CN107629710A - Surface protection film - Google Patents

Surface protection film Download PDF

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Publication number
CN107629710A
CN107629710A CN201710537175.XA CN201710537175A CN107629710A CN 107629710 A CN107629710 A CN 107629710A CN 201710537175 A CN201710537175 A CN 201710537175A CN 107629710 A CN107629710 A CN 107629710A
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CN
China
Prior art keywords
methyl
surface protection
protection film
weight
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710537175.XA
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Chinese (zh)
Inventor
三井数马
野中崇弘
冲田奈津子
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Nitto Denko Corp
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Nitto Denko Corp
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Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to CN202410201032.1A priority Critical patent/CN118064063A/en
Priority to CN202410201789.0A priority patent/CN118064064A/en
Publication of CN107629710A publication Critical patent/CN107629710A/en
Pending legal-status Critical Current

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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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The present invention relates to surface protection film.The present invention provides a kind of surface protection film for being suitable for realizing good tearing property of hand and high re-workability in the lump while with polyesters base material.The surface protection film (X) of the present invention, which has, includes the base material (11) and the stepped construction of adhesive phase (12) as transparent base.Base material (11) is the substrate width direction uniaxial tension polyesters base material with more than 75 μm of thickness.Elmendorf tearing strength on the substrate width direction of surface protection film (X) is below 0.5N, and the Elmendorf tearing strength on the length substrate direction of surface protection film (X) is more than 1N.

Description

Surface protection film
Technical field
The present invention relates to the surface protection film with translucency.
Background technology
In recent years, the surface protection film with high transparency is utilized in various technical fields.Such as in flat-panel monitor (FPD) in technical field, for the various optical components for being assembled in FPD, for its manufacturing process, inspection operation, The purpose of surface protection in transportation etc., sometimes in parts surface coating surface diaphragm.Such surface protection film example Such as it is recorded in following patent documents 1~3.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-17399 publications
Patent document 2：Japanese Unexamined Patent Publication 2015-157964 publications
Patent document 3：Japanese Unexamined Patent Publication 2016-74899 publications
The content of the invention
Invent problem to be solved
For the base material of surface protection film, sometimes using polyesters base material, because its heat resistance, the transparency, size The various excellents such as stability.For the polyesters base of the translucency as the surface protection film for optical component purposes etc. For such as PET film of material, it is known that be in most cases in a manufacturing process extruded into material resin material by T-shaped mould head method Shape is membranaceous and then by including the stretching along the flow direction of the film or length direction (MD) and the drawing of (TD) in the width direction The biaxial stretch-formed processing stretched.
In addition, for surface protection film, consider from viewpoints such as operating efficiencies, also require good tearing property of hand sometimes.
The present invention is found out based on situation as described above, and its object is to provide one kind to be suitable for polyesters base Good tearing property of hand and high re-workability (リ ワ ー Network are realized while material in the lump) surface protection film.
The means used to solve the problem
Stepped construction comprising transparent base and adhesive phase is had according to surface protection film provided by the invention.Transparent base Material is substrate width direction uniaxial tension polyesters base material and has more than 75 μm of thickness.Polyesters base material refers to forming material Contain the base materials such as film or the sheet material of polyester resin in material with maximum weight ratio.Substrate width direction uniaxial tension polyesters base Material refers to squeeze by such as edge and membranaceous after the extrusion molding of material resin material in the manufacturing process of polyesters base material Go out the polyesters base material of the flow direction of formed body or the uniaxial tension processing of the orthogonal width (TD) of length direction (MD). Adhesive phase is for example containing selected from by acrylic adhesives, polyurethane binding, polysiloxane-based adhesive and rubber-like At least one of group that adhesive is formed.In this surface protection film, the Elmendorf tearing strength in substrate width direction Elmendorf tearing strength for below 0.5N, and length substrate direction is more than 1N.
As described above, transparent base possessed by this surface protection film is polyesters base material.Such composition is suitable for Surface protection film base material so enjoyed in this surface protection film the polyesters such as heat resistance, the transparency, dimensional stability base material appearance The various characteristics easily shown.
In addition, as described above, transparent base possessed by this surface protection film is the width that thickness is more than 75 μm Uniaxial tension polyesters base material.The tearing strengths such as the Elmendorf tearing strength of surface protection film are consumingly controlled by base material Mechanical property, it is such to form the Elmendorf tearing strength for being suitable for realizing substrate width direction in this surface protection film The above-mentioned composition that Elmendorf tearing strength for below 0.5N and length substrate direction is more than 1N.
In addition, as described above, the Elmendorf tearing strength in the substrate width direction of this surface protection film is Below 0.5N, and the Elmendorf tearing strength in length substrate direction is more than 1N.Such composition is suitable on this surface Realized in diaphragm along the good of Elmendorf tearing strength intentionally as little as below 0.5N substrate width direction relatively Tearing property of hand.At the same time, Elmendorf tearing strength is more than 2 times of the 1N in substrate width direction on length substrate direction Composition above is suitable for improving the directive property along the tear in substrate width direction in this surface protection film.Therefore, this composition It is suitable for the base material length for making peeling force act on the film in the case where this surface protection film is in the state for fitting in adherend Direction is spent so that the film is suitably peeled off with not ftractureing from adherend.Specifically, be suitable for by this surface protection film with Peeling force is set to act on the base material length of the film during operation (the reprocessing operation) first peeled off and then be bonded again after adherend fitting Direction is spent so that the film is suitably peeled off with not ftractureing from adherend.Not only in substrate width direction but also in length substrate side Tend to easily cracking in the stripping in reprocessing operation to the surface protection film being also easily torn and be difficult to from adherend Suitably peel off.The surface protection film for generating cracking cannot be used in being bonded again.On the other hand, this surface protection film has Compared with being adapted for carrying out the substrate width direction Elmendorf tearing strength along good the tearing property of hand in substrate width direction Sufficiently large length substrate direction Elmendorf tearing strength, thus be suitable for not ftractureing when reprocessing operation from being glued Thing is suitably peeled off.
As described above, this surface protection film is suitable for realizing good tearing property of hand in the lump while with polyesters base material With high re-workability.
It is preferred that the thickness of adhesive phase is more than 5 μm.Such be formed in realizes surface protection film to the abundant of adherend Bonding force in terms of be suitable.
It is preferred that the mist degree of the thickness direction of this surface protection film is less than 3%.Such composition is for such as optical component The surface protection film of purposes is suitable.
Brief description of the drawings
Fig. 1 is the partial sectional view of the surface protection film of an embodiment of the invention.
Reference
X surface protection films
11 base materials
12 adhesive phases
Embodiment
Fig. 1 is the surface protection film X of an embodiment of the invention partial sectional view.Surface protection film X has bag Containing the base material 11 and the stepped construction of adhesive phase 12 as transparent base.It is such as various in flat-panel monitor for being assembled in The purpose of the protection of optical component surfaces in the manufacturing process of optical component, inspection operation, transportation etc., surface protection film X can fit in parts surface and use.
Base material 11 is the position worked in surface protection film X as supporter possessed by surface protection film X, is tool There is the substrate width direction uniaxial tension polyesters base material of translucency.
Polyesters base material refers to the bases such as film or the sheet material for containing polyester resin in constituent material with maximum weight ratio Material.For constituent material as such base material 11, it can enumerate for example：Polyethylene terephthalate, gather to benzene two Formic acid butanediol ester, PEN and poly terephthalic acid 1,4 cyclohexane dimethanol ester.
Substrate width direction uniaxial tension polyesters base material refers in the manufacturing process of polyesters base material in material resin By for example along the width orthogonal with the membranaceous flow direction for being extruded into body or length direction (MD) after the extrusion molding of material Spend the polyesters base material of the uniaxial tension processing of direction (TD).Base as such width uniaxial tension polyesters base material The stretching ratio of the width of material 11 is preferably more than 2.5 times, more preferably more than 3 times.In addition, the stretching ratio is preferably Less than 6 times, more preferably less than 5.5 times.
The thickness of base material 11 is more than 75 μm, is preferably more than 80 μm.In addition, the thickness of base material 11 be preferably 150 μm with Under, more preferably less than 125 μm.
Phase difference is preferably more than 1500nm, more preferably more than 3000nm, more preferably 6000nm in the face of base material 11 More than.In the present embodiment, phase difference refers to the light transmission base material 11 with making wavelength 590nm at 23 DEG C in the face of base material 11 When relevant, orthogonal in the face of the main surface parallel with base material 11 two optical main axis (slow axis and fast axle) of birefringence in Slow-axis direction vibration polarized light component (extraordinary light) with quick shaft direction vibrate polarized light component (ordinary ray) between Caused phase difference.The refractive index (relatively large) of extraordinary light is set to nx, the refractive index (relatively small) by ordinary ray In the case of being set to ny, the thickness of base material 11 being set to d (nm), phase difference is the value represented with (nx-ny) × d in the face.
The surface of the side of adhesive phase 12 in base material 11 can implement for improving the surface with the adhesiveness of adhesive phase Processing.For such surface treatment, it can enumerate：The physical treatment such as sided corona treatment or corona treatment and bottom Painting processing etc. is chemically handled.
Surface protection film X adhesive phase 12 contains adhesive as host and has translucency.Host refers to contained Occupy the composition of maximum weight ratio in some compositions.Adhesive phase 12, which contains, to be selected from by as acrylic adhesives Acrylic polymer, the polyurethane as polyurethane binding, polysiloxane-based adhesive and rubber adhesive are formed At least one of group.The bonding force and high transparency of degree required by the adhesive phase of surface protection film is realized simultaneously Viewpoint considers, it is preferred to use acrylic polymer is as the adhesive in adhesive phase 12.In addition, adhesive phase 12 have can It is pasted on the adhesive surface 12a of adherend.
In the case where adhesive phase 12 contains as the acrylic polymer of acrylic adhesives, the preferred propylene Acids polymers contain from the alkyl acrylate of the alkyl with straight-chain or branched and/or with straight-chain or branch The monomeric unit of the alkyl methacrylate of the alkyl of chain is as most main monomer units in terms of part by weight.With Under, with " (methyl) acrylic acid " expression " acrylic acid " and/or " methacrylic acid ".
As alkyl monomeric unit, that there is straight-chain or branched for forming aforesaid propylene acids polymers (methyl) alkyl acrylate, contained in the monomer components of aforesaid propylene acids polymers there is straight chain as being formed For (methyl) alkyl acrylate of shape or the alkyl of branched, it can enumerate for example：(methyl) methyl acrylate, (methyl) Ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) propylene The secondary butyl ester of acid, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid Isopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid 2- ethyls Own ester, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) acrylic acid Tridecane base ester, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid cetyl Ester, (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate, the different stearyl ester of (methyl) acrylic acid, (methyl) Acrylic acid nonadecane base ester and (methyl) acrylic acid eicosane base ester etc. have the straight-chain or branched that carbon number is 1~20 Alkyl (methyl) alkyl acrylate.For (methyl) alkyl acrylate for acrylic polymer, A kind of (methyl) alkyl acrylate can be used, two or more (methyl) alkyl acrylates can also be used.In this implementation In mode, (methyl) alkyl acrylate is somebody's turn to do as acrylic polymer, preferably using selected from by the positive fourth of acrylic acid At least one of group that ester, 2-EHA and the different stearyl ester of acrylic acid are formed.
(methyl) alkyl acrylate in aforesaid propylene acids polymers, from the alkyl with straight-chain or branched The ratio of the monomeric unit of base ester is preferably more than 50 weight %, is more preferably more than 60 weight %, more preferably 70 weight % Above, more preferably more than 80 weight %, more preferably more than 90 weight %.That is, for forming the acrylic polymer The ratio of (methyl) alkyl acrylate in the monomer component composition of raw material is preferably more than 50 weight %, is more preferably 60 weights Measure more than %, more preferably more than 70 weight %, more preferably more than 80 weight %, more preferably more than 90 weight %.It is above-mentioned Acrylic polymer is with the monomer from the monomer component composition with such (methyl) alkyl acrylate ratio Unit is formed.On (methyl) alkyl acrylate of the alkyl with straight-chain or branched ratio this composition containing The acrylic polymer and the acrylic polymer as acrylic adhesives is suitably shown in the adhesive phase that is formed It is suitable in terms of the fundamental characteristics such as the cohesive of compound.
The acrylic polymer contained in adhesive phase 12 can contain the monomeric unit from ester ring type monomer.Make For the ester ring type monomer of the monomeric unit for forming acrylic polymer, i.e. as forming the acrylic polymer Monomer component in for contained ester ring type monomer, can enumerate for example：(methyl) acrylate base ester, there are two ring types (methyl) acrylate of hydrocarbon ring and (methyl) acrylate with hydrocarbon rings more than three rings.As (methyl) acrylate For base ester, it can enumerate for example：(methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid cycloheptyl Ester and (methyl) acrylic acid ring monooctyl ester.For (methyl) acrylate with two ring type hydrocarbon rings, it can enumerate for example： (methyl) acrylic acid norbornene ester and (methyl) isobornyl acrylate.As (methyl) acrylic acid with hydrocarbon rings more than three rings For ester, it can enumerate for example：(methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester, the polycyclic penta of (methyl) acrylic acid tetrahydrochysene two Dialkylene epoxide ethyl ester, (methyl) acrylic acid tetrahydrochysene trimerization cyclopentadiene base ester, (methyl) acrylic acid 1- adamantane esters, (first Base) acrylic acid 2- methyl -2- adamantane esters and (methyl) acrylic acid 2- ethyl -2- adamantane esters.As for acrylic acid Birds of the same feather flock together for the ester ring type monomer of compound, a kind of ester ring type monomer can be used, two or more ester ring type monomers can also be used. In the present embodiment, as the ester ring type monomer for acrylic polymer, preferably using be selected from by cyclohexyl acrylate, At least one of group that cyclohexyl methacrylate, isobornyl acrylate and isobornyl methacrylate are formed.
From the viewpoint of appropriate flexibility being realized from the adhesive phase formed containing the acrylic polymer, The ratio of monomeric unit in aforesaid propylene acids polymers, from ester ring type monomer is preferably the weight of 5 weight %~60 Measure %, more preferably the weight % of 10 weight %~50.
The acrylic polymer contained in adhesive phase 12 can contain the monomeric unit from hydroxyl monomer.Contain Carboxylic monomer is the monomer for having in monomeric unit at least one hydroxyl.Acrylic polymer in adhesive phase 12 contains In the case of hydroxyl monomeric unit, adhesive phase 12 is readily obtained adhesivity, appropriate cohesive force.
Hydroxyl monomer, i.e. conduct as the monomeric unit for forming aforesaid propylene acids polymers is used to form this In the monomer component of acrylic polymer for contained hydroxyl monomer, it can enumerate for example：Hydroxyl (methyl) propylene Acid esters, vinyl alcohol and allyl alcohol.For (methyl) acrylate of hydroxyl, it can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxyl fourths Ester, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) dihydroxypropyl monooctyl ester, (methyl) dihydroxypropyl last of the ten Heavenly stems ester, (methyl) third Olefin(e) acid hydroxylauric ester and (methyl) acrylic acid (4- hydroxymethylcyclohexyls) methyl esters.Contain hydroxyl as acrylic polymer For base monomer, a kind of hydroxyl monomer can be used, two or more hydroxyl monomers can also be used.In present embodiment In, as the hydroxyl monomer for acrylic polymer, preferably using selected from by acrylic acid 2- hydroxy methacrylates, metering system Sour 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl esters, methacrylic acid 2- hydroxy propyl esters, acrylic acid 4- hydroxybutyls and metering system At least one of group that sour 4- hydroxybutyls are formed.
The ratio of monomeric unit in aforesaid propylene acids polymers, from hydroxyl monomer is preferably 1 weight % Above, more preferably more than 2 weight %, more preferably more than 3 weight %, more preferably more than 5 weight %, more preferably 7 weights Measure more than %, more preferably more than 10 weight %.Monomer list in aforesaid propylene acids polymers, from hydroxyl monomer The ratio of member is preferably below 20 weight %, is more preferably below 18 weight %.These structures on the ratio of hydroxyl monomer Into being suitable in terms of realizing adhesivity, appropriate cohesive force in the adhesive phase formed containing the acrylic polymer 's.
The acrylic polymer contained in adhesive phase 12 can contain the monomeric unit from nitrogen atom monomer. Nitrogen atom monomer is the monomer for having in monomeric unit at least one nitrogen-atoms.Acrylic in adhesive phase 12 In the case that thing contains nitrogen atom monomeric unit, adhesive phase 12 is readily obtained hardness, good gluing reliability.
Nitrogen atom monomer, i.e. conduct as the monomeric unit for forming aforesaid propylene acids polymers is used to be formed In the monomer component of the acrylic polymer for contained nitrogen atom monomer, it can enumerate for example：N- vinyl cyclics Acid amides and (methyl) acrylic amide.N- vinyl cyclics acid amides as nitrogen atom monomer can be enumerated for example：N- ethene Base -2-Pyrrolidone, N- vinyl -2- piperidones, N- vinyl -3- morpholones, N- vinyl -2- caprolactams, N- ethene Base -1,3-Piperazine -2- ketone and N- vinyl -3,5- morpholine diketones.(methyl) acrylic amide as nitrogen atom monomer can To enumerate for example：(methyl) acrylamide, N- ethyls (methyl) acrylamide, N- isopropyls (methyl) acrylamide, the positive fourths of N- Base (methyl) acrylamide, N- octyl groups (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (first Base) acrylamide, N, N- dipropyl (methyl) acrylamide and N, N- diisopropyl (methyl) acrylamide.As for propylene For the nitrogen atom monomer of acids polymers, can use a kind of nitrogen atom monomer, can also use it is two or more nitrogenous Atom monomer.In the present embodiment, as the nitrogen atom monomer for acrylic polymer, preferably using N- ethene Base -2-Pyrrolidone.
For the adhesive phase formed containing the acrylic polymer, from realize appropriate hardness, adhesivity, From the viewpoint of the transparency, the ratio of monomeric unit in aforesaid propylene acids polymers, from nitrogen atom monomer is excellent Elect as more than 1 weight %, more preferably more than 3 weight %, more preferably more than 5 weight %.In addition, for containing the acrylic acid For the adhesive phase birdsed of the same feather flock together compound and formed, from realize sufficiently the viewpoint of the transparency, suppress excessively to be hardened and realize good Gluing reliability from the viewpoint of, monomeric unit in aforesaid propylene acids polymers, from nitrogen atom monomer Ratio is preferably below 30 weight %, is more preferably below 25 weight %.
The acrylic polymer contained in adhesive phase 12 can contain the monomeric unit from carboxyl group-containing monomer.Contain Carboxylic monomer is the monomer for having in monomeric unit at least one carboxyl.Acrylic polymer in adhesive phase 12 contains In the case of carboxyl group-containing monomer unit, adhesive phase 12 can obtain good gluing reliability sometimes.
Carboxyl group-containing monomer, i.e. conduct as the monomeric unit for forming aforesaid propylene acids polymers is used to form this In the monomer component of acrylic polymer for contained carboxyl group-containing monomer, it can enumerate for example：(methyl) acrylic acid, clothing health Acid, maleic acid, fumaric acid, crotonic acid and iso-crotonic acid., can be with for the carboxyl group-containing monomer for acrylic polymer Using a kind of carboxyl group-containing monomer, two or more carboxyl group-containing monomers can also be used.In the present embodiment, as acrylic acid Birds of the same feather flock together the carboxyl group-containing monomer of compound, preferably using acrylic acid.
Obtained from the adhesive phase formed containing the acrylic polymer and polar group be present on adherend surface It is above-mentioned with the contribution of the interaction of the polar group so that it is guaranteed that from the viewpoint of good gluing reliability in the case of group The ratio of the monomeric unit from carboxyl group-containing monomer in acrylic polymer is preferably more than 0.1 weight %, more preferably For more than 0.5 weight %.In addition, excessively it is hardened so as to real from the adhesive phase for suppressing to be formed containing the acrylic polymer From the viewpoint of now good gluing reliability, the monomeric unit from carboxyl group-containing monomer in aforesaid propylene acids polymers Ratio be preferably below 20 weight %, more preferably below 15 weight %.
The acrylic polymer contained in adhesive phase 12 can have from more officials as copolymerizable crosslinking agent The cross-linked structure of energy (methyl) acrylate.For multifunctional (methyl) acrylate, it can enumerate for example：1,6- oneself two Alcohol two (methyl) acrylate, butanediol two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) the third two Alcohol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite Three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, four hydroxyls Methylmethane three (methyl) acrylate, (methyl) allyl acrylate and (methyl) vinyl acrylate.As for propylene For multifunctional (methyl) acrylate of acids polymers, a kind of multifunctional (methyl) acrylate can be used, can also Use two or more multifunctional (methyl) acrylate.In the present embodiment, as more officials for acrylic polymer Energy (methyl) acrylate, preferably using selected from by 1,6- hexanediyl esters, dipentaerythritol acrylate and three At least one of group that hydroxymethyl-propane triacrylate is formed.
The ratio of monomeric unit in aforesaid propylene acids polymers, from multifunctional (methyl) acrylate is preferred For more than 0.01 weight %, more preferably more than 0.03 weight %, more preferably more than 0.05 weight %.Aforesaid propylene acids gathers The ratio of monomeric unit in compound, from multifunctional (methyl) acrylate is preferably below 1 weight %, more preferably Below 0.5 weight %.These on the ratio of multifunctional (methyl) acrylate are formed in and contain the acrylic polymer And it is suitable in terms of appropriate hardness, adhesivity are realized in the adhesive phase formed.
In the case where adhesive phase 12 contains acrylic polymer as described above as adhesive, adhesive phase 12 In the containing ratio of the acrylic polymer be, for example, the weight % of 85 weight %~100.
From the viewpoint of high adherence at room temperature is realized, adhesive phase 12 can for example contain starting monomer composition with The different acrylic compounds oligomer of aforesaid propylene acids polymers.Contain such acrylic compounds oligomer in adhesive phase 12 In the case of, relative to the adhesive in adhesive phase 12 or the parts by weight of acrylic polymer 100, the propylene in adhesive phase 12 The content of acid based oligomerization thing is, for example, the parts by weight of 0.1 parts by weight~20.
Above-mentioned oligomer is preferably containing from (methyl) acrylate ((methyl) third containing ring with cyclic structure Olefin(e) acid ester) monomeric unit and (methyl) alkyl acrylate from the alkyl with straight-chain or branched monomer list The polymer of member.
(methyl) acrylate containing ring, i.e. conduct as the monomeric unit for forming above-mentioned oligomer is used to be formed In the monomer component of the oligomer for contained (methyl) acrylate containing ring, it can enumerate for example：(methyl) acrylic acid Cycloalkyl ester, (methyl) acrylate with two ring type hydrocarbon rings, (methyl) acrylate with hydrocarbon rings more than three rings and (methyl) acrylate with aromatic ring.For (methyl) acrylate base ester, it can enumerate for example：(methyl) Acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid cycloheptyl ester and (methyl) acrylic acid ring monooctyl ester.As tool For having (methyl) acrylate of two ring type hydrocarbon rings, it can enumerate for example：(methyl) acrylic acid norbornene ester and (methyl) propylene Sour isobornyl thiocyanoacetate.For (methyl) acrylate with hydrocarbon rings more than three rings, it can enumerate for example：(methyl) propylene Sour tetrahydrochysene dicyclopentadiene base ester, (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base epoxide ethyl ester, (methyl) acrylic acid four Hydrogen trimerization cyclopentadiene base ester, (methyl) acrylic acid 1- adamantane esters, (methyl) acrylic acid 2- methyl -2- adamantane esters and (methyl) acrylic acid 2- ethyl -2- adamantane esters.For (methyl) acrylate with aromatic ring, it can enumerate Such as：(methyl) phenyl acrylate, (methyl) acrylate and (methyl) benzyl acrylate.As for oligomer (methyl) acrylate containing ring for, can use a kind of (methyl) acrylate containing ring, can also use two kinds with On (methyl) acrylate containing ring.In the present embodiment, it is excellent as (methyl) acrylate containing ring for oligomer What choosing was made up of using being selected from acrylic acid tetrahydrochysene dicyclopentadiene base ester and methacrylic acid tetrahydrochysene dicyclopentadiene base ester At least one of group.
It is above-mentioned low from the viewpoint of realizing appropriate flexibility from the adhesive phase 12 formed containing the oligomer The ratio of monomeric unit in polymers, from (methyl) acrylate containing ring be preferably the weight % of 10 weight %~90, The weight % of the weight % of more preferably 20 weight %~80, more preferably 35 weight %~80.
(methyl) third as alkyl monomeric unit, that there is straight-chain or branched for forming above-mentioned oligomer Olefin(e) acid Arrcostab, i.e. as forming alkyl contained, that there is straight-chain or branched in the monomer component of the oligomer (methyl) alkyl acrylate for, can enumerate for example：(methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) Isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) third The own ester of olefin(e) acid, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) propylene The different monooctyl ester of acid, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid are different Last of the ten Heavenly stems ester, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (first Base) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) propylene Sour heptadecane base ester, (methyl) octadecyl acrylate, the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid nonadecyl Ester and (methyl) acrylic acid eicosane base ester etc. have (methyl) of the alkyl of the straight-chain that carbon number is 1~20 or branched Alkyl acrylate.For (methyl) alkyl acrylate for above-mentioned oligomer, it can use a kind of (methyl) Alkyl acrylate, two or more (methyl) alkyl acrylates can also be used.In the present embodiment, as above-mentioned Oligomer is somebody's turn to do (methyl) alkyl acrylate, preferably using methyl methacrylate.
It is above-mentioned low from the viewpoint of realizing appropriate modulus of elasticity from the adhesive phase formed containing the oligomer The ratio of the monomeric unit of (methyl) alkyl acrylate in polymers, from the alkyl with straight-chain or branched is excellent Elect the weight % of the weight %, more preferably 20 weight % of the weight % of 10 weight %~90, more preferably 15 weight %~80~60 as.
In addition, above-mentioned oligomer can contain from carboxyl group-containing monomer, amide-containing monomer, emulsion stability, containing cyanogen Base monomer, monomer containing sulfonic group, phosphorous acid-based monomers, monomer containing NCO, the monomeric unit of the monomer containing imide.
The weight average molecular weight (Mw) of above-mentioned oligomer is, for example, 1000~30000, is preferably 1000~20000, more preferably For 1500~10000.From the viewpoint of ensuring good bonding force from the adhesive phase formed containing above-mentioned oligomer, The weight average molecular weight of the oligomer is preferably more than 1000.On the other hand, from the adhesive formed containing above-mentioned oligomer Especially it is to ensure that in layer from the viewpoint of bonding force at room temperature, the weight average molecular weight of the oligomer is preferably less than 30000.
The weight average molecular weight of above-mentioned oligomer can be measured by gel permeation chromatography (GPC) method.For example, it can make Device (trade name " HLC-8120GPC ", TOSOH Co., Ltd's manufacture) is determined under following condition determinations with standard polyphenyl with GPC The form of ethene scaled value obtains weight average molecular weight (Mw).
■ posts：By TSKgel SuperAWM-H (upstream side, TOSOH Co., Ltd's manufacture) and TSKgel SuperAW4000 (TOSOH Co., Ltd's manufacture) is connected in series with TSKgel SuperAW2500 (downstream, TOSOH Co., Ltd's manufacture)
■ column dimensions：Each post is
■ column temperatures (measurement temperature)：40℃
■ eluents：Tetrahydrofuran (THF)
■ flows：0.4mL/ minutes
■ sample injection rates：20μL
■ sample concentrations：About 2.0g/L (tetrahydrofuran solution)
■ standard specimens：Polystyrene
■ detectors：Differential refractometer (RI)
Adhesive phase 12 can contain silane coupler.For silane coupler, it can enumerate for example：γ-epoxy Propoxypropyl trimethoxy silane, γ-glycidoxypropyl group triethoxysilane, gamma-amino propyl trimethoxy silicane With N- phenyl amino propyl trimethoxy silanes.For silane coupler, trade name " KBM-403 " (letter can also be enumerated More chemical industry Co., Ltd. manufacture) etc. commercially available product.For silane coupler, preferred γ-glycidoxypropyl group three Methoxy silane.
In the case where adhesive phase 12 contains silane coupler, relative to the adhesive or acrylic acid in adhesive phase 12 Birds of the same feather flock together the parts by weight of compound 100, the content of the silane coupler in adhesive phase 12 is preferably more than 0.01 parts by weight, more preferably It is more than 0.02 parts by weight.In addition, the content of the silane coupler in adhesive phase 12 is relative to the weight of acrylic polymer 100 Part is preferably below 1 parts by weight, more preferably below 0.5 parts by weight.On silane coupler content this composition containing The silane coupler and the high adhesivity under humidified condition is realized in the adhesive phase 12 that is formed, particularly to the high glue of glass Sticky aspect is suitable.
Adhesive phase 12 can contain ultra-violet absorber.Ultra-violet absorber be can efficiently absorb ultraviolet and The chemical substance that the energy conversion absorbed can be discharged for heat, infrared ray etc..As such ultra-violet absorber Speech, can be enumerated for example：Benzotriazole Ultraviolet Stabilizer, Hydroxyphenyltriazines ultra-violet absorber, salicylic acid esters are purple Ultraviolet absorbers, benzophenone ultraviolet absorbent, hydroxy benzophenone ketone ultra-violet absorber and cyanoacrylate Ultra-violet absorber.Adhesive phase 12 can contain a kind of ultra-violet absorber, can also contain two or more ultraviolet radiation absorptions Agent.
For Benzotriazole Ultraviolet Stabilizer, it can enumerate for example：2- (2- hydroxyl -5- tert-butyl-phenyls) - 2H- BTAs (trade name " TINUVIN PS ", BASF AG manufacture), 3- (2H- BTA -2- bases) -5- (1,1- bis- Methylethyl) -4- hydroxy phenylpropionic acids carbon number be 7~9 Arrcostab (" TINUVIN 384-2 ", BASF are public for trade name Department's manufacture), 3- [3- tertiary butyl-4-hydroxies -5- (the chloro- 2H- BTAs -2- bases of 5-) phenyl] octyl propionates and 3- [the tertiary fourths of 3- Base -4- hydroxyls -5- (the chloro- bases of 2H- BTAs -2 of 5-) phenyl] propionic acid 2- ethylhexyls mixture (trade name " TINUVIN 109 ", BASF AG's manufacture), double (1- methyl isophthalic acids-phenylethyl) phenol (commodity of 2- (2H- BTA -2- bases) -4,6- Name " TINUVIN 900 ", BASF AG manufacture), 2- (2H- BTA -2- bases) -6- (1- methyl isophthalic acids-phenylethyl) -4- (1,1,3,3- tetramethyl butyl) phenol (trade name " TINUVIN 928 ", BASF manufacture), 3- (3- (2H- BTAs -2- Base) -5- tert-butyl-hydroxy phenyls) methyl propionate and Liquid Macrogol reaction product (trade name " TINUVIN 1130 ", BASF AG manufacture), 2- (2H- BTA -2- bases) paracresol (trade name " TINUVIN P ", BASF AG manufacture), Double (1- methyl isophthalic acids-phenylethyl) phenol (trade name " TINUVIN 234 ", the BASFs of 2- (2H- BTA -2- bases) -4,6- Company manufacture), 2- [the chloro- 2H- BTAs -2- bases of 5-] -4- methyl-6-tert-butylphenols (trade name " TINUVIN 326 ", BASF AG manufacture), 2- (2H- BTA -2- bases) -4,6- di-tert-pentyl phenols (trade name " TINUVIN 328 ", bar Si Fu companies manufacture), 2- (2H- BTA -2- bases) -4- (1,1,3,3- tetramethyl butyls) phenol (trade name " TINUVIN 329 ", BASF AG manufacture), 2,2'- di-2-ethylhexylphosphine oxides [6- (2H- BTA -2- bases) -4- (1,1,3,3- tetramethyl fourths Base) phenol] (trade name " and TINUVIN 360 ", BASF AG manufacture), 2- (2H- BTA -2- bases) -6- dodecyls - 4- methylphenols (trade name " TINUVIN 571 ", BASF AG manufacture), 2- [2- hydroxyls -3- (3,4,5,6- tetrahydrochysene neighbour's benzene Dicarboximide ylmethyl) -5- aminomethyl phenyls] BTA (trade name " Sumisorb 250 ", Sumitomo Chemical Co's system Make) and 2,2'- di-2-ethylhexylphosphine oxide [6- (2H- BTA -2- bases) -4- tert-octyl phenols] (trade name " ADK STAB LA-31 ", Asahi Denka Co., Ltd. manufactures).
For Hydroxyphenyltriazines ultra-violet absorber, it can enumerate for example：2- (double (the 2,4- dimethyl benzenes of 4,6- Base) -1,3,5- triazine -2- bases) -5- hydroxyl phenols and [(carbon number be 10~16 alkyl oxy) methyl] oxirane Reaction product (trade name " TINUVIN 400 ", BASF AG's manufacture), 2- [4,6- double (2,4- 3,5-dimethylphenyls) -1,3,5- Triazine -2- bases] -5- [3- (dodecyl epoxide) -2- hydroxy propyloxy groups] phenol), 2- (2,4- dihydroxy phenyls) -4,6- it is double (2,4- 3,5-dimethylphenyls) -1,3,5- triazines and the reaction product (trade name " TINUVIN of glycidic acid 2- ethylhexyls 405 ", BASF AG's manufacture), double (2- hydroxyl -4- the butoxy phenyls) -6- (2,4- dibutoxy phenyl) -1,3,5- of 2,4- Triazine (trade name " TINUVIN 460 ", BASF AG manufacture), 2- (4,6- diphenyl -1,3,5-triazines -2- bases) -5- oneself Base epoxide phenol (trade name " TINUVIN 1577 ", BASF AG manufacture), 2- (4,6- diphenyl -1,3,5-triazines -2- Base) -5- [2- (2- ethyl hexanoyls epoxide) ethyoxyl] phenol (trade name " ADK STAB LA-46 ", Asahi Denka Co., Ltd.'s system Make) and double (4- the phenyls) -1,3,5- triazine (business of 2- (2- hydroxyls -4- [1- octyl group Epoxide carbonyls ethyoxyl] phenyl) -4,6- The name of an article " TINUVIN 479 ", BASF AG's manufacture).
For salicylate ultraviolet absorbent, it can enumerate for example：2- acryloxies phenol benzoate, 2- Acryloxy -3- methyl benzoic acids phenyl ester, 2- acryloxy -4- methyl benzoic acids phenyl ester, 2- acryloxy -5- methyl Phenol benzoate, 2- acryloxy -3- methoxy benzoic acids phenyl ester, 2 hydroxybenzoic acid phenyl ester, 2- hydroxy-3-methyl benzene first Acid phenenyl ester, 2- hydroxy-4-methyls phenol benzoate, 2- hydroxy-5-methyl yl benzoic acids phenyl ester, 2- hydroxy 3-methoxybenzene formic acid Phenyl ester and 3,5- di-tert-butyl-4-hydroxybenzoic acid 2, (" TINUVIN 120 ", BASF are public for trade name for 4- 6- di-tert-butyl phenyl esters Department's manufacture).
For benzophenone ultraviolet absorbent, hydroxy benzophenone ketone ultra-violet absorber, example can be enumerated Such as：2,4 dihydroxyl benzophenone, ESCALOL 567, BP-4, 2- hydroxyl -4- octyl group epoxides benzophenone, 4- dodecyl epoxide -2- dihydroxy benaophenonels, 4- benzyl epoxide -2- hydroxyl hexichol (" KEMISORB 111 ", CHEMIPRO are melted into Co. Ltd. system to trade name for ketone, 2,2'- dihydroxy -4- methoxy benzophenones Make), 2,2', 4,4'- tetrahydroxybenzophenones (trade name " SEESORB 106 ", SHIPRO are melted into Co., Ltd.'s manufacture) and 2, 2'- dihydroxy -4,4'- dimethoxy-benzophenones.
For cyanoacrylate ultraviolet absorbent, it can enumerate for example：2- alkyl cyanoacrylates, 2- Alpha-cyanoacrylate cycloalkyl ester, 2- alpha-cyanoacrylates alkoxy alkyl, 2- alpha-cyanoacrylates alkenyl esters and 2- alpha-cyanoacrylates Alkynyl ester.
It is from viewpoint while with high ultraviolet-absorbing with high photostability or transparent high from being readily obtained Adhesive phase 12 from the viewpoint of, the ultra-violet absorber that contains in adhesive phase 12 is preferably selected from purple by benzotriazole At least one in the group that ultraviolet absorbers, Hydroxyphenyltriazines ultra-violet absorber and benzophenone ultraviolet absorbent are formed Kind.The ultra-violet absorber contained in adhesive phase 12 is more preferably with the alkyl and hydroxyl conduct that carbon number is more than 6 The Benzotriazole Ultraviolet Stabilizer of nitrogen atom bonding of the phenyl of substituent with forming BTA ring.
In the case where adhesive phase 12 contains ultra-violet absorber, from the wavelength 350nm's in control adhesive phase 12 The transmissivity of light and from the viewpoint of realizing high ultraviolet-absorbing, relative to the adhesive or acrylic compounds in adhesive phase 12 The parts by weight of polymer 100, the content of the ultra-violet absorber in adhesive phase 12 is preferably more than 0.01 parts by weight, more preferably More than 0.05 parts by weight, more preferably more than 0.1 parts by weight.In addition, from suppressing in adhesive phase 12 with ultra-violet absorber Addition adhesive yellowing phenomenon generation so as to realize excellent optical characteristics, high transparency from the viewpoint of, relative to Adhesive or the parts by weight of acrylic polymer 100 in adhesive phase 12, ultra-violet absorber in adhesive phase 12 contain Amount is preferably below 10 parts by weight, more preferably below 9 parts by weight, more preferably below 8 parts by weight.
Adhesive phase 12 can contain light stabilizer.In the case where adhesive phase 12 contains light stabilizer, preferably simultaneously Contain ultra-violet absorber.Light stabilizer can be caught by irradiating the light such as ultraviolet and the chemistry of free radical that can generate Material.For light stabilizer, it can enumerate for example：Phenols light stabilizer, phosphorous light stabilizer, thioether class light stabilizer and The amine light stabilizer such as hindered amines stabilizer.Adhesive phase 12 can contain a kind of light stabilizer, can also contain two kinds with Upper light stabilizer.
For phenols light stabilizer, it can enumerate for example：2,6 di tert butyl 4 methyl phenol, 4- methylol -2, 6- DI-tert-butylphenol compounds, 2,6- di-t-butyl -4- ethyl -phenols, butylated hydroxyanisol, 3- (two tertiary fourths of 4- hydroxyls -3,5- Base phenyl) propionic acid n-octadecane base ester, (the 4- hydroxy-3-methyl -5- tert-butyl groups) benzyl malonic acid distearyl ester, tocopherol, 2, 2'- di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols), 2,2' methylene bis (4- ethyl -6- tert-butyl phenols), 4,4'- methylenes Base bis(2,6-di-butyl phenol), 4,4' butylidene biss (6- tert-butyl-m-cresols), 4,4'- thiobis (first between the 6- tert-butyl groups Phenol), styrenated phenol, N, N'- hexamethylene bis (3,5- di-t-butyl -4- hydroxyhydrocinnamamides), double (uncles of 3,5- bis- Butyl -4- benzylphosphonic acids ethyl ester) calcium, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, 1,3,5- tri- Methyl -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionyl oxygen Ylmethyl] methane, 1,6-HD-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 2,2' methylene bis (4- Methyl -6- cyclohexylphenols), 2,2' methylene bis [6- (1- methylcyclohexyls) paracresol], (the 4- tert-butyl groups -3- of 1,3,5- tri- Hydroxyl -2,6- dimethyl benzyls) isocyanuric acid, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid, three second two Double [3- (3,5- di-t-butyls-the 4- of alcohol double [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters], 2,2'- oxalyl amido Hydroxy phenyl) ethyl propionate], 6- (4- hydroxyl -3,5- di-tert-butyls amido) pungent sulfenyl -1,3,5- triazines of -2,4- two, to benzene Double [the 2- tert-butyl group -4- methyl -6- (the 2- hydroxyl -3- tert-butyl group -5- methyl-benzyls) phenyl] esters of dioctyl phthalate, the double { 2- [3- of 3,9- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] -1,1- dimethyl ethyls } four oxaspiros [5.5] of -2,4,8,10- Hendecane and double { 2- [3- (3,5- di-tert-butyl-hydroxy phenyls) the propionyloxy] -1,1- dimethyl ethyls } -2,4 of 3,9-, The oxaspiros of 8,10- tetra- [5.5] hendecane.
For phosphorous light stabilizer, it can enumerate for example：Phosphorous acid three (nonyl phenyl) ester, (2,4- of phosphorous acid three Di-tert-butyl-phenyl) ester, [the 2- tert-butyl groups -4- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls the sulfenyl) -5- methylbenzenes of phosphorous acid three Base] ester, the decyl ester of phosphorous acid three, phosphorous acid octyl group ester diphenyl, phosphorous acid didecyl base ester list phenylester, pentaerythrite two be sub- Phosphate two (tridecyl) ester, pentaerythritol diphosphites distearyl the ester, (nonyl benzene of pentaerythritol diphosphites two Base) ester, double (2,4- di-tert-butyl-phenyls) ester of pentaerythritol diphosphites, the double (uncles of 2,6- bis- of pentaerythritol diphosphites Butyl -4- aminomethyl phenyls) ester, double (the 2,4,6- tri-terts phenyl) ester of pentaerythritol diphosphites, isopropylidene bis-phenol two be sub- Double (the tridecanes of (the 2- tert-butyl group -5- methylphenols) diphosphites four of phosphate four (tridecyl) ester, the positive butanes of 4,4'- Base) ester, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane triphosphite ester six (tridecyl) ester, biphenylene Two phosphinate four (2,4- di-tert-butyl-phenyls) esters, the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies and three (2- [(2,4,8,10- tetra-terts dibenzo [d, f] [1,3,2] dioxaphosphepin cycloheptadiene -6- bases) epoxide] ethyl) amine.
For thioether class light stabilizer, it can enumerate for example：Dilauryl thiodipropionate, the meat of thio-2 acid two The dialkyl thiodipropionate such as cardamom ester and distearylthiodi-propionate compound and four [methylene (3- dodecyls Sulfenyl) propionic ester] polyalcohol such as methane β-alkylmercaptopropionates compound.
For amine light stabilizer, it can enumerate for example：Dimethyl succinate and 4- hydroxyl -2,2,6,6- tetramethyls Polymer (trade name " TINUVIN 622 ", BASF AG's manufacture), the polymer and N, N', the N " of base -1- piperidine ethanols, N " '-four (double (butyl-(N- methyl -2,2,6,6- tetramethyl piperidine -4- bases) amino) triazine -2- bases of 4,6-) -4,7- diazas The 1 of decane -1,10- diamines:1 reaction product (trade name " TINUVIN 119 ", BASF AG manufacture), it is poly- [6- (1,1,3, 3- tetramethyl butyls) amino -1,3,5- triazine -2,4- diyls } { 2,2,6,6- tetramethyl -4- piperidyls } imino group] six methylenes Base { (2,2,6,6- tetramethyl -4- piperidyls) imino group } (trade name " TINUVIN 944 ", BASF AG manufacture), the last of the ten Heavenly stems two Sour double (2,2,6,6- tetramethyl -4- piperidyls) esters (trade name " TINUVIN 770 ", BASF AG's manufacture), decanedioic acid are double The reaction of (2,2,6,6- tetramethyls -1- (octyl group epoxide) -4- piperidyls) ester and 1,1- dimethyl ethyls hydrogen peroxide and octane Product (trade name " TINUVIN 123 ", BASF AG's manufacture), [[3,5- double (1,1- dimethyl ethyl) -4- hydroxy phenyls] Methyl] double (1,2,2,6,6- pentamethyl -4- piperidyls) ester (trade name " TINUVIN 144 ", the BASF AG of butylmalonic acid Manufacture), three chloro- 1,3,5- triazines of hexamethylene and peroxidating N- butyl -2,2,6,6- tetramethyl -4- piperidinamines -2,4,6- it is anti- Reaction product (trade name " TINUVIN 152 ", BASF AG's manufacture), the decanedioic acid of answering product and 2- ethylaminoethanols it is double (1, 2,2,6,6- pentamethyl -4- piperidyls) ester and decanedioic acid methyl esters 1,2,2,6,6- pentamethyl -4- piperidines base esters mixture (business The name of an article " TINUVIN 292 ", BASF AG's manufacture) and 1,2,3,4- ethylene-dimalonic acids and 1,2,2,6,6- pentamethyl -4- Four oxaspiros [5.5] of -2,4,8,10- are undecanoic mixes esterification by piperidine alcohols and 3,9- double (2- hydroxyl -1,1- dimethyl ethyls) Thing (trade name " ADK STAB LA-63P ", Asahi Denka Co., Ltd.'s manufacture).As amines stabilizer, particularly preferred hindered amine Class stabilizer.
In the case where adhesive phase 12 contains light stabilizer, sufficiently sunproof sight is realized from adhesive phase 12 Point considers that, relative to the adhesive in adhesive phase 12 or the parts by weight of acrylic polymer 100, the light in adhesive phase 12 is steady The content for determining agent is preferably more than 0.1 parts by weight, more preferably more than 0.2 parts by weight.In addition, suppress from adhesive phase 12 From the viewpoint of being coloured caused by light stabilizer so as to realize high transparency, relative to the adhesive in adhesive phase 12 or third The parts by weight of alkene acids polymers 100, the content of the light stabilizer in adhesive phase 12 is preferably below 5 parts by weight, more preferably 3 Below parts by weight.
It not is above-mentioned copolymerizable crosslinking agent that the adhesive or acrylic polymer contained in adhesive phase 12, which can utilize, Crosslinking agent be crosslinked.Using the crosslinking of the adhesive or acrylic polymer carried out by the crosslinking agent, can adjust The gel fraction of adhesive phase 12.For such crosslinking agent, it can enumerate for example：Isocyanates crosslinking agent, epoxy Class crosslinking agent, melamine class crosslinking agent, peroxide crosslinking agent, ureas crosslinking agent, metal alkoxide class crosslinking agent, metal chelating Compound class crosslinking agent, metallic salt crosslinking agent, carbodiimide class crosslinking agent,Oxazolines crosslinking agent, aziridines crosslinking agent and Amine cross-linking agent.Adhesive phase 12 can contain a kind of crosslinking agent, can also contain the two or more crosslinking agents.In this implementation In mode, preferably using isocyanates crosslinking agent and/or epoxies crosslinking agent.
For isocyanates crosslinking agent, it can enumerate for example：Lower aliphatic polyisocyanates, ester ring type are more Isocyanates and aromatic polyisocyanate class.As lower aliphatic polyisocyanates, can enumerate for example：1,2- is sub- Ethyl diisocyanate, 1,4- tetramethylene diisocyanates and 1,6- hexamethylene diisocyanates.As the more isocyanides of ester ring type Esters of gallic acid, it can enumerate for example：Cyclopentylene diisocyanate, cyclohexylene diisocyanate, IPDI, Hydrogenated toluene diisocyanate and hydrogenated xylene diisocyanate.As aromatic polyisocyanate class, can enumerate for example： 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 4,4'- methyl diphenylene diisocyanates and phenylenedimethylidyne two Isocyanates.In addition, as isocyanates crosslinking agent, can also enumerate：Trimethylolpropane/toluene di-isocyanate(TDI) addition Thing (trade name " Coronate L ", Nippon Polyurethane Industry Co., Ltd. manufacture), the isocyanide of trimethylolpropane/hexa-methylene two Acid esters addition product (trade name " Coronate HL ", Nippon Polyurethane Industry Co., Ltd. manufacture), trimethylolpropane/benzene two Methylene diisocyanate addition product (trade name " Takenate D-110N ", Mitsui Chemicals, Inc manufacture) etc. commercially available product.
For epoxies crosslinking agent (multi-functional epoxy's compound), it can enumerate for example：N, N, N', N'- tetra- shrinks sweet Double (N, the N- diglycidyl amino methyl) hexamethylenes of oil base m-xylene diamine, diglycidylaniline, 1,3-, 1,6- oneself Hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, ethylene glycol diglycidylether, propylene glycol diglycidylether, The more glycidols of polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, sorbitol polyglycidylether, glycerine Ether, pentaerythrite polyglycidyl ether, polyglycereol polyglycidyl ether, anhydrosorbitol polyglycidyl ether, trihydroxy methyl Propane polyglycidyl ether, adipic acid 2-glycidyl ester, o-phthalic acid diglycidyl ester, three (2- hydroxyethyls) isocyanides Urea acid esters triglycidyl group ether, resorcinolformaldehyde resin and bisphenol-S diglycidyl ether.In addition, as epoxies Crosslinking agent, the epoxylite with two or more epoxy radicals can also be enumerated.In addition, as epoxies crosslinking agent, go back Trade name " TETRAD C " (Mitsubishi Gas Chemical Co., Ltd's manufacture) etc. commercially available product can be enumerated.
Contain the crosslinking agent as described above for being used to be crosslinked between acrylic polymer in adhesive phase 12 In the case of, from the viewpoint of being realized from adhesive phase 12 to the sufficient gluing reliability of adherend, relative to adhesive Adhesive or the parts by weight of acrylic polymer 100 in layer 12, the content of the crosslinking agent in adhesive phase 12 are preferably More than 0.001 parts by weight, more preferably more than 0.01 parts by weight.In addition, show appropriate softness from adhesive phase 12 From the viewpoint of property is so as to realize good bonding force, relative to the adhesive or acrylic polymer in adhesive phase 12 100 parts by weight, the content of the crosslinking agent in adhesive phase 12 is preferably below 10 parts by weight, more preferably below 5 parts by weight.
Adhesive phase 12 can be as needed also containing crosslinking accelerator, tackifying resin, antiaging agent, filler, pigment Or the additive such as the colouring agent such as dyestuff, antioxidant, chain-transferring agent, plasticizer, softening agent, surfactant and antistatic agent. For tackifying resin, it can enumerate for example：Rosin derivative, polyterpene resin (Port リ テ Le ペ Application Trees fat), Petropols With oil-soluble phenol resin.
From surface protection film X is realized from the viewpoint of the side of adhesive phase 12 is to the sufficient bonding force of adherend, bond The thickness of oxidant layer 12 is preferably more than 5 μm, more preferably more than 10 μm, more preferably more than 15 μm.In addition, from the easy of formation Property from the viewpoint of, the thickness of adhesive phase 12 is preferably less than 1000 μm, more preferably less than 900 μm, is more preferably 800 μm Below.
In the surface protection film X with the stepped construction comprising base material 11 and adhesive phase 12 as described above, base material The Elmendorf tearing strength of width is below 0.5N and the Elmendorf tearing strength in length substrate direction is 1N More than.The Elmendorf tearing strength in surface protection film X substrate width direction is preferably below 0.45N, is more preferably Below 0.4N, more preferably below 0.3N.The Elmendorf tearing strength in surface protection film X length substrate direction is preferably More than 1.1N, more preferably more than 1.3N, more preferably more than 1.5N.Elmendorf tearing strength is according to JIS K The value of 7128-2 measure.
In addition, the mist degree of the surface protection film X of optics thickness direction is preferably less than 3%, more preferably 2.5% with Under, more preferably less than 2%, more preferably less than 1.5%, more preferably less than 1%.Mist degree is to be determined according to JIS K 7136 Value.Total light transmittance in surface protection film X visible wavelength range is, for example, more than 85%.Total light transmittance is according to JIS The value of K 7361-1 measure.
Surface protection film X can be to be provided with release liner (partition) in the form of the adhesive surface 12a for covering adhesive phase 12. Release liner is the element for protecting surface protection film X adhesive phase 12 to make it not expose, by surface protection film X and quilt Peeled off during viscous thing fitting from surface protection film X.For release liner, it can enumerate for example：Base with lift-off processing layer Material, the low adhesivity base material comprising fluoropolymer and the low adhesivity base material comprising non-polar polymer.The table of release liner Face can implement demoulding processing, antifouling process or antistatic process.The thickness of release liner is, for example, 5 μm~200 μm.It is specific and Speech, surface protection film X can use the lamellar morphology of the release liner of the adhesive surface 12a with covering adhesive phase 12, also may be used It is wound into a roll by using without release liner in the form of surface protection film X base material 11 is alternately arranged with adhesive phase 12 The form of tubular.
The surface protection film X formed as described above can for example be manufactured in the following manner：Adhesive phase 12 is formed, Then adhesive phase 12 is fitted in into base material 11.Adhesive phase 12 can for example be formed in the following manner：In defined stripping The adhesive composition of the formation of coating adhesive layer 12 on pad and form adhesive composition layer, in the adhesive composition Further stacking release liner, and make adhesive composition solidify between the release liner on layer.
For adhesive composition as the formation of adhesive phase 12, such as make using by irradiating active energy beam Obtain adhesive composition of the polymerisation progress so as to solidification.That is, adhesive phase 12 is, for example, active energy ray-curable The solidfied material of type adhesive composition.The active energy ray curable adhesive composition of acrylic adhesive layer formation At least contain the monomer, oligomer and Photoepolymerizationinitiater initiater for being used for forming acrylic polymer.Monomer in said composition and Oligomer can be for the so-called partial polymer of the monomer mixture of the composition requirement of formation acrylic polymer Form provides.In addition, the adhesive composition can contain the other compositions used as needed as the bonding to be formed The composition of oxidant layer 12.As the solidification for adhesive phase 12 to the irradiation of active energy ray curable adhesive composition For active energy beam, it can enumerate for example：Ultraviolet, alpha ray, β rays, gamma-rays, neutron ray and electron ray, it is excellent Choosing uses ultraviolet.Irradiation, acrylic adhesive layer formation active-energy for receiving active energy beam For ray curing adhesive composition, produce initiation reaction by the activation of Photoepolymerizationinitiater initiater, polymerisation towards The formation of acrylic polymer is carried out.Using ultraviolet irradiation isoreactivity energy-ray irradiation as adhesive phase formation It is also easy in the case that the film of the adhesive composition is thicker to obtain during the curing of curing adhesive composition To suitable adhesive phase when cured.Therefore, adhesive phase 12 is the solidification of active energy ray curable adhesive composition Although being formed in for thing realizes that thicker but fully after solidification the aspect of adhesive phase 12 is suitable.
For above-mentioned Photoepolymerizationinitiater initiater, it can enumerate for example：Benzoin ethers Photoepolymerizationinitiater initiater, acetophenones Photoepolymerizationinitiater initiater, α -one alcohols Photoepolymerizationinitiater initiater, aromatic sulfonyl class Photoepolymerizationinitiater initiater, photolytic activity oximes photopolymerization Initiator, benzoin class Photoepolymerizationinitiater initiater, dibenzoyl class Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater, ketal Class Photoepolymerizationinitiater initiater and thioxanthene ketone class Photoepolymerizationinitiater initiater.For benzoin ethers Photoepolymerizationinitiater initiater, it can enumerate Such as：Benzoin methylether, benzoin ethyl ether, benzoin propyl ether, benzoin iso-propylether, benzoin isobutyl ether and 2,2- dimethoxies Base -1,2- diphenylethane -1- ketone.For acetophenones Photoepolymerizationinitiater initiater, it can enumerate for example：2,2- diethoxies Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 1- hydroxycyclohexyl phenyl ketones (Alpha-hydroxy cyclohexyl phenyl ketone), 4- phenoxydichloroacetophenones and 4- tert-butyl group dichloroacetophenones.For α -one alcohols Photoepolymerizationinitiater initiaters, it can enumerate Such as：2- methyl -2- hydroxypropiophenonepreparations and 1- [4- (2- hydroxyethyls) phenyl] -2- methylpropane -1- ketone.As aromatic series sulphur For acyl chloride Photoepolymerizationinitiater initiater, such as 2- naphthalene sulfonyl chlorides can be enumerated.For photolytic activity oximes Photoepolymerizationinitiater initiater, Such as 1- phenyl -1,2- propanedione -2- (O- ethoxy carbonyls) oxime can be enumerated.As benzoin class Photoepolymerizationinitiater initiater Speech, can enumerate such as benzoin.For dibenzoyl class Photoepolymerizationinitiater initiater, such as dibenzoyl can be enumerated.As two For Benzophenone class Photoepolymerizationinitiater initiater, it can enumerate for example：Benzophenone, benzoyl benzoic acid, 3,3'- dimethyl -4- Methoxy benzophenone and polyvinyl benzophenone.For ketal class Photoepolymerizationinitiater initiater, it can enumerate for example：Biphenyl Acyl dimethyl ketal.For thioxanthene ketone class Photoepolymerizationinitiater initiater, it can enumerate for example：Thioxanthones, CTX, 2- first Base thioxanthones, 2,4- dimethyl thioxanthones, isopropyl thioxanthone, 2,4- diisopropylthioxanthones and dodecyl thioxanthones.It is living The content of Photoepolymerizationinitiater initiater in property energy ray-curable adhesive composition is, for example, the weight % of 0.01 weight %~3.
As the adhesive composition of the formation of adhesive phase 12, can use containing the acrylic compounds as adhesive Polymer so as to for example can be by heat drying to solidify solvent type adhesive composition, Emulsion Adhesive composition. Said composition can contain composition of the other compositions used as needed as the adhesive phase 12 to be formed.The adhesive Acrylic polymer in composition can be by the way that the starting monomer composition of acrylic polymer formation be polymerize And obtain.For polymerization, it can enumerate for example：Polymerisation in solution, emulsion polymerization and polymerisation in bulk.Carry out polymerisation in solution When, as solvent, such as aromatic hydrocarbon, aliphatic hydrocarbon, ester ring type hydro carbons, esters and ketone can be used.As fragrance For the solvent of race's hydro carbons, such as toluene and benzene can be enumerated.For the solvent of aliphatic hydrocarbon, it can enumerate for example just Hexane and normal heptane.For solvent as ester ring type hydro carbons, such as hexamethylene and hexahydrotoluene can be enumerated.As esters Solvent for, such as ethyl acetate and n-butyl acetate can be enumerated.For the solvent of ketone, it can enumerate for example： Methyl ethyl ketone and methyl iso-butyl ketone (MIBK).In polymerisation in solution, can use a kind of solvent, can also use it is two or more molten Agent.
When starting monomer composition is polymerize in order to obtain acrylic polymer, polymerization initiator can be used.According to The species of polymerisation can use such as Photoepolymerizationinitiater initiater, thermal polymerization.During polymerization, a kind of polymerization can be used to draw Hair agent, two or more polymerization initiators can also be used.
For Photoepolymerizationinitiater initiater, it can enumerate for example：Above-mentioned benzoin ethers Photoepolymerizationinitiater initiater, acetophenone Class Photoepolymerizationinitiater initiater, α -one alcohols Photoepolymerizationinitiater initiater, aromatic sulfonyl class Photoepolymerizationinitiater initiater, photolytic activity oximes light gather Close initiator, benzoin class Photoepolymerizationinitiater initiater, dibenzoyl class Photoepolymerizationinitiater initiater, benzophenone Photoepolymerizationinitiater initiater, contracting Ketone Photoepolymerizationinitiater initiater and thioxanthene ketone class Photoepolymerizationinitiater initiater.The usage amount of Photoepolymerizationinitiater initiater is for example relative to monomer component Total amount (100 parts by weight) is the parts by weight of 0.01 parts by weight~3.
For thermal polymerization, it can enumerate for example：Azo type polymerization initiator, peroxide type polymerization trigger Agent and oxidation-reduction type polymerization initiator.For azo type polymerization initiator, it can enumerate for example：2,2'- azos two are different Butyronitrile, 2,2'- azos double (2- methylbutyronitriles), double (2 Methylpropionic acid) dimethyl esters of 2,2'- azos and double (the 4- cyanogen of 4,4'- azos Base valeric acid).For peroxide type polymerization initiator, it can enumerate for example：Benzoyl peroxide and peroxidating maleic acid The tert-butyl ester.The usage amount of thermal polymerization is 0.05 parts by weight~0.3 for example relative to monomer component total amount (100 parts by weight) Parts by weight.
When carrying out for obtaining the polymerization of aforesaid propylene acids polymers, in order to adjust the molecule of acrylic polymer Amount, can use chain-transferring agent.For chain-transferring agent, it can enumerate for example：α-thioglycerol, 2 mercapto ethanol, 2,3- Dimercapto -1- propyl alcohol, octyl mercaptan, tertiary nonyl mercaptan, lauryl mercaptan (lauryl mercaptan), tert-dodecylmercaotan, contracting Water glyceryl mercaptan, TGA, methyl thioglycolate, ethyl thioglycolate, TGA propyl ester, TGA butyl ester, mercapto The guanidine-acetic acid tert-butyl ester, 2-ethylhexyl mercaptoacetate, TGA monooctyl ester, isooctyl thioglycolate, TGA last of the ten Heavenly stems ester and mercapto Guanidine-acetic acid dodecyl ester.For chain-transferring agent, a kind of chain-transferring agent can be used, two or more chains can also be used to turn Move agent.In the present embodiment, as chain-transferring agent, preferably using α-thioglycerol.The usage amount of chain-transferring agent is for example relative In the monomer component total amount (100 parts by weight) for obtaining acrylic polymer be the parts by weight of 0.01 parts by weight~0.5.
Active energy ray curable adhesive composition, solvent type adhesive composition, Emulsion Adhesive composition Deng, in the case that the adhesive composition of the formation of adhesive phase 12 includes aforesaid propylene acid based oligomerization thing, the oligomer can With by the way that the starting monomer composition of composition requirement is polymerize to obtain.For polymerization, it can enumerate for example：It is molten Liquid polymerization, emulsion polymerization and polymerisation in bulk.For the solvent for polymerisation in solution, can enumerate as can for The material as described above of the solvent used into the polymerisation in solution of acrylic polymer.In the polymerisation in solution, it can make With a kind of solvent, two or more solvents can also be used.In addition, starting monomer composition is carried out in order to obtain above-mentioned oligomer During polymerization, polymerization initiator can be used.For the polymerization initiator, it can enumerate as can be for obtaining propylene The above-mentioned Photoepolymerizationinitiater initiater or thermal polymerization of the polymerization initiator used in the polymerization of acids polymers., can during polymerization To use a kind of polymerization initiator, two or more polymerization initiators can also be used.
Such as according to base material 11 possessed by the surface protection film X manufactured with upper type it is polyesters base material as described above. Such composition is suitable for enjoying heat resistance, the transparency, dimensional stability in surface protection film base material and surface protection film X The various characteristics easily shown etc. polyesters base material.
In addition, base material 11 possessed by surface protection film X is width uniaxial tension polyesters base material as described above.Should The thickness of base material 11 is as described above more than 75 μm, is preferably more than 80 μm.The thickness of the base material 11 is preferably 150 as described above Below μm, be preferably less than 125 μm.The tearing strengths such as the Elmendorf tearing strength of surface protection film are consumingly controlled by base The mechanical property of material, these compositions are suitable for realizing that the Elmendorf tear in substrate width direction is strong in surface protection film X The Elmendorf tearing strength spent for below 0.5N and length substrate direction is more than 1N above-mentioned composition.
In addition, the Elmendorf tearing strength in surface protection film X substrate width direction is 0.5N as described above Below, it is preferably below 0.45N, more preferably below 0.4N, more preferably below 0.3N.At the same time, surface protection film X The Elmendorf tearing strength in length substrate direction is as described above more than 1N, is preferably more than 1.1N, more preferably 1.3N Above, more preferably more than 1.5N.These compositions are suitable for realizing along Elmendorf tearing strength phase in surface protection film X To good the tearing property of hand in intentionally as little as below 0.5N substrate width direction.Also, Elmendorf tearing strength is in base More than 2 times of composition on material length direction for substrate width direction is suitable for improving along substrate width in surface protection film X The directive property of the tear in direction.Therefore, this composition is suitable for being in the situation for the state for fitting in adherend in surface protection film X Under make peeling force act on surface protection film X length substrate direction so that surface protection film X do not ftracture from adherend Suitably peel off.Specifically, it is suitable for the work first peeled off and then be bonded again after surface protection film X is bonded with adherend Make during industry (reprocessing operation) peeling force act on surface protection film X length substrate direction so that surface protection film X not Suitably peeled off from adherend on cracking ground.Not only also it is torn in substrate width direction but also easily on length substrate direction Surface protection film tends to easily cracking when reprocessing the stripping of operation and is difficult to suitably peel off from adherend.Generate out The surface protection film split cannot be used for being bonded again.On the other hand, surface protection film X has with being adapted for carrying out along substrate width The substrate width direction Elmendorf tearing strength of good the tearing property of hand in direction compares sufficiently large length substrate direction angstrom Er Menduofu tearing strengths, therefore be suitable for not peeling off suitably from adherend with not ftractureing when reprocessing operation.
As described above, surface protection film X is suitable for realizing good tearing property of hand in the lump while with polyesters base material With high re-workability.
As described above, phase difference is preferably more than 1500nm, is more preferably in the face of surface protection film X base material 11 More than 3000nm, more preferably more than 6000nm.Such composition is suitable in the display screen as liquid crystal display device most The surface of the transparent cover plate of front member suppresses to carry such as across polarized sunglasses in the case of being fitted with surface protection film X The lens of polarizing function produce so-called blank screen (Block ラ ッ Network ア ウ ト) phenomenon when carrying out visuognosis to the display screen.In addition, Phase difference is bigger in the face of base material 11, then the display screen as liquid crystal display device foremost part transparent cover plate table Face tends to more suppress to carry the lens of polarizing function such as across polarized sunglasses in the case of being fitted with surface protection film X So-called rainbow shaped laser spot (rainbow system ラ) phenomenon during visuognosis is carried out to the display screen.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in more detail, but the invention is not restricted to these embodiments.
[Production Example of acrylic compounds oligomer]
In reaction vessel, 60 weight parts of methacrylic acid tetrahydrochysene dicyclopentadiene base esters (DCPMA), 40 weights will be contained Part methyl methacrylate (MMA), 3.5 parts by weight are measured as α-thioglycerol of chain-transferring agent and 100 parts by weight as polymerization The mixture of the toluene of solvent stirs 1 hour at 70 DEG C, in a nitrogen atmosphere.Then, trigger 0.2 parts by weight as polymerization 2, the 2'- azodiisobutyronitriles of agent are added in the mixture in reaction vessel and prepare reaction solution, and are carried out at 70 DEG C 2 hours react.Then, carried out reacting for 2 hours at 80 DEG C.Then, the reaction solution in reaction vessel is placed in 130 DEG C Temperature atmosphere under, dried from the reaction solution and remove toluene, chain-transferring agent and unreacted monomer.Thus, solid has been obtained The acrylic compounds oligomer of shape.The weight average molecular weight (Mw) of the acrylic compounds oligomer is 5.1 × 103。
[acrylic pressure-sensitive adhesive compositions C1 preparation example]
Containing 78 parts by weight of acrylic acid 2- ethylhexyls (2EHA), 18 parts by weight NVPs (NVP) 0.035 the first Photoepolymerizationinitiater initiater of parts by weight is added with the monomer mixture of 4 parts by weight of acrylic acid 2- hydroxy methacrylates (HEA) (trade name " Irgacure 651 ", BASF AG's manufacture) and 0.035 parts by weight the second Photoepolymerizationinitiater initiater (trade name " Irgacure 184 ", BASF AG's manufacture), then determining its viscosity using viscosimeter for the mixture Ultraviolet is irradiated until the viscosity of the mixture reaches about 20Pas using ultraviolet lamp simultaneously.In viscosimetric analysis, The rotary speed of rotator of device is set as 10rpm, and measurement temperature is set as 30 DEG C.Thus, obtained as the list in mixture The partial polymer that a part for body composition is polymerized prepolymer composite (contain without polymerisation monomer into Point).Then, by the 100 parts by weight prepolymer composites, 11.8 parts by weight aforesaid propylene acid based oligomerization things, 17.6 parts by weight third Olefin(e) acid 2- hydroxy methacrylates (HEA), 0.294 parts by weight 1,6 hexanediol diacrylate (HDDA) and 0.353 parts by weight silane are even Join agent (trade name " KBM-403 ", Shin-Etsu Chemial Co., Ltd's manufacture) mixing, resulting in acrylic adhesives group Compound (acrylic pressure-sensitive adhesive compositions C1).
[acrylic pressure-sensitive adhesive compositions C2 preparation example]
In the flask (reaction vessel) with reflux condenser, nitrogen ingress pipe, agitator and thermometer, it will contain 100 parts by weight of acrylic acid 2- ethylhexyls (2EHA), 4 parts by weight of acrylic acid 2- hydroxy methacrylates (HEA), 0.2 parts by weight are as poly- Close initiator 2,2'- azodiisobutyronitriles and 205 parts by weight as the ethyl acetate of polymer solvent mixture in nitrogen gas At 63 DEG C react within 4 hours while gentle agitation under atmosphere.Thus, obtained containing third with about 35 weight % concentration The solution (acrylic polymer solution) of alkene acids polymers.Then, it is molten using ethyl acetate dilution acrylic polymer Liquid to cause acrylic polymer concentration to turn into 29 weight %, then in the acrylic polymer solution addition relative to The parts by weight of acrylic polymer 100 are trimethylolpropane/toluene di-isocyanate(TDI) addition product (trade name of 4 parts by weight " Coronate L ", Nippon Polyurethane Industry Co., Ltd. manufacture), tin dilaurate two of 0.02 parts by weight as tin-containing catalyst Tin octylate (trade name " EMBILIZER OL-1 ", the manufacture of Tokyo fine chemistry industry Co., Ltd.) and the conduct crosslinking delay of 3 parts by weight The acetylacetone,2,4-pentanedione of agent, the mixing of about 1 minute is carried out at 25 DEG C.It resulting in solvent type acrylic adhesives combination Thing (acrylic pressure-sensitive adhesive compositions C2).
[embodiment 1]
It is being 80 μm of the first polyethylene terephthalate film (trade name " COSMOSHINE SRF ", face to thickness Interior phase difference 8400, Japan spin Co., Ltd. manufacture) two-sided implementation sided corona treatment obtained from film (film F1) on be coated with it is above-mentioned Acrylic pressure-sensitive adhesive compositions C1, so as to form adhesive composition layer.Then, by polyethylene terephthalate (PET) class release liner (125 μm of thickness, Nitto Denko Corp's manufacture) is laminated in the adhesive composition layer, is covered The adhesive composition layer and blocking oxygen.There is [release liner/adhesive composition layer/film in this way F1] stacking form layered product.Then, using black light lamp (Toshiba Corporation's manufacture) from release liner side to the stacking It is 3mW/cm that body, which irradiates 300 seconds illumination,2Ultraviolet.Thus the adhesive composition layer of layered product is made to be solidified to form adhesive Layer.The thickness of the adhesive phase is 100 μm.Having made in the manner has [release liner/adhesive phase (thickness 100 μm)/film F as base material1(80 μm of thickness)] stacking form embodiment 1 surface protection film.
[embodiment 2]
Obtained from the two-sided implementation sided corona treatment to the second polyethylene terephthalate film that thickness is 80 μm Film (film F2) on be coated with aforesaid propylene acrylic binder composition C2, so as to form adhesive composition layer.Second is poly- to benzene Naphthalate film is using as the first polyethylene terephthalate film, " COSMOSHINE SRF's " is easy to be gluing Process layer replaces the film for spinning Co., Ltd.'s manufacture for Japan of the easy gluing process layer of hard conating purposes.Then, this is bonded Agent composition layer heats at 130 DEG C makes it dry and solidify for 60 seconds, so as in film F2On form adhesive phase.The adhesive The thickness of layer is 21 μm.Then, the surface of adhesive phase fitting PET classes release liner (25 μm of thickness, day east electrician strain formula Commercial firm manufactures).Make in the manner with the [film of release liner/adhesive phase (21 μm of thickness)/as base material F2(80 μm of thickness)] stacking form embodiment 2 surface protection film.
[comparative example 1]
Using to the 3rd polyethylene terephthalate film (trade name " XD500P ", phase in face that thickness is 75 μm Poor 3000, Dongli Ltd. manufacture) two-sided implementation sided corona treatment obtained from film (film F3) replace film F1As surface protection The base material of film, the surface protection film of comparative example 1 is made in the same manner as example 1 in addition.
[comparative example 2]
Use film F3Instead of film F2As the base material of surface protection film, make in the same way as in example 2 in addition The surface protection film of comparative example 2.
<Elmendorf tearing strength>
For each sample piece (60mm × 75mm) cut out from the surface protection film of embodiment and comparative example, using angstrom Er Menduofu tearing strengths determine device (trade name " Elmendorf tear test machine ", Tester Industry Co., Ltd system Make), respectively determine adhesive band base the Elmendorf tearing strength (N) of width (TD) and the length direction of adhesive band base (MD) Elmendorf tearing strength (N).The measure is carried out according to JIS K 7128-2.In the sample strip being measured, It is previously provided with the otch for being 20mm along the length of measure direction (TD or MD) extension from its end.In the measure, measure To the resistance for the tear load for assigning sample strip by device in a manner of causing the otch further to extend.In addition, the measure The measurement maximum of the middle said apparatus used is 1N.The result of the measure is shown in Table 1.
<Tearing property of hand>
For embodiment and each surface protection film of comparative example, the tearing property of hand in its substrate width direction has been investigated.It is specific and Speech, the surface protection film for having peeled off release liner, tests and is torn as caused by the handwork along its substrate width direction Split.In handwork inspection, situation about can easily tear is evaluated as tearing property of hand good (zero), tear will be failed It is bad (×) that situation is evaluated as tearing property of hand.It the results are shown in table 1.
<Mist degree>
Advised using haze meter HM-150 types (manufactured by Murakami K. K.'s dye technology research) according in JIS K 7136 Fixed method determines the mist degree (%) of each surface protection film of embodiment and comparative example.The measure is stripped for release liner And it is in and fits in slide (trade name " Slide glass S1112 ", thickness 1.0mm~1.2mm, the loose industrial strain of ripple nitre Formula commercial firm manufacture) state surface protection film carry out.It the results are shown in table 1.
[evaluation]
The surface protection film of the embodiment 1,2 of composition with the present invention realizes good tearing property of hand.On the other hand, The surface protection film of comparative example 1,2 can not be torn along substrate width direction with hand, be not carried out good tearing property of hand.

Claims (8)

1. a kind of surface protection film, wherein,
The surface protection film has the stepped construction comprising transparent base and adhesive phase,
The transparent base is substrate width direction uniaxial tension polyesters base material and has more than 75 μm of thickness, and
Elmendorf tearing strength of the surface protection film on substrate width direction is below 0.5N and in length substrate Elmendorf tearing strength on direction is more than 1N.
2. surface protection film as claimed in claim 1, wherein, the thickness of the transparent base is less than 150 μm.
3. surface protection film as claimed in claim 1, wherein, the stretching ratio of the width of the transparent base is 2.5 ~6 times.
4. surface protection film as claimed in claim 1, wherein, the thickness of described adhesive layer is more than 5 μm.
5. surface protection film as claimed in claim 1, wherein, described adhesive layer contain selected from by acrylic adhesives, At least one of group that polyurethane binding, polysiloxane-based adhesive and rubber adhesive are formed.
6. surface protection film as claimed in claim 1, wherein, described adhesive layer is active energy ray curable adhesive The solidfied material of composition.
7. surface protection film as claimed in claim 1, wherein, the mist degree of the surface protection film is less than 3%.
8. such as surface protection film according to any one of claims 1 to 7, wherein, the transparent base has more than 1500nm Face in phase difference.
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