropylene-based resin as used herein, crystalline polypropylene can be listed, the random copolymer of propylene and a small amount of alpha-olefin, block copolymer etc., more specifically, as crystalline polypropylene resin, can list at middle insoluble isotactic propylene homopolymers of normal heptane used such as common extrusion moldings, or containing the propylene of more than 60 % by weight propylene and the copolymer of other alpha-olefin, the copolymer of this Noblen or propylene and other alpha-olefin can be used alone or used in combination.Preferably make the propylene units comprising more than 50 % by weight in substrate layer, preferably comprise the propylene units of more than 60 % by weight further.If propylene is lower than 50 % by weight, then making film become sometimes does not have toughness, makes process become difficulty.
Here, so-called normal heptane is insoluble to be referred to the character of polyacrylic crystallinity for index and simultaneously display security, in the present invention, preferred scheme be use meet No. 20th, Showa in February, 57 Health and human services department bulletin regulation normal heptane insoluble (25 DEG C extract 60 minutes time stripping quantity be below 150ppm (being below 30ppm when serviceability temperature is more than 100 DEG C)) isotactic propylene homopolymer.
As the alpha-olefin copolymer composition of the copolymer of propylene and other alpha-olefin, preferred carbon number is the alpha-olefin of 2 ~ 8, such as, be the alpha-olefin of more than the C4 such as ethene or 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene.Here, so-called copolymer preferably makes one kind or two or more above-mentioned illustrated alpha-olefin and propylene polymerization and the random or block copolymer that obtains.The melt flow rate (MFR) (MFR:230 DEG C, 2.16Kgf) of the polypropylene-based resin used is preferably the scope of 1.0 ~ 15g/10 minute, is more preferably the scope of 2.0 ~ 10.0g/10 minute.In addition, also the copolymer of propylene and other alpha-olefin can be mixed with two or more.And then, also the scrap film of generation when the film obtained in the present invention being carried out to Product processing can be carried out granulation again as recovery raw material, and add in substrate layer.Reclaiming raw material by using, can production cost be suppressed.
(adhesive layer)
For the adhesive layer of polyolefin mesentery of the present invention, as long as known adhesive then all can use, but be preferably styrene series elastomer, olefin-based elastomer.Especially in order to embody high bonding force, and can be suitable for using styrene series elastomer.In addition, in order to control bonding force, also polyolefin-based resins, tackifying resin, softening agent can be mixed as required.
Styrene series elastomer can be enumerated: the A-B-A type block polymer such as s-B-S, styrene-isoprene-phenylethene, styrene-ethylene/butylene copolymer-styrene, styrene-ethylene/propylene copolymer-styrene; The A-B type block polymer such as styrene-butadiene, styrene-isoprene, styrene-ethylene/butylene copolymer, styrene-ethylene/propylene copolymer; The polystyrene random copolymers such as SBR styrene butadiene rubbers; And their hydride.
The melt flow rate (MFR) (MFR:230 DEG C, 2.16Kgf) of the styrene series elastomer used is preferably the scope of 0.5 ~ 20g/10 minute, be more preferably the scope of 2.0 ~ 15.0g/10 minute, the more preferably scope of 3 ~ 10g/10 minute, is particularly preferably the scope of 4 ~ 7g/10 minute.
Styrene series elastomer is preferably more than 50 % by weight in the adhesive layer resinous principle of adhesive layer (form), is more preferably more than 60 % by weight, and more preferably more than 70 % by weight, be more preferably more than 75 % by weight further; Be preferably less than 100 % by weight, be more preferably less than 99 % by weight, more preferably less than 98 % by weight, be more preferably less than 97 % by weight further.
Styrene content in styrene series elastomer is preferably more than 5 % by weight and less than 30 % by weight.If styrene content is lower than 5 % by weight, then granulation when making resin becomes difficulty, if styrene content is more than 30 % by weight, then bonding force reduces, and becomes and is difficult to obtain required bonding force.In addition, the styrene content in styrene series elastomer is preferably more than 10 % by weight and less than 25 % by weight, is more preferably more than 10 % by weight and less than 20 % by weight, and more preferably more than 10 % by weight and less than 15 % by weight.In addition, composition beyond styrene content in styrene series elastomer is preferably made up of the composition such as ethene, butylene, component amount beyond styrene content is preferably 70 ~ 95 % by weight in styrene series elastomer, be more preferably 75 ~ 90 % by weight, more preferably 80 ~ 90 % by weight, be more preferably 85 ~ 90 % by weight further.
It is the alpha-olefine polymers of 2 ~ 10 or the copolymer etc. of copolymer, ethene and unsaturated carboxylic acid or esters of unsaturated carboxylic acids that olefin-based elastomer can list carbon number.The elastomeric melt flow rate (MFR) of the olefin-based used (MFR:230 DEG C, 2.16Kgf) is preferably the scope of 0.5 ~ 20g/10 minute, is more preferably the scope of 2.0 ~ 10.0g/10 minute.
Polyolefin-based resins is not particularly limited, and can list the copolymer, polystyrene etc. of the copolymer of the copolymer of crystalline polypropylene, propylene and a small amount of alpha-olefin, low density polyethylene (LDPE), high density polyethylene (HDPE), ethene and a small amount of alpha-olefin, ethene and unsaturated carboxylic acid or esters of unsaturated carboxylic acids.Wherein, because substrate layer is made up of polypropylene-based resin, so from the relation of melt viscosity etc., also can be suitable for using polypropylene-based resin.The melt flow rate (MFR) (MFR:230 DEG C, 2.16Kgf) of the polyolefin-based resins used is preferably the scope of 1.0 ~ 100.0g/10 minute, be more preferably the scope of 2.0 ~ 30.0g/10 minute, the more preferably scope of 2 ~ 10g/10 minute, is particularly preferably the scope of 2 ~ 7g/10 minute.
The use level of the polyolefin-based resins in adhesive layer is preferably less than 25 % by weight.If the use level of polyolefin-based resins is more than 25 % by weight, then bonding force can be made to reduce according to used resin and can not get sufficient bonding force.The use level of polyolefin-based resins is preferably more than 5 % by weight.If the use level of polyolefin-based resins is lower than 5 % by weight, then make sometimes cross by force the bonding force of release layer and make the selection narrowed width of release layer.The use level of polyolefin-based resins is more preferably more than 6 % by weight and less than 20 % by weight, and more preferably more than 6 % by weight and below 15 weight.
Tackifying resin include, for example out aliphatic hydrocarbon resin, aromatic hydrocarbon resin, alicyclic hydrocarbon resin, terpene resin, coumarone-indene resin (coumarone-indene resin), phenylethylene resin series, abietic resin etc., wherein preferred alicyclic hydrocarbon resin (such as Petropols).The molecular weight of tackifying resin is not particularly limited, can suitably set, if but molecular weight diminishes, then may cause the material transport or re-separation etc. from adhesive layer to clung body, on the other hand, if molecule quantitative change is large, then exists and make the raising effect of bonding force become the tendency of shortcoming, so the number-average molecular weight of tackifying resin is preferably 1000 ~ about 100,000.
The use level of the tackifying resin in adhesive layer is preferably more than 5 % by weight and the scope of less than 30 % by weight.If the use level of tackifying resin is more than 30 % by weight, then melt viscosity is made to become extremely low because the molecular weight of tackifying resin is low sometimes, carrying out making when using the coextrusion masking of T mould etc. to become difficulty with using polypropylene-based resin as the stacked of the substrate layer of principal component.In addition, if the use level of the tackifying resin in adhesive layer is lower than 5 % by weight, then the bonding force change of adhesive layer may be helpless to.The use level of tackifying resin is more preferably more than 6 % by weight and less than 25 % by weight, more preferably more than 6 % by weight and less than 20 % by weight, be more preferably more than 6 % by weight further and less than 15 % by weight, be particularly preferably more than 6 % by weight and less than 10 % by weight.
As softening agent, include, for example out low-molecular-weight diene polymer, polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer or their derivative, polybutene etc.The molecular weight of softening agent is not particularly limited, can suitably set, if but molecular weight diminishes, then may cause the material transport or re-separation etc. from adhesive layer to clung body, on the other hand, if molecule quantitative change is large, then exists and make the raising effect of bonding force become the tendency of shortcoming, so the number-average molecular weight of softening agent is preferably 1000 ~ about 100,000.
In addition, the tackifying resin used in adhesive layer, softening agent root digs its kind liquid or powder, also has the material polluting extruder when extruding.Such problem can make for improving after tackifying resin, softening agent and polyolefin-based resins are made masterbatch, so use after preferably tackifying resin, softening agent and polyolefin-based resins being made masterbatch.
When considering for various coating body, polyolefin mesentery of the present invention is preferably the scope of 200 ~ 900cN/25mm at 23 DEG C to the bonding force of acrylic board.If bonding force is lower than 200cN/25mm, then can produces when protecting it according to the difference of coating body and crispatura, the function as diaphragm cannot be undertaken.On the other hand, if bonding force is more than 900cN/25mm, then may cannot successfully peel off from during prismatic lens stripping film.Bonding force suitably can set by changing the resin composition, thickness etc. of adhesive layer.Bonding force is more preferably more than 300cN/25mm and below 900cN/25mm, more preferably more than 400cN/25mm and below 800cN/25mm.
Polyolefin mesentery of the present invention can contain known additive as required.Such as also lubricant, anti-blocking agent, heat stabilizer, antioxidant, antistatic agent, photostabilizer, shock-resistant modifying agent etc. can be contained.But, preferably make the low molecular weight substance on adhesive layer surface lower than 1mg/m 2.
Here, the mensuration of the low molecular weight substance on adhesive layer surface is implemented according to the following steps.After adhesive layer surface ethanol etc. not being corroded the organic solvent washing of the resin forming adhesive layer, remove organic solvent with evaporimeter etc. from this cleaning solution, then the numerical value weighed calculated by this residue is tried to achieve divided by the surface area on washed adhesive layer surface.Here, if there is 1mg/m 2above residue, then make to there is foreign matter between adhesive layer is surperficial and clung body is surperficial, cause contact area reduction, Van der Waals force reduction, so make bonding force reduce, thus not preferred.Adding in additivated situation, needing by selecting the additive of polymer electrolyte etc. or studying addition and adding method etc. and make it to adhesive layer migration or can not be transferred on adhesive layer.
(release layer)
Polyolefin mesentery of the present invention forms release layer on the face contrary with the adhesive layer of the one side being laminated in substrate layer, even if thus film is overlapped each other, film adhesion is each other also few, particularly when being also difficult to when extracting film afterwards out to extend with causing membrane portions or the problem such as distortion with roller volume state keeping film, make the flexibility (adaptability) of operation of film excellent.Even if film adhesion each other also can not be there is in order to be overlapped each other by film, effectively make release layer forms concave-convex surface and reduces the contact area with adhesive layer.
In order to form concave-convex surface as described above, can be suitable for using propylene-ethylene block copolymer.By increasing the molecular weight of the ethylene-propylene rubber in propylene-ethylene block copolymer or increasing the amount of ethene, thus rough surface can be increased.In addition, by mixing resin inconsistent with it in propylene-ethylene block copolymer, thus rough surface can be increased further.And then, extruding in operation, by reduction to the shear rate of resin applying or prolongation holdup time, thus also can increase rough surface further.On the other hand, rough surface can also be reduced by the poly-acrylic resin that is mixed in propylene-ethylene block copolymer.
As resin inconsistent with propylene-ethylene block copolymer, can be suitable for using the carbon numbers such as 4-methyl-1-pentene system (being total to) polymer be more than 4 alpha-olefin (being total to) polymer.In addition, the copolymer, polystyrene, polyester based resin, polyamide series resin etc. of the copolymer of low density polyethylene (LDPE), high density polyethylene (HDPE), ethene and a small amount of alpha-olefin, ethene and vinylacetate can also be listed.Particularly 4-methyl-1-pentene system (being total to) polymer not only makes surface roughening with matt shape, but also estimates fissility to be improved further by reducing the surface free energy on film surface.
In addition, also the concavo-convex of surface can be realized by adding above-mentioned non-conforming resin in homo-polypropylene, random polypropylene, but when using propylene-ethylene block copolymer, by produce board change, masking time melting mixing condition be difficult to change concavo-convex state, stable production can be realized.
Carbon number in release layer (forming the resinous principle of release layer) is that the use level of alpha-olefin (being total to) polymer of more than 4 is more than 5 % by weight and the scope of less than 35 % by weight.Carbon number be the use level of alpha-olefin (being total to) polymer of more than 4 more than 35 % by weight time, use at the general temperature extruding polypropylene-based resin if want T mould etc. the one side of the substrate layer formed by polypropylene-based resin by coextrusion masking stacked release layer, then the masking of release layer can be made to be deteriorated.Carbon number be alpha-olefin (being total to) polymer of more than 4 use level lower than 5 % by weight time, be helpless to the peeling force improving release layer.Carbon number is that the use level of alpha-olefin (being total to) polymer of more than 4 is preferably more than 7 % by weight and less than 33 % by weight.In addition, it is the molecular weight of alpha-olefin (being total to) polymer of more than 4 about carbon number, if molecular weight diminishes, then may cause the material transport etc. from release layer to adhesive layer, so the number-average molecular weight of tackifying resin is preferably 10,000 ~ about 1,000,000.
The weight ratio (propylene-ethylene block copolymer/4-methyl-1-pentene system (being total to) polymer) of the propylene-ethylene block copolymer in release layer and 4-methyl-1-pentene system (being total to) polymer is preferably 95/5 ~ 65/35, is more preferably 93/7 ~ 67/33.
If in view of the resin of the adhesive layer in the present invention forms, then preferably make the average surface roughness SRa on release layer surface be more than 0.20 μm and less than 0.50 μm.The protective value of resistance to adhesive and clung body can be improved thus.If the surface roughness of release layer is lower than 0.20 μm, then the extractable of film when film being made roller scroll state is made to be deteriorated.If the surface roughness of release layer is higher than 0.50 μm, then the concave-convex surface of release layer can be transferred to the surface of adhesive layer and bonding force is significantly reduced sometimes.
Now, the concave-convex surface of release layer be more preferably formed as surface average surface roughness SRa reach more than 0.25 μm and the surface of less than 0.45 μm.
The mist degree of the film be laminated by the release layer with this kind of surface roughness is preferably more than 20% and less than 80%.In order to easily confirm the attaching of diaphragm to coating body, and making the mist degree of film be more preferably more than 30%, in addition, in order to make when masking foreign matter easily be found by foreign-body locator, and making mist degree be more preferably less than 70%.
The adhesive surface of polyolefin mesentery of the present invention is the scope of below 200cN/25mm to the peeling force of stripping surface at 23 DEG C, and this is preferred from the viewpoint of the extractable of film when bonding film being made roller scroll state.If peeling force is more than 200cN/25mm, then extend with producing membrane portions in the extraction of the film when bonding film being made roller scroll state or the problem such as distortion.Peeling force can be the addition of the alpha olefin copolymer of more than 4 by the carbon number changed in release layer, surface roughness and suitably setting.
In addition, the lower limit of adhesive surface to the peeling force of stripping surface of polyolefin mesentery counts about 1cN/25mm with actual value, is about 5cN/25mm further.
The thickness of the adhesive layer of the polyolefin mesentery in the present invention is preferably more than 1 μm and lower than 30 μm.If the thickness of adhesive layer is lower than 1 μm, be then difficult to utilize coextrusion to carry out stable masking, if the thickness of adhesive layer is more than 30 μm, then can become disadvantageous film in cost.
Now, when increasing bonding force, considering its viscosity, and preferably increasing thickness.By increasing the thickness of adhesive layer, thus easily increase the contact area with clung body.The thickness of adhesive layer is preferably more than 2 μm and less than 20 μm, more preferably more than 3 μm and less than 15 μm, is particularly preferably more than 4 μm and less than 8 μm.
The thickness of the substrate layer of polyolefin mesentery of the present invention is preferably more than 5 μm and lower than 100 μm, is more preferably more than 10 μm and lower than 75 μm, more preferably more than 15 μm and lower than 40 μm.If the thickness of substrate layer is lower than 5 μm; then there is the problem that toughness dies down, easily produces gauffer etc., cannot obtain bonding force fully when being attached at coating body as diaphragm; if the thickness of substrate layer is more than 100 μm, then can become disadvantageous film in cost.
The thickness of the release layer of polyolefin mesentery of the present invention is preferably more than 1 μm and lower than 30 μm.If the thickness of release layer is lower than 1 μm, be then difficult to utilize coextrusion to carry out stable masking, if the thickness of release layer is more than 30 μm, then can become disadvantageous film in cost.
Now, the thickness of release layer is preferably more than 2 μm and less than 20 μm, more preferably more than 3 μm and less than 15 μm, is particularly preferably more than 4 μm and less than 8 μm.
Polyolefin mesentery of the present invention by comprise the substrate layer of above-mentioned resinous principle, adhesive layer, release layer each layer form, as long as each layer plays effect of the present invention, then can be more than 1 layer or 2 layers.The extruder of such as singe screw, twin-screw etc. can be used to be delivered directly in the T mould of feed block-type by the resin forming each layer with molten condition, and to carry out stacked extruding, thus make the polyolefin mesentery of at least 3 layers.In order to make each layer be in molten condition, the temperature of the extruder of each layer can be considered the forming temperature of the composition that suitable each layer uses and suitably regulate, such as, can regulate in the scope of 200 DEG C ~ 260 DEG C.The temperature of T mould also can be identical with said temperature.Such as, as long as the speed of getting of drawing from T mould to casting roll makes each layer reach the speed of suitable thickness, is 10m/min ~ 50m/min, be preferably 10m/min ~ 30m/min.
Consider from process, polyolefin mesentery of the present invention is suitable for the form making roller volume.The width of film volume and the upper limit of volume length are not particularly limited, and from the easiness of process, preferably: bandpass is below 1.5m, volume is long is below 6000m when film thickness is 30 μm.In addition, as batching core, plastic core or the metal coremaking of 3 inches, 6 inches, 8 inches etc. can usually be used.In addition, from the adaptability of processing, the film volume coiled into according to the size of more than length 200m, more than width 450mm is preferably.
Polyolefin mesentery of the present invention can be used in the parts such as the prismatic lens used in optical applications, synthetic resin board (such as construction material is used), corrosion resistant plate (such as construction material is used), aluminium sheet, fancy plywood, steel plate, glass plate, household appliances, precision optical machinery etc.In addition, polyolefin mesentery of the present invention can being used for protecting the surface of body of a motor car when manufacturing, be used for protecting article piling up, keeping, the situation use that escapes injury and protect article to escape injury when secondary operations (such as bending machining or press process) when carrying in transport or manufacturing process.
This application claims the interests of the priority of No. 2011-238935, the Japanese patent application based on application on October 31st, 2011.The full content of the description of No. 2011-238935, the Japanese patent application of application on October 31st, 2011 is referred in the application as a reference.
Embodiment
Below, list embodiment and further illustrate the present invention.But the present invention only otherwise departing from its purport is just not limited to following embodiment.In addition, the evaluation method of the physical property in following embodiment, comparative example is as described below.
(1) fusible evaluation
According to JIS-Z-0237 (2000) adhesive tape bonding sheet test method, measure with following method.
As clung body, prepare acrylic board (the Mitsubishi Rayon Co. of 50mm × 150mm, Ltd. make: ACRYLITE (registration mark) 3mm is thick), as test film, the take-up direction cut out when film manufactures is 150mm and is the test film of 25mm in the direction orthogonal with this take-up direction, service property (quality) is that (roller surface is 80Hs by elastic hardness (spring hardness) for the rubber rollers of 2000g, thickness is that the rubber layer of 6mm is coating and width is 45mm, the rubber rollers that diameter (comprising rubber layer) is 95mm), and with the speed of 5mm/ second reciprocal 1 time and clung body and test film are crimped.After crimping, place under the environment of temperature 23 DEG C, relative humidity 65% after 30 minutes, use " AUTOGRAPH (registration mark) " (AGS-J) manufactured by (strain) island Feng making, with the speed of 300mm/ minute, 180 degree of strippings are carried out to it, and using Resistance Value now as bonding force [cN/25mm].So-called 180 degree of strippings make the peel angle of acrylic board and film remain on 180 degree when referring to the Resistance Value when measuring stripping.
When measuring, as the grasping part measuring sample, prepare thickness to be 190 μm, to be of a size of the polyester sheet of 25mm × 170mm, adhesive paste part is used to be attached on the end of the bonding film side of the mensuration sample that bonding film crimps with acrylic board for the cellophane tape (registration mark) that 15mm is wide, as grasping part during mensuration.By shown in Figure 1 for the schematic diagram measuring sample.Measure and 3 times are implemented for a sample, using the bonding force of its mean value as this sample.
(2) evaluation of resistance to adhesive
At acrylic board (the Mitsubishi Rayon Co. of 50mm × 150mm, Ltd. make: ACRYLITE (registration mark) 3mm is thick) whole on attach double-sided adhesive tape (day east electrician (strain) system: No.535A), the mode that the another side of double-sided adhesive tape comes alongside according to the adhesive surface of test film attaches the test film of 150mm while manufacturing (film take-up direction) × 50mm (direction that take-up direction when manufacturing with film is orthogonal).
As new test film, the take-up direction of cutting mountain when film manufactures is 150mm and is the test film of 25mm in the direction orthogonal with this take-up direction, after superimposed for the stripping surface of the test film that its adhesive surface and acrylic board attach by double-sided adhesive tape, service property (quality) be 2000g rubber rollers (roller surface by elastic hardness be 80Hs, thickness is the rubber rollers that the coating and width of the rubber layer of 6mm is 45mm, diameter (comprising rubber layer) is 95mm), and with the speed of 5mm/ second reciprocal 1 time and stripping surface and test film are crimped.After crimping, place under the environment of temperature 23 DEG C, relative humidity 65% after 30 minutes, use " AUTOGRAPH (registration mark) " (AGS-J) manufactured by (strain) island Feng making, with the speed of 300mm/ minute, 180 degree of strippings are carried out to it, and using Resistance Value now as peeling force [cN/25mm].
When measuring, as the grasping part measuring sample, prepare thickness to be 190 μm, to be of a size of the polyester sheet of 25mm × 170mm, use adhesive paste part to be attached on the end of the test film of 150mm × 25mm for the cellophane tape that 15mm is wide, as grasping part when measuring.Measure and 3 times are implemented to a sample, using the peeling force of its mean value as this sample.
(3) mensuration of average surface roughness
The contact-type 3 D median plane surface roughness meter (model ET-30HK) using (strain) little Ban research institute to manufacture, utilizes tracer method to measure the median plane mean roughness (SRa) on the surface of release layer under the following conditions.Condition is as described below, and the mean value measured 3 times is as average surface roughness value.
Stylus tip radius: 0.5 μm
Contact pilotage pressure: 20mgf
Removal amount: 80 μm
Measure long: 1000 μm
Finding speed: 100 μm/second
Bei Ding interval: 2 μm
(4) mensuration of mist degree
According to the optical characteristics test method of JIS-K-7105 plastics, the haze meter (NDH-1000) using Japanese electric look industry to manufacture measures.
(5) rough surface of release layer is to the transfer printing of adhesive layer
Use the digital microscope (VHX-200F) that KEYENCE manufactures, with the digital picture of the multiplying power of 100 times shooting film adhesive surface.Substantially situation about not occurring from the transfer printing of release layer is set to "○", situation serious for the transfer printing from release layer is set to "×".
(6) masking
The situation that can be filmed with uniform thickness when masking is set to "○", and the situation that can not be filmed with uniform thickness is set to "×".
[embodiment 1]
(making of substrate layer)
By HOPP resin (Sumitomo Chemical system: FLX80E4, MFR:7.5g/10min) 100wt%, melt extrude at 240 DEG C with 120mm φ single screw extrusion machine, make substrate layer.
(making of adhesive layer)
By styrene series elastomer (Asahi Kasei Chemicals system: TAFTEC (registration mark) H1221, styrene copolymerized than 12wt%, MFR:4.5g/10min) 85wt%, HOPP resin (Sumitomo Chemical system: FS2011DG3, MFR:2.5g/10min) 7.5wt% and Petropols (waste river chemical industry system: Arkon (registration mark) P125) 7.5wt%, melt extrude at 220 DEG C with 90mm φ single screw extrusion machine, make adhesive layer.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC4FC) 92wt% and polymethylpentene (Mitsui Chemicals system: RT31) 8wt%, melt extrude at 250 DEG C with 90mm φ single screw extrusion machine, make release layer.
(making of film)
Utilize each extruder to make substrate layer, adhesive layer, release layer be in the state of melting respectively, in 3 layers of T mould (feed block-type, die lip width are 850mm, die lip gap be 1mm) of 245 DEG C, carry out stacked extruding in this condition.The film extruded is drawn with the speed of 20m/min to get temperature be on the casting roll of 30 DEG C, carry out cooling curing, obtain 3 kinds of 3 layers of unstretching films that substrate layer thickness is 28 μm, bondline thickness is 6 μm, release layer thickness is 6 μm.
[embodiment 2]
Adhesive layer, substrate layer keep identical with embodiment 1, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC3HF) 76wt% and polymethylpentene (Mitsui Chemicals system: RT31) 24wt%, squeeze mountain machine with 90mm φ singe screw at 250 DEG C, to carry out melting squeeze mountain, make release layer.
[embodiment 3]
Substrate layer keeps identical with embodiment 1, adhesive layer, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of adhesive layer)
By styrene series elastomer (Asahi Kasei Chemicals system: TAFTEC (registration mark) H1221, styrene copolymerized than 12wt%, MFR:4.5g/10min), Petropols (waste river chemical industry system: Arkon (registration mark) P125) and HOPP resin (Sumitomo Chemical system: FS2011DG3, MFR:2.5g/10min) with after the mixing of the ratio of 80/7.5/12.5wt%, melt extrude at 220 DEG C with 90mm φ single screw extrusion machine, make adhesive layer.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC3HF) 92wt% and polymethylpentene (Mitsui Chemicals system: RT31) 8wt%, melt extrude at 250 DEG C with 90mm φ single screw extrusion machine, make release layer.
[embodiment 4]
Substrate layer keeps identical with embodiment 1, adhesive layer, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of adhesive layer)
By styrene series elastomer (Asahi Kasei Chemicals system: TAFTEC (registration mark) H1221, styrene copolymerized than 12wt%, MFR:4.5g/10min) and HOPP resin (Sumitomo Chemical system: FS2011DG3, MFR:2.5g/10min) with after the mixing of the ratio of 90/10wt%, melt extrude at 240 DEG C with 90mm φ single screw extrusion machine, make adhesive layer.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC3HF) 92wt% and polymethylpentene (Mitsui Chemicals system: RT31) 8wt%, melt extrude at 250 DEG C with 90mm φ single screw extrusion machine, make release layer.
[reference example 1]
Substrate layer keeps identical with embodiment 1, adhesive layer, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of adhesive layer)
By styrene series elastomer (Asahi Kasei Chemicals system: TAFTEC (registration mark) H1221, styrene copolymerized than 12wt%, MFR:4.5g/10min) 100wt%, melt extrude at 240 DEG C with 90mm φ single screw extrusion machine, make adhesive layer.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC4FC) 68wt% and polymethylpentene (Mitsui Chemicals system: RT31) 32wt%, melt extrude at 250 DEG C with 90mm φ single screw extrusion machine, make release layer.
[comparative example 1]
Substrate layer, adhesive layer keep identical with embodiment 1, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC4FC) 100wt%, melt extrude at 250 DEG C with 90mm φ single screw extrusion machine, make release layer.
[comparative example 2]
Substrate layer, adhesive layer keep identical with embodiment 1, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC4FC) 96wt% and polymethylpentene (Mitsui Chemicals system: RT31) 4wt%, melt extrude at 250 DEG C with 90mm single screw extrusion machine, make release layer.
[comparative example 3]
Substrate layer, adhesive layer keep identical with embodiment 1, release layer is changed to following content, wants to obtain 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1, but thickness and precision is poor and cannot obtain the film that can tolerate evaluation.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC3HF) 50wt% and polymethylpentene (Mitsui Chemicals system: RT31) 50wt%, melt extrude at 250 DEG C with 90mm φ single screw extrusion machine, make release layer.
[comparative example 4]
Substrate layer, adhesive layer keep identical with embodiment 1, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC3HF) 75wt%, polymethylpentene (Mitsui Chemicals system: RT31) 6wt% and HOPP resin (Sumitomo Chemical system: FLX80E4, MFR:7.5g/10min) 19wt%, melt extrude at 250 DEG C with 90mm φ single screw extrusion machine, make release layer.
[comparative example 5]
Substrate layer, adhesive layer keep identical with embodiment 1, release layer is changed to following content, obtains 3 kinds of 3 layers of unstretching films by method for making similarly to Example 1.
(making of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation system: BC4FC) 64wt%, polymethylpentene (Mitsui Chemicals system: RT31) 16wt% and ldpe resin, (space portion is emerging to be produced: R300) 20wt%, melt extrude at 250 DEG C with single screw extrusion machine in 90mm, make release layer.
The above results is shown in table 1 and 2.
As indicated in table 1, the film obtained in embodiment 1 ~ 4 has sufficient bonding force in practicality when using as diaphragm, also do not have shaggy transfer printing, and fissility when extracting out after film being made roller volume is also good, and masking is also good.
On the other hand, for the film obtained in comparative example 1,2 and 4, fissility when extracting out after film being made roller volume may not deserve to be called good.In the film obtained in comparative example 5, comparatively serious to the shaggy transfer printing from release layer of adhesive layer.In the method for making of comparative example 3, masking is poor and cannot obtain the film that can tolerate evaluation.The film obtained in comparative example is made to be poor quality, film that practicality is low thus.
Utilizability in industry
Polyolefin mesentery of the present invention may be used in synthetic resin board (such as construction material is used), corrosion resistant plate (such as construction material is used), aluminium sheet, fancy plywood, steel plate, glass plate, household appliances, precision optical machinery etc.In addition; polyolefin mesentery of the present invention also can be suitable for for protection manufacture time body of a motor car surface, be used for protection article pile up, keeping, transport or manufacturing process in carry time escape injury and be used for protection article escape injury in secondary operations (such as bending machining or press process) time, larger to the contribution of industrial circle.
Symbol description
1: upper jaw
2: polyester sheet
3: acrylic board
4: cellophane tape
5: bonding film
6: lower jaw
7: draw direction

Claims (5)

1. a polyolefin mesentery, it is characterized in that, it is by the one side laminate adhesive layer of coextrusion at the substrate layer formed by polypropylene-based resin, and form at the stacked release layer of opposing face, the resin forming release layer at least comprises the block copolymer of propylene and ethene, with alpha-olefine polymers or alpha olefin copolymer that carbon number is more than 4, carbon number is that the alpha-olefine polymers of more than 4 or the use level of alpha olefin copolymer are more than 5 % by weight and lower than 35 % by weight in the resinous principle forming release layer, the surface roughness SRa of release layer is more than 0.20 μm and less than 0.50 μm,
In described adhesive layer, at least use styrene series elastomer, the use level of described styrene series elastomer is more than 50 % by weight and lower than 100 % by weight.
2. polyolefin mesentery according to claim 1, wherein, described carbon number be more than 4 alpha-olefine polymers or alpha olefin copolymer be 4-methyl-1-pentene based polymer or 4-methyl-1-pentene based copolymer.
3. polyolefin mesentery according to claim 1 and 2, wherein, described polypropylene-based resin 230 DEG C, MFR under the condition of 2.16Kgf is 1.0 ~ 15g/10 minute.
4. polyolefin mesentery according to claim 1 and 2, wherein, described styrene series elastomer 230 DEG C, MFR under the condition of 2.16Kgf is 0.5 ~ 20g/10 minute.
5. polyolefin mesentery according to claim 3, wherein, described styrene series elastomer 230 DEG C, MFR under the condition of 2.16Kgf is 0.5 ~ 20g/10 minute.
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Families Citing this family (11)

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Publication number Priority date Publication date Assignee Title
CN106459684B (en) * 2014-06-18 2020-07-03 东洋纺株式会社 Self-adhesive surface protective film
JP2017146492A (en) * 2016-02-18 2017-08-24 リンテック株式会社 Film with protective film for laminating transparent conductive film, and method of manufacturing transparent conductive film
JP6851721B2 (en) * 2016-02-18 2021-03-31 リンテック株式会社 A film for laminating a transparent conductive film with a protective film, and a method for manufacturing a transparent conductive film.
KR102399713B1 (en) * 2016-12-16 2022-05-19 도레이 필름 카코우 가부시키가이샤 Release film and protective film
WO2019134120A1 (en) * 2018-01-05 2019-07-11 Baxter International Inc Multi-layer articles and methods for producing the same
CN111699091B (en) * 2018-04-16 2022-06-28 东丽薄膜先端加工股份有限公司 Laminated film
JP7238290B2 (en) * 2018-08-03 2023-03-14 東洋紡株式会社 laminated film.
CN109554137B (en) * 2018-12-04 2021-08-17 宁波激智科技股份有限公司 High-viscosity protective film and preparation method thereof
KR20210148093A (en) * 2019-03-29 2021-12-07 도레이 필름 카코우 가부시키가이샤 laminated film
JP7306228B2 (en) 2019-11-08 2023-07-11 三菱ケミカル株式会社 Laminated film, Laminated film for flexible printed circuit board process
CN113122160A (en) * 2021-04-29 2021-07-16 东莞市金恒晟新材料科技有限公司 Preparation method of novel thermal tackifying protective film

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1720310A (en) * 2002-10-25 2006-01-11 三菱化学株式会社 Release agent and release sheet

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4367082B2 (en) * 2002-10-25 2009-11-18 三菱化学ポリエステルフィルム株式会社 Release agent and release sheet
JP5047575B2 (en) * 2006-09-29 2012-10-10 三井化学株式会社 Surface protection film
JP2008265302A (en) * 2007-03-22 2008-11-06 Japan Polypropylene Corp Propylene resin film for surface protection
JP2011042757A (en) * 2009-08-24 2011-03-03 Mitsui Chemicals Inc Surface protection film
JP5600905B2 (en) * 2009-08-24 2014-10-08 東洋紡株式会社 Adhesive film
KR20120112848A (en) * 2010-02-02 2012-10-11 미쓰이 가가쿠 토세로 가부시키가이샤 Surface protective film
WO2011096350A1 (en) * 2010-02-02 2011-08-11 三井化学東セロ株式会社 Surface protective film
KR101932000B1 (en) * 2010-03-31 2018-12-24 도레이 필름 카코우 가부시키가이샤 Surface protection film
JP2012087164A (en) * 2010-10-15 2012-05-10 Dic Corp Surface protective film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1720310A (en) * 2002-10-25 2006-01-11 三菱化学株式会社 Release agent and release sheet

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