CN110157350A - Self adhesion surface protective film - Google Patents
Self adhesion surface protective film Download PDFInfo
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- CN110157350A CN110157350A CN201910490592.2A CN201910490592A CN110157350A CN 110157350 A CN110157350 A CN 110157350A CN 201910490592 A CN201910490592 A CN 201910490592A CN 110157350 A CN110157350 A CN 110157350A
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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
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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
- 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
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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
- 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
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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
- C09J7/20—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
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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
-
- 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
Abstract
Self adhesion surface protective film of the invention is that adhesive layer is laminated in the one side of the substrate layer formed by polypropylene-based resin by coextrusion, release layer is laminated on opposing sides and is formed, the resin for constituting above-mentioned adhesive layer includes at least styrene series elastomer in hydride selected from the block copolymer with styrenic block and butadiene-based polymer blocks etc., and polyethylene-based resin, the content of styrene series elastomer in above-mentioned adhesive layer is 35 mass % or more and 99 mass % or less, the content of polyethylene-based resin is 1 mass % or more and 65 mass % or less, and the sum of ethylene ingredient and polyethylene-based resin in styrene series elastomer is 35 mass % more than or lower than 70 mass % in bonding composition of layer.
Description
It is on April 2nd, 2013 that the application, which is the applying date, application No. is 201380019463.6, entitled " autoadhesion
The divisional application of the application of property surface protective film ".
Technical field
The present invention relates to adhesive films.Adhesive film of the invention is suitable for following situations: making in protection optical applications
The components such as prismatic lens, stainless steel plate (such as construction material use), aluminium sheet, cover synthetic resin board (such as construction material use)
The surface of body of a motor car when film glued board, steel plate, glass plate, household appliances, precision machinery and manufacture, is used for protection
Product stacking, keeping, transport, in manufacturing process convey when from scratch, and for protect article secondary operation (such as
Bending machining, press process) when from scratch.
Background technique
All the time, the adhesive film for the purpose of the surface protection of nappe construction material, electrical, electronic product,
It is used when the processing of automobile etc., keeping, transport, this adhesive film must have good adhesiveness, and after use can
It is enough easily peeled off without making each surface by adhesive contamination.
Above-mentioned nappe is gradually diversified in recent years, is not only the smooth object of covering surface, and have concave-convex surface
Object it is also very common.As the nappe with concave-convex surface, such as prismatic lens used in optical component can be enumerated
The lens section etc. of prism-type.For having the nappe of concave-convex surface as prismatic lens, in order to show using upper sufficient
Bonding force, it may be considered that the bonding force etc. for improving adhesive layer makes that bonding force can be obtained contact area is small.
In order to improve the bonding force of adhesive layer, as resin, the polystyrene elasticity for showing high adhesion can be used
Body etc. is used as main component, still, if improving the bonding force of adhesive layer, by film with volume state keeping, then film submitting
When, stick together, film local elongation or deformation etc. problem generate.
As above-mentioned countermeasure, add in substrate layer fluorine resin, organic silicon-type resin (for example, referring to special
Sharp document 1 etc.), supra polymer dimethyl silicone polymer (for example, referring to patent document 2 etc.), saturated fatty acid bisamide (example
Such as, referring to patent document 3 etc.) etc. research, but these resins are possible to move into adhesive layer when being taken care of with volume state, nothing
Method eliminates the worry for reducing bonding force or polluting nappe etc..
Polyethylene-based resin is added in adhesive layer (for example, referring to patent document 4, patent document 5 in addition, also studied
Deng), but be unable to satisfy above-mentioned when taking care of with volume state to the bonding force of prism and by film, then send out film
Problem.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2008-81589 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2008-308559 bulletin
Patent document 3: No. 4565058 bulletins of Japanese Patent No.
Patent document 4: Japanese Unexamined Patent Publication 08-73822 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2007-161882 bulletin
Summary of the invention
Problems to be solved by the invention
The problem to be solved in the present invention, which is to provide, shows strong adhesive power to nappe, can be used in various nappes,
And film local elongation or deformation etc. are not easy to produce when taking care of adhesive film with volume state, then sending out film and is asked
Topic, the excellent self adhesion surface protective film of the fitness of process of film.
The solution to the problem
The inventors of the present invention have made intensive studies, as a result, it has been found that, by by the type of the resin used in adhesive layer and
Mix ratio is set as defined range, can eliminate the above problem, to reach the present invention.
That is, the present invention relates to a kind of self adhesion surface protective films, which is characterized in that its be by coextrusion by
Adhesive layer is laminated in the one side for the substrate layer that polypropylene-based resin is formed, release layer is laminated on opposing sides and is formed, constitutes
The resin of above-mentioned adhesive layer include at least styrene series elastomer and polyethylene-based resin, above-mentioned styrene series elastomer be with
The hydride of the block copolymer of styrenic block and butadiene-based polymer blocks has polystyrene polymerization
The hydride of the block copolymer of the block of random copolymer of object block and styrene and butadiene, above-mentioned polyethylene-based resin are
Alathon and/or ethylene-alpha-olefin copolymer, the content of the styrene series elastomer in above-mentioned adhesive layer are 35 mass %
Above and 99 mass % are hereinafter, the content of polyethylene-based resin is 1 mass % or more and 65 mass % are hereinafter, and polystyrene
The sum of ethylene ingredient and polyethylene-based resin in elastomer is 35 mass % more than or lower than 70 matter in bonding composition of layer
Measure %.
In accordance with the invention it is possible to obtain showing strong adhesive power to nappe, it can be used in various nappes, and inciting somebody to action
Adhesive film is not easy to produce the problems such as film local elongation or deformation, film when taking care of with volume state, then sending out film
The excellent self adhesion surface protective film of fitness of process.
At this point, the bending elastic modulus of vinylite used in adhesive layer is to close more than or lower than 90MPa for 10MPa
Suitable.
In addition, at this point, the MFR (190 DEG C, 2.16kgf) of the polyethylene-based resin in aforementioned adhesion layer is 0.5~8g/10
Minute is suitable.
In addition, at this point, the MFR (230 DEG C, 2.16kgf) of the styrene series elastomer in aforementioned adhesion layer is 0.5~8g/
10 minutes are suitable.
In addition, at this point, the MFR (230 DEG C, 2.16kgf) of the polypropylene-based resin in aforementioned substrates layer is 1.0~15g/10
Minute is suitable.
The effect of invention
Adhesive film of the invention, which has the advantage that, shows strong adhesive power to nappe, can be used in various cover
Lid, and film local elongation or change are not easy to produce when taking care of adhesive film with volume state, then sending out film
The fitness of process of the problems such as shape, film are excellent.
Detailed description of the invention
Fig. 1 is the schematic diagram for measuring sample.
Specific embodiment
Hereinafter, illustrating the embodiment of adhesive film of the invention.
(substrate layer)
Adhesive film of the invention needs to make substrate layer as main component with polypropylene-based resin.As used herein
Polypropylene-based resin can enumerate random copolymer or block copolymer of crystalline polypropylene, propylene and a small amount of alhpa olefin etc..
More specifically, as crystalline polypropylene resin, it is insoluble that the normal heptane used in common extrusion molding etc. can be enumerated
Property isotactic Noblen or propylene containing the 60 above propylene of mass % and other alpha-olefins copolymer.This third
The copolymer of polyamino alkenyl object or propylene and other alpha-olefins can be used alone or as a mixture.
The above propylene units of 60 mass % are preferably comprised in substrate layer, further preferably include 70 mass % or more, more excellent
Choosing is preferred comprising 80 mass % or more, particularly preferably comprising 90 mass % or more.It is thin when propylene units are lower than 60 mass %
Film becomes no stiff feel, and processing becomes difficult sometimes.In addition, making propylene units amount lower than 60 mass % or using polyethylene
When being resin, film is soft and becomes easy elongation, and film local elongation or deformation etc. are not easy to produce when sending out film
Problem.
Herein, normal heptane is insoluble refers to, using polyacrylic crystallinity as index, while indicating safety, in the present invention,
Using meet based on Showa Health and human services department bulletin in 2 months in 57 years the 20th normal heptane it is insoluble (25 DEG C, 60 minutes extract when dissolution
Ingredient is 150ppm or less (the use of the substance that temperature is more than 100 DEG C being 30ppm or less)) substance be preferred embodiment.
As the alpha-olefin copolymer ingredient for the copolymer for constituting propylene and other alpha-olefins, can enumerate carbon number is 2~8
Alpha-olefin, such as the alpha-olefin of the C4 or more such as ethylene or 1- butylene, 1- amylene, 1- hexene, 4-methyl-1-pentene.Herein, it is copolymerized
Object preferably makes random copolymer or block copolymer obtained from propylene and one kind or two or more above-mentioned alpha-olefine polymerizing.
In addition, propylene can be used alone or mix two or more use with the copolymer of other alpha-olefins.
The melt flow rate (MFR) (MFR:230 DEG C, 2.16kgf) of used polypropylene-based resin is preferably 1.0~15g/
10 minutes ranges, more preferably 2.0~10.0g/10 minutes ranges.
In addition it is also possible to former as recycling using the broken film generated when product processing is carried out to film obtained in the present invention
Material is granulated again, is added in substrate layer.By using recycling raw material, it is able to suppress production cost.
(adhesive layer)
Adhesive layer of the invention is needed to show high adhesion comprising styrene series elastomer.In addition, for table
Reveal the deliverability of bonding force and film from volume state, adhesive layer is needed comprising polyethylene-based resin.It is polyethylene-based by adding
Resin can reduce autoadhesion surface side to the peeling force of stripping surface.In addition, in adhesive layer, it, can also root in order to control bonding force
Tackifying resin, softening agent, the polystyrene etc. in addition to polyethylene-based resin are mixed according to needs.
About the styrene series elastomer amount in adhesive layer, in order to which the performance for showing high adhesion and film are from web-like
The deliverability of state is needed relative to bonding 100 mass % of composition of layer for 35 mass % or more and 99 mass % or less.Lower than 35
When quality %, bonding force is reduced, it is difficult to obtain required bonding force.Styrene series elastomer amount in adhesive layer is preferably 38 matter
Measure % or more and 95 mass % ranges below.More preferably 40 mass % or more and 90 mass % ranges below.
As styrene series elastomer, it is poly- that the A-B-A type block such as styrene-butadiene-styrene can be enumerated
Close hydride, the SBR styrene butadiene rubbers etc. of the A-B type block polymers such as hydride, the styrene-butadiene copolymer of object
The hydride etc. of polystyrene random copolymer.It should be noted that these hydride can be part hydride, or
Completely hydrogenated object.
Styrene content in styrene series elastomer is 5 mass % or more and 40 mass % or less are ideal.Lower than 5
When quality %, granulation when making resin is become difficult, and when more than 40 mass %, bonding force is reduced, and becomes difficult to obtain sometimes
Required bonding force.It should be noted that the styrene content in styrene series elastomer is preferably 8 mass % or more and 35 matter
Measure % range below, more preferably 10 mass % or more and 30 mass % ranges below.
On the other hand, the ethylene ingredient in styrene series elastomer is 15 mass % or more and 70 mass % or less are ideal
's.Ethylene ingredient in styrene series elastomer has the effect of improving the compatibility with polyethylene-based resin, in addition, also having
Improve effect of the film from the deliverability of volume state.Accordingly, it is believed that the improvement of deliverability is imitated when ethylene component amount is more
Fruit tends to get bigger.Accordingly, it may be concluded that the ethylene ingredient in styrene series elastomer also greatly contributes to the performance of bonding force,
When ethylene component amount is more than 70 mass %, worry that the bonding force of adhesive layer becomes excessively high.
In addition, preferably there is butylene ingredient in styrene series elastomer.When butylene ingredient is 50 mass % or more, addition is poly-
When vinylite, it is not easy reduced tendency there are bonding force, is preferred.
The melt flow rate (MFR) (MFR:230 DEG C, 2.16kgf) of used styrene series elastomer is excellent in terms of film formation property
It is selected as 0.5~8g/10 minutes ranges, more preferably 2.0~7.0g/10 minutes ranges.
About the polyethylene-based resin amount in adhesive layer, in order to which the performance for showing high adhesion and film are from volume state
Deliverability, need for 1 mass % or more and 65 mass % or less.Polyethylene-based resin amount in adhesive layer is more than 65 mass %
When, bonding force reduces, it becomes difficult to obtain required bonding force.Polyethylene-based resin amount in adhesive layer is preferably 3 mass %
Above and 60 mass % ranges below.
As polyethylene-based resin, the copolymer etc. of low density polyethylene (LDPE), ethylene and alpha-olefin can be enumerated.Wherein, low
Density polyethylene is especially known as the straight-chain low density polyethylene (LDPE) of LLDPE, is referred to as the ultra-low density polyethylene of VLDPE
It is able to maintain bonding force and improves the deliverability of film, so it is preferred that.They are led in ethylene chain and making alpha-olefin copolymer
Enter short-chain branches, according to the type of alpha-olefin, copolymerization amount, flexibility can be assigned to polyethylene-based resin.
As alpha-olefin, 1- butylene, 1- amylene, 1- hexene, 4-methyl-1-pentene, 1- octene etc. can be enumerated.
In adhesive layer of the invention, the sum of ethylene ingredient and polyethylene-based resin in styrene series elastomer is in adhesive layer
It is range of the 35 mass % more than or lower than 70 mass % in ingredient.The sum of ethylene ingredient and polyethylene-based resin adhesive layer at
When being 70 mass % or more in point, bonding force is reduced, and cannot get sufficient bonding force.Ethylene ingredient and polyethylene-based resin and
When being lower than 35 mass % in bonding composition of layer, film adhesive layer gets higher the peeling force of release layer.Preferably, ethylene ingredient
Sum with polyethylene-based resin is 40 mass % more than or lower than 70 mass % in bonding composition of layer.It is further preferred that ethylene
The sum of ingredient and polyethylene-based resin is 45 mass % or more and 65 mass % or less in bonding composition of layer.It is particularly preferred
It is that the sum of ethylene ingredient and polyethylene-based resin is 45 mass % or more and 63 mass % or less in bonding composition of layer.
The bending elastic modulus of polyethylene-based resin is ideal more than or lower than 90MPa for 10MPa.When lower than 10MPa,
Film is reduced from the deliverability of volume state, and when being 90MPa or more, adhesive layer is hardened, and there are the tendencies that bonding force reduces.Polyethylene
The bending elastic modulus for being resin is preferably the range of 15MPa~80MPa, the range of more preferably 20MPa~70MPa.
In order to which bending elastic modulus to be set as in above range, the ethylene ingredient adjusted in polyethylene-based resin is a plan
Slightly.From the above point of view, the ethylene ingredient in polyethylene-based resin is preferably 70 mass % or more.The second of polyethylene-based resin
Alkene ingredient is more preferably 75 mass % or more, further preferably 80 mass % or more.In addition, the ethylene of polyethylene-based resin
Content is preferably 98 mass % or less, more preferably 96 mass % or less, is more preferably 95 mass % or less, particularly preferred
For 94 mass % or less.When ethylene ingredient in polyethylene-based resin is lower than 70 mass %, there are films from the submitting of volume state
The tendency that the improvement of property becomes smaller.The polyvinyl resin for being 70 mass % or more as the ethylene ingredient in polyethylene-based resin
Example, CX3007, VL100 etc. of Sumitomo Chemical Co's manufacture can be enumerated.
The density of polyethylene-based resin is preferably 850kg/m3~920kg/m3, further preferably 860kg/m3~
910kg/m3, particularly preferably 870kg/m3~908kg/m3, be most preferably 880kg/m3~906kg/m3.By being set as above-mentioned model
It encloses, takes into account good adhesiveness and deliverability to become easy.
The melt flow rate (MFR) (MFR:190 DEG C, 2.16kgf) of used polyethylene-based resin is preferably 0.5g/10 points
Clock~8g/10 minutes range, more preferably 0.8g/10 minutes~7.0g/10 minutes ranges.By being set as above range,
The film in homogeneous thickness of each layer is set to become easy progress.
Adhesive layer also may include the polyolefin-based resins other than polyethylene-based resin, its type is not particularly limited,
Such as the copolymer etc. of crystalline polypropylene, propylene and a small amount of alpha-olefin can be enumerated.Even if these resins are usually only matched on a small quantity
Mixed there is also the tendencies that bonding force is easily reduced, therefore preferably with 1 mass % or more and 20 mass % ratio compounding below.
As tackifying resin, such as aliphatic hydrocarbon resin, aromatic hydrocarbon resin, terpene resin, coumarone-indenes can be enumerated
Resin, phenylethylene resin series, rosin resin etc..The molecular weight of tackifying resin can be suitably set without particular limitation, molecule
Quantitative change hour worries that auto-adhesive layer is caused to occur to substance movement of nappe, re-separation etc., another aspect, molecule quantitative change
When big, there is the tendency for the improvement effect for lacking bonding force.Therefore, the number-average molecular weight of tackifying resin is preferably 1000~100,000
Left and right.Number-average molecular weight can be measured by gel permeation chromatography (standard substance: polystyrene) etc..
About the compounding amount of the tackifying resin in adhesive layer, composition of layer, preferably 5 matter are bonded relative to 100 mass %
Measure % or more and 20 mass % ranges below.When the compounding amount of tackifying resin being made to be more than 20 mass %, tackifying resin is due to dividing
Son amount is low, therefore melt viscosity terrifically reduces, when be film-made using the coextrusion of T mould etc. and based on polypropylene-based resin
The stacking of the substrate layer of ingredient is wanted to become difficult, and adhesive layer stickness, film exists from the deliverability of volume state to be difficult to improve
Tendency.In addition, being difficult to help to bond compounding when the compounding amount of the tackifying resin in adhesive layer is lower than 5 mass %
The bonding force variation of layer.Therefore, the compounding amount of tackifying resin is preferably 6 mass % or more and 20 mass % or less.It is further excellent
It is selected as 6 mass % or more and 15 mass % ranges below.
When so that melt viscosity is there is reduced tendency due to the addition tackifying resin into adhesive layer, by adhesive layer
The polystyrene resin of 1 mass of mass %~15 % or so is added, so as to improve the melting between substrate layer and adhesive layer
Differences in viscosity becomes easy stacking.Polystyrene resin compounding amount is preferably 3 mass % or more and 12 mass % or less, more preferably
For 5 mass % or more and 10 mass % or less.
As softening agent, such as the diene polymer, polyisobutene, the poly- isoamyl two of hydrogenation of low molecular weight can be enumerated
Alkene, hydrogenated butadiene polymer, their derivative, polybutene etc..The molecular weight of softening agent can suitably be set without particular limitation
It is fixed, when molecular weight becomes smaller, worry to cause auto-adhesive layer to substance movement of nappe, re-separation etc., another aspect, molecular weight
When becoming larger, there is the tendency for the improvement effect for lacking bonding force.Therefore, the number-average molecular weight of softening agent is preferably 1000~100,000
Left and right.The case where number-average molecular weight can be by with tackifying resin same method measurement.
In addition, tackifying resin, softening agent used in adhesive layer are liquid, powder according to type, also sometimes when squeezing out
Pollute extruder.This problem can be by by tackifying resin, softening agent and polyethylene-based resin, polyolefin-based resins masterbatch
Improve to use.Therefore, tackifying resin, softening agent preferably with polyethylene-based resin, polyolefin-based resins masterbatch come using.
The bonding force of adhesive film (adhesive layer) of the invention at 23 DEG C, for acrylic board be 200cN/25mm~
The range of 1000cN/25mm is in view of being preferred for various nappes.When bonding force is lower than 200cN/25mm, using covering
Curling etc. is generated when lid is protected, and cannot undertake the function as protective film.On the other hand, bonding force is more than
When 1000cN/25mm, when from nappe stripping film, worry is removed in which can not be successfully.
In addition, considering that use is preferred at 23 DEG C, for the range that prismatic lens are 2cN/25mm~20cN/25mm
's.When bonding force is lower than 2cN/25mm, curling etc. is generated when protection, cannot undertake the function as protective film.On the other hand,
When bonding force is more than 20cN/25mm, worry can not be successfully removing in stripping film.Bonding force can be by changing adhesive layer
Resin composition, thickness etc. and suitably set.
Well known additive can also be contained in adhesive layer of the invention as needed.For example, lubricant can be contained, resisted
Adhesion agent, heat stabilizer, antioxidant, antistatic agent, light stabilizer, impact resistance modifying agent etc..But the molecule of these ingredients
Measure it is lower, sometimes bonding layer surface exudation and reduce the bonding force of adhesive layer.When therefore, using additive, preferably make to glue
The low molecular weight substance amount for closing layer surface is lower than 1mg/m2。
The measurement for bonding the low molecular weight substance of layer surface is implemented according to following step.Structure will not be corroded using ethyl alcohol etc.
After organic solvent cleaning bonding layer surface at the resin of adhesive layer, organic solvent evaporator etc. is removed from the cleaning solution
Afterwards, its residue will be weighed and the numerical value that finds out divided by the bonding layer surface after cleaning surface area, so as to find out.Residue exists
1mg/m2When above, foreign matter can be had by bonding between layer surface and nappe surface, cause to reduce the contact area with nappe,
Van der Waals force is reduced, therefore bonding force reduces, and is undesirable.When adding additive, need to select the addition of polymer electrolyte etc.
Agent or research additive amount and adding method etc., so that transfer, transfer of the low molecular weight substance (foreign matter) to adhesive layer will not be sent out
It is raw.
(release layer)
Adhesive film of the invention has release layer on the face opposite with the adhesive layer for the one side for being laminated in substrate layer.By
This can also inhibit the mutual adhesion of adhesive film to occur even if adhesive film is overlapped each other.By the way that release layer is arranged, especially
It is to be not easy to produce film local elongation or deformation etc. when taking care of adhesive film with volume state, then sending out film to ask
Topic, can be made the excellent film of fitness of process.In order to which adhesive film does not occur each other adhesive film overlaps each other yet
Adhesion, effectively, on release layer formed concave-convex surface and reduce the contact area with adhesive layer.
Release layer is preferably using polypropylene-based resin as main component (about 50 mass % or more).As specific polypropylene
It is resin, propylene-ethylene block copolymer etc. can be enumerated.
In order to form concave-convex surface as described above on release layer, incompatible resin is mixed in polypropylene-based resin
It is effective.Thereby, it is possible to form shaggy layer with matt shape.It should be noted that making as polypropylene-based resin
When with propylene-ethylene block copolymer, it can expect that same effect is incompatible without using in polypropylene-based resin
Resin.It should be noted that certainly, can also further be added and polypropylene-based tree in propylene-ethylene block copolymer
The incompatible resin of rouge.
As the resin incompatible with polypropylene-based resin, low density polyethylene (LDPE), 4- methyl-1-pentene can be properly used
The alpha-olefin (co) polymer of 4 or more the carbon numbers such as alkene system (co) polymer.In addition, can enumerate straight-chain low density polyethylene (LDPE),
High density polyethylene (HDPE), ethylene and the copolymer of a small amount of alpha-olefin, the copolymer of ethylene and vinyl acetate, polystyrene, polyester
It is resin, polyamide resin etc..Especially when using 4-methyl-1-pentene system (co) polymer, not only make release layer
Surface is coarse with matt shape, and the surface free energy of film surface reduces, so as to expect further mentioning for fissility
It is high.
In view of the resin composition of adhesive layer of the invention, the three-dimensional average surface roughness of layer surface will be preferably demoulded
SRa is set as 0.10 μm or more and 0.50 μm or less.Thereby, it is possible to improve the protective value of adhesion resistance and nappe.Release layer
Surface roughness be lower than 0.10 μm when, the deliverability of film when scroll state is made in film is deteriorated sometimes.The table of release layer
When surface roughness is higher than 0.50 μm, the concave-convex surface of release layer is transferred on the surface of adhesive layer, and bonding force is substantially reduced sometimes.
At this point, the concave-convex surface for more preferably forming release layer is calculated as 0.25 μm or more and 0.45 μ with the average surface roughness SRa on surface
The surface below m.
It should be noted that demoulding layer surface three-dimensional average surface roughness SRa refer to, by surface roughness curve with
The mean roughness of median plane when sine curve takes approximation, can be measured by surface roughness measurement device etc..
(self adhesion surface protective film)
Self adhesion surface protective film of the invention is by the substrate layer comprising above-mentioned resin component, adhesive layer, release layer
Each layer constitute.The thickness of self adhesion surface protective film of the invention is preferably 10 μm or more and 150 μm or less, more preferably
It is 15 μm or more and 120 μm or less, further preferably 20 μm or more and 100 μm or less.When the overall thickness of film is excessively thin, sometimes
Deteriorate in processes, when blocked up, formed sometimes rigidity get higher, treatability deterioration and also unfavorable film in terms of cost.
The thickness of substrate layer of the invention be preferably 5 μm more than or lower than 100 μm, more preferably 10 μm or more and 75 μm with
Under, further preferably 15 μm or more and 55 μm or less.When the thickness of substrate layer is lower than 5 μm, stiff feel dies down, thin as protecting
Film is easy to produce fold etc. when being pasted on nappe, there are problems that being unable to fully obtain bonding force, when being 100 μm or more, shape
At film unfavorable in terms of cost.
The thickness of adhesive layer of the invention is preferably 1 μm more than or lower than 30 μm.When the thickness of adhesive layer is lower than 1 μm, base
It is become difficult in the film of stablizing of coextrusion, when being 30 μm or more, forms film unfavorable in terms of cost.At this point, increasing viscous
When resultant force, considers its viscosity, preferably increase the thickness of adhesive layer.Contact surface by increasing the thickness of adhesive layer, with nappe
Product tends to get bigger.The thickness of adhesive layer is preferably 2 μm or more and 20 μm or less, further preferably 3 μm or more and 15 μm or less,
Particularly preferably 4 μm or more and 8 μm or less.
The thickness of release layer of the invention is preferably 1 μm more than or lower than 30 μm.When the thickness of release layer is lower than 1 μm, base
It is become difficult in the film of stablizing of coextrusion, when being 30 μm or more, forms film unfavorable in terms of cost.The thickness of release layer
Preferably 2 μm or more and 20 μm or less, further preferably 3 μm or more and 15 μm or less.
The peeling force for stripping surface of the adhesive surface of the adhesive film of the application is 250cN/40mm or less at 23 DEG C
Range when, be preferred from the viewpoint of the deliverability of film when adhesive film to be made to roller form.Peeling force is more than
When 250cN/40mm, when the submitting of the film when roller form is made in adhesive film, film local elongation or deformation etc. are generated
The problem of.More preferably 200cN/40mm or less.It should be noted that adhesive surface about adhesive film for stripping surface
The lower limit of peeling force is 1cN/40mm or so, is further 5cN/40mm or so as the value of reality.
Self adhesion surface protective film of the invention is by the substrate layer comprising above-mentioned resin component, adhesive layer, release layer
Each layer constitute, the resin for constituting each layer can for example obtain as follows: using single screw rod, twin-screw extruder etc. directly molten
Melt the T mould that feed block (feed block) type, branch manifold type are sent under state, with 3 layers (substrate layer, adhesive layer, release layers)
The above stacking squeezes out, to obtain.The temperature of extruder about each layer can be examined suitably to make each layer molten condition
The forming temperature for considering ingredient used in each layer is suitably adjusted, such as can also be adjusted in the range of 200 DEG C~260 DEG C.T
The temperature of mould can be same as above-mentioned temperature.As long as the speed of collecting from T mould to casting roller makes each layer become suitable thickness
Speed, for example, 10m/ minutes~200m/ minutes, preferably 10m/ minutes~100m/ minutes.
The form that volume is made in adhesive film of the invention is suitable in processing.To the width and volume length of film roll
The upper limit is not particularly limited, from the easness of processing, it is usually preferred that width is 1.5m hereinafter, volume length is in film
It is 5000m or less in the case where 40 μm of thickness.In addition, usually can be used 3 inches, 6 inches, 8 inches etc. as core is batched
Plastic core, metal coremaking.In addition, from fitness of process preferably with the size rolls of length 200m or more, width 450mm or more
The film roll taken.
Adhesive film of the invention can be used for following situations: the components such as protection prismatic lens used in optical applications,
Synthetic resin board (such as construction material use), stainless steel plate (for example, construction material use), aluminium sheet, film coating plywood, steel plate, glass
Glass plate, household appliances, precision machinery and manufacture when body of a motor car surface, for protect article stacking, keeping or
From scuffing when transporting or being conveyed in manufacturing process, and for protecting article in secondary operation (for example, bending machining, pressure
System processing) when from scratch.
This application claims the excellent of Japanese Patent Application No. 2012-89184 to be filed an application based on April 10th, 2012
The right first weighed.The whole for Japanese Patent Application No. 2012-89184 specification filed an application on April 10th, 2012
Content is cited as reference in this application.
Embodiment
Hereinafter, enumerating embodiment further illustrates the present invention.But the present invention is then not limited to without departing from the main idea
Following embodiments.It should be noted that physical property in embodiment below, comparative example evaluation method is as follows described.
(1) evaluation of adhesiveness
It is measured according to JIS-Z-0237 (2000) adhesive tape/bonding sheet test method by following methods.
As nappe, prepare acrylic board (Mitsubishi Rayon Co., Ltd's manufacture: Acrylite (registered trademark) 3mm is thick)
(lens section is made of triangular prism, and the height of triangular prism is 25 μm, and the width of triangular prism is 50 μ for 50mm × 150mm and prismatic lens
m)50mm×150mm.As test film, cut out in the take-up direction in thin film fabrication for 150mm, in orthogonal to that direction
The test film of the upper size for 25mm.
Using quality 2000g rubber rollers (roller surface by spring hardness 80Hs, thickness 6mm rubber layer cover, width
45mm, diameter (include rubber layer) 95mm), nappe is crimped with test film with reciprocal 1 time of 5mm/ seconds speed.Crimping
Afterwards, it places 30 minutes in the environment of 23 DEG C of temperature, relative humidity 65%, is manufactured using Shimadzu Scisakusho Ltd
" Autograph (registered trademark) " (AGS-J) carries out 180 degree removing to sample obtained above with 300mm/ minutes speed,
Using Resistance Value at this time as bonding force [cN/25mm].180 degree removing refers to, by measurement remove when Resistance Value when Ya Ke
The peel angle of power plate and film is maintained at 180 degree.
When measurement, as the collet of measurement sample, prepare the polyester piece of 190 μm of thickness, size 25mm × 170mm, is inciting somebody to action
Above-mentioned test film measures the end of the test film side of sample to paste the width of position 15mm made of crimping with acrylic board
Above-mentioned polyester piece is pasted with adhesive tape, collet when measurement is made.The signal for measuring sample is illustrated in Fig. 1.Measurement for
3 samples made by each film manufactured in Examples and Comparative Examples are implemented, using its average value as the bonding force of the sample.
The case where prismatic lens, is similarly measured.
(2) evaluation of peeling force
Acrylic board (Mitsubishi Rayon Co., Ltd's manufacture: Acrylite (registered trademark) 3mm is thick) 50mm × 150mm's
Double-sided adhesive tape (Nitto Denko Corp's manufacture) is pasted in whole face, to face test film on the another side of double-sided adhesive tape
The mode of adhesive surface paste 150mm (take-up direction when thin film fabrication) × 50mm (just with take-up direction when thin film fabrication
The direction of friendship) test film.
As new test film, the length of take-up direction when cutting out thin film fabrication is 150mm, orthogonal to that direction
Length is the test film of the size of 40mm, and the test film on acrylic board is pasted by its adhesive surface and via double-sided adhesive tape
Stripping surface overlapping after, using quality 2000g rubber rollers (roller surface by spring hardness 80Hs, thickness 6mm rubber layer cover,
Width 45mm, diameter (include rubber layer) 95mm), stripping surface is crimped with test film with reciprocal 1 time of 5mm/ seconds speed.Pressure
After connecing, for the gross area 4000mm in take-up direction being 100mm, on orthogonal to that direction being 40mm2Apply 60Kg
Load be cooled to 23 DEG C after being placed 24 hours in the environment of 40 DEG C of temperature, relative humidity 65%, use Co., Ltd. island
Saliva production manufactured " Autograph (registered trademark) " (AGS-J), with 300mm/ minutes speed to sample obtained above
180 degree removing is carried out, using Resistance Value at this time as peeling force [cN/40mm].
When measurement, as the collet of measurement sample, prepare the polyester piece of 190 μm of thickness, size 40mm × 170mm,
The end of the test film of 150mm × 40mm is pasted with the width for pasting position 15mm with adhesive tape, collet when as measurement.
A sample is implemented in measurement 3 times, using its average value as the peeling force of the sample.
(3) from the deliverability of volume
After obtaining 550mm wide, 500m volumes of coiling body by cutting, under 23 DEG C of temperature, the shading environment of humidity 75%
With volume state keeping 7 days.After just by the film roll debatching 300m after keeping to another plastic core (diameter 9cm), hand is used
It holds film end to be pulled, debatching 3m.The visual confirmation elongation or deformation of film with the presence or absence of part in debatching.To not have
Have the case where local elongation or deformation as zero (good), there are local elongation or deformations the case where conduct × (bad).
(4) the MFR measurement of resin
It is measured according to JIS-K7210.
(5) the bending elastic modulus measurement of resin
It is measured according to ASTM D747-70.
(6) measurement of the ethylene ingredient in styrene series elastomer
About 330mg resin sample is dissolved in deuterated chloroform, is measured13C-NMR (BRUKER manufacture, AVANCE500).It utilizes
Obtained measurement result identifies the ethylene component amount in styrene series elastomer.
[embodiment 1]
(production of substrate layer)
By sym-propene polymer resin (Sumitomo Chemical Co's manufacture: FLX80E4,230 DEG C of MFR:7.5g/10min) 100 matter
% is measured to useSingle screw extrusion machine melting extrusion at 240 DEG C, is made substrate layer.
(production of adhesive layer)
By styrene series elastomer (hydride of the block copolymer of styrene and butadiene, Asahi Chemical Industry's chemistry strain formula meeting
Society's manufacture: TUFTEC (registered trademark) H1221, styrene content are than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C
MFR:4.5g/10min) 40 mass %, ethylene-alpha-olefin copolymer (Sumitomo Chemical Co's manufacture: CX3007,190 DEG C
MFR:3.7g/10min, elasticity modulus: 26MPa) 50 mass % and Petropols (Arakawa Chemical Industries, Ltd.'s manufacture:
Alcon (registered trademark) P125) 10 mass % 45mm φ single screw extrusion machine melting extrusion at 210 DEG C, adhesive layer is made.
(production of release layer)
By propylene-ethylene block copolymer (Japan Polypropylene Corporation manufacture: BC3HF) 90 matter
Measure % and ldpe resin (Ube Industries, Ltd's manufacture: R300) 10 mass % 65mm φ single screw extrusion machine
The melting extrusion at 230 DEG C, is made release layer.
(production of film)
Substrate layer, adhesive layer, release layer are respectively directly in 245 DEG C of 3 layers of T mould in the state of being melted with each extruder
Stacking extrusion is carried out in (feeding type, lip width 850mm, lip gap 1mm).By the film of extrusion to 30 DEG C of temperature of stream
Prolong and collected on roller with 20m/min speed, cooled and solidified, obtaining substrate layer with a thickness of 28 μm, bondline thickness is 6 μm, release layer
With a thickness of 6 μm, thin-film width 600mm, 3 kinds of 3 layers of non-stretched films that film length is 1100m.Then on one side by the film
Apply 50N contact pressure in the case where collecting tension 40N, with rubber rollers relative to thin-film width, is cut on one side with the speed of 50m/min
It cuts, to obtain the non-stretched film that thin-film width is 550mm, film length is 500m.
[embodiment 2]
Substrate layer, release layer are still that embodiment 1 is such, adhesive layer are changed to following the description, by similarly to Example 1
Preparation method obtain 3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1221, styrene
Ingredient is than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C of MFR:4.5g/10min) 60 mass % and ethylene-alpha-olefin be total
Polymers (Sumitomo Chemical Co's manufacture: CX3007,190 DEG C of MFR:3.7g/10min, elasticity modulus: 26MPa) 40 mass %
With the melting extrusion at 210 DEG C of 45mm φ single screw extrusion machine, adhesive layer is made.
[embodiment 3]
Substrate layer, release layer are still that embodiment 1 is such, adhesive layer are changed to following the description, by similarly to Example 1
Preparation method obtain 3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (hydride of the block copolymer of styrene and butadiene, Asahi Chemical Industry's chemistry strain formula meeting
Society's manufacture: TUFTEC (registered trademark) H1221, styrene content are than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C
MFR:4.5g/10min) 40 mass %, ethylene-alpha-olefin copolymer (Sumitomo Chemical Co manufacture: VL100,190 DEG C of MFR:
0.8g/10min, elasticity modulus: 64MPa) (Arakawa Chemical Industries, Ltd.'s manufacture: Alcon of 50 mass % and Petropols
(registered trademark) P125) 10 mass % 40mm φ single screw extrusion machine melting extrusion at 210 DEG C, adhesive layer is made.
[embodiment 4]
Substrate layer, release layer are still that embodiment 1 is such, adhesive layer are changed to following the description, by similarly to Example 1
Preparation method obtain 3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1041, styrene
Ingredient is than 30 mass %, ethylene ingredient than 49 mass %, 230 DEG C of MFR:5.0g/10min) 85 mass %, ethylene-alpha-olefin copolymerization
Object (Sumitomo Chemical Co's manufacture: CX3007,190 DEG C of MFR:0.8g/10min, elasticity modulus: 26MPa) 5 mass % and stone
Oleoresin (Arakawa Chemical Industries, Ltd.'s manufacture: Alcon (registered trademark) P125) 10 mass % are squeezed with 40mm φ single screw rod
Machine melting extrusion at 210 DEG C out, is made adhesive layer.
[embodiment 5]
Substrate layer, release layer are still that embodiment 1 is such, and adhesive layer is changed to following the description, substrate layer thickness is set as
26 μm, bondline thickness be set as 8 μm, release layer thickness be set as 6 μm, in addition to this, obtained by preparation method similarly to Example 1
3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1221, styrene
Ingredient is than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C of MFR:4.5g/10min) 60 mass % and ethylene-alpha-olefin be total
Polymers (Sumitomo Chemical Co's manufacture: CX3007,190 DEG C of MFR:3.7g/10min, elasticity modulus: 26MPa) 40 mass %
With the melting extrusion at 210 DEG C of 45mm φ single screw extrusion machine, adhesive layer is made.
[embodiment 6]
Substrate layer, release layer are still that embodiment 1 is such, and adhesive layer is changed to following the description, substrate layer thickness is set as
30 μm, bondline thickness be set as 4 μm, release layer thickness be set as 6 μm, in addition to this, obtained by preparation method similarly to Example 1
3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1221, styrene
Ingredient is than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C of MFR:4.5g/10min) 40 mass %, ethylene-alpha-olefin copolymerization
Object (Sumitomo Chemical Co manufacture: CX3007,190 DEG C of MFR:3.7g/10min, elasticity modulus: 26MPa) 55 mass % and
Petropols (Arakawa Chemical Industries, Ltd.'s manufacture: Alcon (registered trademark) P125) 5 mass % are squeezed with 45mm φ single screw rod
Machine melting extrusion at 210 DEG C out, is made adhesive layer.
[comparative example 1]
Substrate layer, release layer are still that embodiment 1 is such, adhesive layer are changed to following the description, by similarly to Example 1
Preparation method obtain 3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1221, styrene
Ingredient is than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C of MFR:4.5g/10min) 70 mass %, ethylene-alpha-olefin copolymerization
Object (Sumitomo Chemical Co manufacture: CX3007,190 DEG C of MFR:3.7g/10min, elasticity modulus: 26MPa) 20 mass % and
Petropols (Arakawa Chemical Industries, Ltd.'s manufacture: Alcon (registered trademark) P125) 10 mass % 40mm φ single screw rod
Extruder melting extrusion at 210 DEG C, is made adhesive layer.
[comparative example 2]
Substrate layer, release layer are still that embodiment 1 is such, adhesive layer are changed to following the description, by similarly to Example 1
Preparation method obtain 3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1221, styrene
Ingredient is than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C of MFR:4.5g/10min) 70 mass %, ethylene-alpha-olefin copolymerization
Object (Sumitomo Chemical Co's manufacture: VL100,190 DEG C of MFR:0.8g/10min, elasticity modulus: 64MPa) 20 mass % and stone
Oleoresin (Arakawa Chemical Industries, Ltd.'s manufacture: Alcon (registered trademark) P125) 10 mass % are squeezed with 40mm φ single screw rod
Machine melting extrusion at 210 DEG C out, is made adhesive layer.
[comparative example 3]
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1221, styrene
Ingredient is than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C of MFR:4.5g/10min) 20 mass %, ethylene-alpha-olefin copolymerization
Object (Sumitomo Chemical Co manufacture: CX3007,190 DEG C of MFR:3.7g/10min, elasticity modulus: 26MPa) 70 mass % and
Petropols (Arakawa Chemical Industries, Ltd.'s manufacture: Alcon (registered trademark) P125) 10 mass % 40mm φ single screw rod
Extruder melting extrusion at 210 DEG C, is made adhesive layer.
[comparative example 4]
Substrate layer, release layer are still that embodiment 1 is such, adhesive layer are changed to following the description, by similarly to Example 1
Preparation method obtain 3 kinds 3 layers of non-stretched film.
(production of adhesive layer)
By styrene series elastomer (Asahi Chemical Corp's manufacture: TUFTEC (registered trademark) H1221, styrene
Ingredient is than 12 mass %, ethylene ingredient than 18 mass %, 230 DEG C of MFR:4.5g/10min) 40 mass %, homo-polypropylene (Sumitomo
Chemical Co., Ltd. manufacture: FLX80E4,190 DEG C of MFR:7.5g/10min) 50 mass % and Petropols (Arakawa Chemical Industries
Co., Ltd. manufactures: Alcon (registered trademark) P125) 10 mass % are melted at 210 DEG C with 40mm φ single screw extrusion machine squeezes
Out, adhesive layer is made.
The above results are shown in table 1,2.
[table 1]
[table 2]
Show that film obtained in Examples 1 to 6 has practical sufficient bonding when being used as protective film by table 2
Power, fissility when film is sent out from volume are also good.
On the other hand, fissility of the film obtained in comparative example 1 and 2 when sending out film from volume is it's hard to say certain good
It is good.Bonding force of the film obtained in comparative example 3 and 4 on nappe is it's hard to say sufficiently.In this way, film obtained in comparative example
Quality it is all poor, practicability is low.
Claims (5)
1. a kind of self adhesion surface protective film, which is characterized in that it is by coextrusion by polypropylene-based resin shape
At substrate layer one side on be laminated adhesive layer, on opposing sides be laminated release layer and formed,
The release layer is by acrylic resin and selected from the alpha-olefine polymers and carbon by low density polyethylene (LDPE), 4 or more carbon number
One or more of alpha olefin copolymer of 4 or more number composition,
The resin for constituting the adhesive layer includes at least styrene series elastomer and polyethylene-based resin,
The styrene series elastomer is the block copolymerization with styrenic block and butadiene-based polymer blocks
The block copolymerization of the hydride of object or the block of random copolymer with styrenic block and styrene and butadiene
The hydride of object,
The polyethylene-based resin be Alathon and/or ethylene-alpha-olefin copolymer,
The content of styrene series elastomer in the adhesive layer is 35 mass % or more and 99 mass % are hereinafter, polyethylene-based tree
The content of rouge be 1 mass % or more and 65 mass % hereinafter, also,
The sum of ethylene ingredient and polyethylene-based resin in styrene series elastomer bonding composition of layer in for 50.8 mass % with
70 mass % are gone up and are lower than,
Ethylene ingredient in the polyethylene-based resin is 70 mass % or more and 98 mass % or less.
2. the polypropylene-based film of self adhesion according to claim 1, wherein polyethylene-based used in the adhesive layer
The bending elastic modulus of resin is 10MPa more than or lower than 90MPa.
3. the polypropylene-based film of self adhesion according to claim 1 or 2, wherein polyethylene-based in the adhesive layer
190 DEG C of resin, the MFR under 2.16kgf be 0.5~8g/10 minutes.
4. the polypropylene-based film of self adhesion according to claim 1 or 2, wherein the polystyrene in the adhesive layer
230 DEG C of elastomer, the MFR under 2.16kgf be 0.5~8g/10 minutes.
5. the polypropylene-based film of self adhesion according to claim 1 or 2, wherein polypropylene-based in the substrate layer
230 DEG C of resin, the MFR under 2.16kgf be 1.0~15g/10 minutes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-089184 | 2012-04-10 | ||
| JP2012089184 | 2012-04-10 | ||
| CN201380019463.6A CN104220548A (en) | 2012-04-10 | 2013-04-02 | Self-adhesive surface protection film |
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| CN201380019463.6A Division CN104220548A (en) | 2012-04-10 | 2013-04-02 | Self-adhesive surface protection film |
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| CN201380019463.6A Pending CN104220548A (en) | 2012-04-10 | 2013-04-02 | Self-adhesive surface protection film |
| CN201910491827.XA Pending CN110283545A (en) | 2012-04-10 | 2013-04-02 | Self adhesion surface protective film |
| CN201910490592.2A Pending CN110157350A (en) | 2012-04-10 | 2013-04-02 | Self adhesion surface protective film |
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| CN201910491827.XA Pending CN110283545A (en) | 2012-04-10 | 2013-04-02 | Self adhesion surface protective film |
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| Country | Link |
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| JP (2) | JP6286856B2 (en) |
| KR (2) | KR102089231B1 (en) |
| CN (3) | CN104220548A (en) |
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| JP6323690B2 (en) * | 2013-04-11 | 2018-05-16 | 東洋紡株式会社 | Self-adhesive surface protective film |
| WO2015129426A1 (en) * | 2014-02-28 | 2015-09-03 | 東レフィルム加工株式会社 | Surface protection film for heating process |
| JP6515917B2 (en) * | 2014-06-18 | 2019-05-22 | 東洋紡株式会社 | Self-adhesive surface protection film |
| US20170247580A1 (en) * | 2014-09-22 | 2017-08-31 | Rohm And Haas Company | Foil wrap with cling properties |
| US10150896B2 (en) | 2014-12-19 | 2018-12-11 | Tredegar Film Products Corporation | Surface protection film |
| JP6097466B2 (en) * | 2015-02-14 | 2017-03-15 | 三菱樹脂株式会社 | Polyester film for polarizing plate manufacturing process |
| CN104789143B (en) * | 2015-03-24 | 2017-08-29 | 昆山金华安电子科技有限公司 | A kind of polypropylene dedicated diaphragm of light guide plate smooth surface |
| CN105500859A (en) * | 2015-06-26 | 2016-04-20 | 宝丽菲姆保护膜（苏州）有限公司 | High-viscosity self-adhesive protection film and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| KR102020085B1 (en) | 2019-09-09 |
| KR20150005519A (en) | 2015-01-14 |
| JP2013234321A (en) | 2013-11-21 |
| CN104220548A (en) | 2014-12-17 |
| JP2018087332A (en) | 2018-06-07 |
| JP6286856B2 (en) | 2018-03-07 |
| TWI599633B (en) | 2017-09-21 |
| KR102089231B1 (en) | 2020-03-13 |
| WO2013153990A1 (en) | 2013-10-17 |
| CN110283545A (en) | 2019-09-27 |
| TW201402760A (en) | 2014-01-16 |
| JP6569723B2 (en) | 2019-09-04 |
| KR20190058710A (en) | 2019-05-29 |
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