WO2020110772A1 - Adhesive film, foldable device, and rollable device - Google Patents
Adhesive film, foldable device, and rollable device Download PDFInfo
- Publication number
- WO2020110772A1 WO2020110772A1 PCT/JP2019/044831 JP2019044831W WO2020110772A1 WO 2020110772 A1 WO2020110772 A1 WO 2020110772A1 JP 2019044831 W JP2019044831 W JP 2019044831W WO 2020110772 A1 WO2020110772 A1 WO 2020110772A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adhesive film
- weight
- pressure
- sensitive adhesive
- layer
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
- 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
-
- 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]
Definitions
- the present invention relates to an adhesive film.
- the present invention also relates to a foldable device provided with such an adhesive film and a rollable device provided with such an adhesive film.
- Adhesive films are used for reinforcement of various shaped members and surface protection.
- thermocompression bonding is usually performed with an anisotropic conductive film (ACF).
- ACF anisotropic conductive film
- an adhesive film may be bonded and reinforced in advance on the back side of the substrate of the semiconductor element (for example, Patent Document 1).
- a peeling layer and a flexible or rollable film substrate are formed on a supporting substrate such as glass, and the film substrate.
- a TFT substrate is formed, and an organic EL layer is formed thereon.
- the supporting substrate is peeled off to manufacture a flexible device or a rollable device.
- an adhesive film may be attached to the back side to reinforce (for example, Patent Document 2).
- a semiconductor device substrate, flexible device, or rollable device may be repeatedly bent, and if the adhesive film attached to the back side of the substrate has poor bending properties, the recoverability after bending may deteriorate, and at worst, it may be repeated. It may break due to bending. Specifically, when an adhesive film is attached to a bent portion (for example, a movable bent portion of a folding member), the following problems occur, for example.
- the thickness of the bendable part or the stretched part of the pressure-sensitive adhesive film will change greatly, and even in such a state, wrinkles are likely to occur and floating may occur. To do. For example, when the pressure-sensitive adhesive film is pulled, the thickness of the pressure-sensitive adhesive film is significantly reduced, and the adhesive film is apt to float from the adherend.
- IC integrated circuit
- FPC flexible printed circuit board
- An object of the present invention is to provide an adhesive film having excellent flexibility and transparency. Another object of the present invention is to provide a foldable device and a rollable device having excellent flexibility.
- the adhesive film of the present invention An adhesive film having a base material layer and an adhesive layer,
- the tan ⁇ (0.7%) at a strain of 0.7% measured in the tensile mode of the viscoelasticity measuring device is 0.1 or less.
- the adhesive film of the present invention An adhesive film having a base material layer and an adhesive layer,
- the difference between tan ⁇ (0.7%) at a strain of 0.7% and tan ⁇ (0.1%) at a strain of 0.1% measured in the tensile mode of the viscoelasticity measuring device (tan ⁇ (0.7%)-tan ⁇ (0.1%)) is 0.05 or less.
- the pressure-sensitive adhesive film of the present invention is bent at 6 ⁇ and held at 90° C. for 48 hours, after which the bending is released and left at 23° C. and 50% RH for 24 hours. Has a bending angle of 60 to 180 degrees.
- the pressure-sensitive adhesive film of the present invention has a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer.
- the top coat layer contains a binder containing at least one selected from polyester resins and urethane resins.
- the binder contains urethane resin.
- the top coat layer contains an antistatic component.
- the base material layer has a Young's modulus at 23° C. of 6.0 ⁇ 10 7 Pa or more.
- the material of the base material layer is at least one selected from polyimide and polyether ether ketone.
- the pressure-sensitive adhesive film of the present invention has a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer, and the topcoat layer contains a binder containing a urethane resin. And an antistatic component, and the material of the base material layer is at least one selected from polyimide and polyether ether ketone.
- the adhesive film of the present invention has a total light transmittance of 20% or more.
- the adhesive film of the present invention has a haze of 15% or less.
- the pressure-sensitive adhesive layer has an adhesive force of 1 N/25 mm or more with respect to a SUS plate at a pulling speed of 300 mm/min and a peel of 180 degrees at 23°C.
- the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive.
- the adhesive film of the present invention is attached to a foldable member.
- the foldable member is an OLED.
- the adhesive film of the present invention is attached to a rollable member.
- the rollable member is an OLED.
- the foldable device of the present invention includes the above-mentioned adhesive film.
- the rollable device of the present invention includes the above adhesive film.
- an adhesive film having excellent flexibility and transparency can be provided. According to the present invention, it is also possible to provide a foldable device and a rollable device having excellent flexibility.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of the foldable device of the present invention, showing one usage mode of the adhesive film of the present invention.
- FIG. 2 is a schematic cross-sectional view illustrating a method for evaluating the bending recovery property.
- FIG. 3 is a schematic cross-sectional view illustrating an evaluation method for evaluation of peeling.
- the adhesive film of the present invention has a base material layer and an adhesive layer. That is, the pressure-sensitive adhesive film of the present invention may have any appropriate other layer as long as it has a base material layer and a pressure-sensitive adhesive layer, as long as the effects of the present invention are not impaired.
- the base material layer may be one layer or two or more layers.
- the base material layer is preferably one layer from the viewpoint that the effect of the present invention can be further exhibited.
- the pressure-sensitive adhesive layer may be one layer or two or more layers.
- the pressure-sensitive adhesive layer is preferably one layer from the viewpoint that the effect of the present invention can be further exhibited.
- the pressure-sensitive adhesive film of the present invention may be provided with any suitable release liner on the surface of the pressure-sensitive adhesive layer on the side opposite to the base material layer for protection before use.
- the release liner examples include a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicone, or a surface of a base material (liner base material) such as paper or plastic film is formed of a polyolefin resin.
- a base material such as paper or plastic film
- Examples include laminated release liners.
- the plastic film as the liner substrate for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Examples thereof include a polyurethane film and an ethylene-vinyl acetate copolymer film.
- the thickness of the release liner is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 450 ⁇ m, further preferably 5 ⁇ m to 400 ⁇ m, and particularly preferably 10 ⁇ m to 300 ⁇ m.
- the adhesive film of the present invention has a total thickness d of preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 200 ⁇ m, further preferably 10 ⁇ m to 150 ⁇ m, particularly preferably 20 ⁇ m to 100 ⁇ m, and most preferably It is 30 ⁇ m to 80 ⁇ m.
- the total thickness d of the adhesive film of the present invention is within the above range, the effect of the present invention can be more exhibited.
- the adhesive film of the present invention has a tan ⁇ (0.7%) at a strain of 0.7% measured in a tension mode of a viscoelasticity measuring device of 0.1 or less, preferably 0.09 or less, and more preferably Is 0.08 or less, more preferably 0.07 or less, and particularly preferably 0.06 or less. If the tan ⁇ (0.7%) at a strain of 0.7% of the pressure-sensitive adhesive film of the present invention measured in a tension mode of a viscoelasticity measuring device is within the above range, the effect of the present invention can be more exhibited.
- Tan ⁇ (0.7%) at a strain of 0.7% measured in the tension mode of the viscoelasticity measuring device of the adhesive film is an index showing the loss tangent when the adhesive film is largely bent.
- the method for measuring tan ⁇ (0.7%) at a strain of 0.7% measured in the tensile mode of the viscoelasticity measuring device will be described in detail later.
- the adhesive film of the present invention has a tan ⁇ (0.1%) at a strain of 0.1% measured in a tensile mode of a viscoelasticity measuring device of preferably 0.1 or less, more preferably 0.08 or less. , More preferably 0.06 or less, and particularly preferably 0.05 or less. If the tan ⁇ (0.1%) at a strain of 0.1% measured in the tensile mode of the viscoelasticity measuring device of the pressure-sensitive adhesive film of the present invention is within the above range, the effect of the present invention can be more exhibited.
- Tan ⁇ (0.1%) at a strain of 0.1% measured in the tension mode of the viscoelasticity measuring device of the adhesive film is an index showing the loss tangent when the adhesive film is bent slightly.
- Tan ⁇ (0.1%) at a strain of 0.1% measured in the tension mode of the viscoelasticity measuring device of the adhesive film is an index showing the loss tangent when the adhesive film is bent slightly.
- the pressure-sensitive adhesive film of the present invention has a difference (tan ⁇ (tan ⁇ (0.1%) between a tan ⁇ (0.7%) at a strain of 0.7% and a tan ⁇ (0.1%) at a strain of 0.1% measured in a tensile mode of a viscoelasticity measuring device.
- 0.7%)-tan ⁇ (0.1%)) is preferably 0.05 or less, more preferably 0.04 or less, still more preferably 0.03 or less.
- the difference (tan ⁇ (0.7%) between tan ⁇ (0.7%) at a strain of 0.7% and tan ⁇ (0.1%) at a strain of 0.7%, which was measured in a tensile mode of a viscoelasticity measuring device, of the adhesive film. %)-Tan ⁇ (0.1%)) is an index showing the difference between the loss tangent when the pressure-sensitive adhesive film is largely bent and the loss tangent when the pressure-sensitive adhesive film is slightly bent.
- the pressure-sensitive adhesive film of the present invention is preferably bent at 6 ⁇ and held at 90° C. for 48 hours, then released from the bending, and allowed to stand at 23° C. and 50% RH for 24 hours. It is 60 to 180 degrees, more preferably 80 to 180 degrees, further preferably 100 to 180 degrees, particularly preferably 120 to 180 degrees, and most preferably 150 to 180 degrees. is there.
- the bending angle of the pressure-sensitive adhesive film of the present invention after being bent at 6 ⁇ and held at 90° C. for 48 hours, then released, and allowed to stand at 23° C. and 50% RH for 24 hours is within the above range. Within the range, the effect of the present invention can be more exerted.
- the bending angle of the pressure-sensitive adhesive film after being bent at 6 ⁇ and held at 90° C. for 48 hours, then released, and allowed to stand at 23° C. and 50% RH for 24 hours is the recoverability after bending. Is an index indicating.
- the method of measuring the bending angle after bending at 6 ⁇ and holding at 90° C. for 48 hours, releasing the bending, and leaving at 23° C. and 50% RH for 24 hours will be described in detail later.
- the adhesive film of the present invention has a total light transmittance of preferably 20% or more, more preferably 30% or more, further preferably 40% or more, particularly preferably 50% or more, most preferably Is 60% or more.
- a total light transmittance of the pressure-sensitive adhesive film of the present invention is within the above range, excellent transparency can be further exhibited.
- the adhesive film of the present invention has a haze of preferably 15% or less, more preferably 13% or less, further preferably 10% or less, particularly preferably 8% or less, and most preferably 6%. It is below. When the haze of the pressure-sensitive adhesive film of the present invention is within the above range, excellent transparency can be more exhibited.
- the adhesive film of the present invention has excellent flexibility and transparency, it is preferably attached to a foldable member.
- Any appropriate member can be adopted as the foldable member as long as it can be repeatedly bent. Examples of such a foldable member include a foldable optical member, a foldable electronic member, and the like. Typically, a foldable OLED is used.
- the pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, and thus is preferably attached to a rollable member.
- Any appropriate member can be adopted as the rollable member as long as it can be repeatedly wound and unwound.
- Examples of such a rollable member include a rollable optical member and a rollable electronic member, and typically, a rollable OLED is used.
- the thickness of the base material layer is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, further preferably 10 ⁇ m to 100 ⁇ m, particularly preferably 15 ⁇ m to 80 ⁇ m, and most preferably 20 ⁇ m to 60 ⁇ m. .. When the thickness of the base material layer is within the above range, the effect of the present invention can be more exhibited.
- the Young's modulus of the base material layer at 23° C. is preferably 6.0 ⁇ 10 7 Pa or higher, more preferably 1.0 ⁇ 10 8 Pa or higher, and further preferably 5.0 ⁇ 10 8 Pa or higher. And particularly preferably 8.0 ⁇ 10 8 Pa or higher, and most preferably 1.0 ⁇ 10 9 Pa or higher.
- the upper limit of the Young's modulus of the base material layer at 23° C. is typically and preferably 1.0 ⁇ 10 11 Pa or less. When the Young's modulus at 23° C. of the base material layer is within the above range, the effect of the present invention can be more exhibited. If the Young's modulus of the base material layer at 23° C.
- the adhesive film is bent at an angle, the tension on the outer diameter side may not be sufficiently retained against the compression on the inner diameter side, and the thickness may change. There is a possibility that it will be easy to float from the adherend. If the Young's modulus at 23° C. of the base material layer is too high, the pressure-sensitive adhesive film may not be easily deformed. The method of measuring Young's modulus will be described in detail later.
- any appropriate material can be adopted as long as the effect of the present invention is not impaired.
- a material of such a base material layer a resin material is typically mentioned.
- Examples of the resin material as the material of the base material layer include polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polymethyl methacrylate.
- PI polyimide
- PEEK polyether ether ketone
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- Acrylic resin such as (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) , Polyamide (nylon), wholly aromatic polyamide (aramid), polyvinyl chloride (PVC), polyvinyl acetate, polyphenylene sulfide (PPS), fluorine resin, cyclic olefin polymer, and the like.
- PMMA polycarbonate
- TAC triacetyl cellulose
- PES ethylene-propylene copolymer
- EVA ethylene-vinyl acetate copolymer
- Polyamide nylon
- ArVC wholly aromatic polyamide
- PVC polyvinyl chloride
- PPS polyphenylene sulfide
- fluorine resin cyclic olefin polymer, and the like.
- the resin material as the material of the base material layer is preferably at least one selected from polyimide (PI), polyether ether ketone (PEEK), and cyclic olefin-based polymer from the viewpoint that the effect of the present invention can be further exhibited. And more preferably at least one selected from polyimide (PI) and polyether ether ketone (PEEK).
- PI polyimide
- PEEK polyether ether ketone
- the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, further preferably 10 ⁇ m to 100 ⁇ m, particularly preferably 15 ⁇ m to 80 ⁇ m, and most preferably 20 ⁇ m to 60 ⁇ m. .. When the thickness of the pressure-sensitive adhesive layer is within the above range, the effect of the present invention can be more exhibited.
- the adhesive force of the pressure-sensitive adhesive layer to the glass plate at a pulling speed of 300 mm/min and a peel of 180 degrees at 23° C. is preferably 1 N/25 mm or more, more preferably 5 N/25 mm or more, and further preferably It is 10 N/25 mm or more, particularly preferably 12 N/25 mm or more, and most preferably 15 N/25 mm or more.
- the upper limit of the adhesive force of the pressure-sensitive adhesive layer to the glass plate at a tensile rate of 300 mm/min and 180 degree peeling at 23° C. is typically preferably 1000 N/25 mm or less, more preferably 5000 N/25 mm.
- the adhesive strength of the pressure-sensitive adhesive layer to the glass plate at a tensile rate of 300 mm/min at 180° peel at 23° C. is within the above range, the effect of the present invention can be further exhibited.
- the adhesive layer contains a base polymer.
- the base polymer may be only one type, or may be two or more types.
- the content ratio of the base polymer in the pressure-sensitive adhesive layer is preferably 20% by weight to 100% by weight, more preferably 30% by weight to 95% by weight, from the viewpoint that the effect of the present invention can be further exhibited. It is preferably 40% by weight to 90% by weight, particularly preferably 45% by weight to 85% by weight, and most preferably 50% by weight to 80% by weight.
- the base polymer any suitable polymer can be adopted as long as the effect of the present invention is not impaired.
- the base polymer is preferably at least one selected from acrylic polymers, rubber polymers, silicone polymers, and urethane polymers from the viewpoint that the effects of the present invention can be further exhibited.
- the pressure-sensitive adhesive layer is preferably composed of an acrylic pressure-sensitive adhesive containing an acrylic polymer, a rubber-based pressure-sensitive adhesive containing a rubber-based polymer, a silicone-based pressure-sensitive adhesive containing a silicone-based polymer, and a urethane-based pressure-sensitive adhesive containing a urethane-based polymer. At least one selected is included.
- the pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive.
- an acrylic pressure-sensitive adhesive will be described in detail as a typical example of the pressure-sensitive adhesive that can be contained in the pressure-sensitive adhesive layer.
- the acrylic pressure-sensitive adhesive contains an acrylic polymer as a base polymer.
- the acrylic adhesive may contain a tackifying resin.
- the acrylic pressure-sensitive adhesive may contain a crosslinking agent.
- the acrylic pressure-sensitive adhesive contains an acrylic polymer, a tackifying resin, and a crosslinking agent
- the content ratio of the total amount of the acrylic polymer, the tackifying resin, and the crosslinking agent with respect to the total amount of the acrylic pressure-sensitive adhesive is From the viewpoint that the effect can be further exhibited, it is preferably 95% by weight or more, more preferably 97% by weight or more, and further preferably 99% by weight or more.
- acrylic polymer for example, a polymer of a monomer component containing an alkyl (meth)acrylate as a main monomer and further containing a sub-monomer copolymerizable with the main monomer is preferable.
- the main monomer means a component which accounts for more than 50% by weight of the whole monomer component.
- alkyl (meth)acrylate for example, a compound represented by the following formula (1) can be preferably used.
- CH 2 C(R 1 )COOR 2 (1)
- R 1 in the above formula (1) is a hydrogen atom or a methyl group
- R 2 is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms is referred to as “C1- 20").
- R 2 is preferably a C1-14 chain alkyl group, more preferably a C2-10 chain alkyl group, and further preferably a C4-8 chain alkyl group. It is a chain alkyl group.
- the term “chain” means a straight chain and a branched chain.
- alkyl(meth)acrylate in which R 2 is a C1-20 chain alkyl group examples include, for example, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl.
- the alkyl (meth)acrylate is preferably n-butyl acrylate (BA) or 2-ethylhexyl acrylate (2EHA) from the viewpoint that the effect of the present invention can be further exhibited.
- the content ratio of the alkyl (meth)acrylate in all the monomer components used for the synthesis of the acrylic polymer is preferably 70% by weight or more, more preferably 85% by weight, from the viewpoint that the effect of the present invention can be further exhibited. It is above, and more preferably 90% by weight or more.
- the upper limit of the content ratio of the alkyl (meth)acrylate is preferably 99.5% by weight or less, more preferably 99% by weight or less.
- the acrylic polymer may be obtained by polymerizing substantially only alkyl (meth)acrylate.
- alkyl R 2 is a linear alkyl group of C4-8 among alkyl (meth) acrylates contained in the monomer components
- the ratio of (meth)acrylate is preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 90% by weight or more, particularly from the viewpoint that the effect of the present invention can be further exhibited. It is preferably 95% by weight or more, and most preferably 99% by weight to 100% by weight.
- an acrylic polymer in which 50% by weight or more of all monomer components is n-butyl acrylate (BA) can be mentioned.
- the content ratio of n-butyl acrylate (BA) in all the monomer components is preferably more than 50% by weight and 100% by weight or less, and more preferably 55% by weight, from the viewpoint that the effect of the present invention can be further exhibited.
- % To 95% by weight more preferably 60 to 90% by weight, particularly preferably 63 to 85% by weight, most preferably 65 to 80% by weight.
- the total monomer component may further include 2-ethylhexyl acrylate (2EHA) in a proportion smaller than n-butyl acrylate (BA).
- an acrylic polymer is an acrylic polymer in which less than 50% by weight of all monomer components is 2-ethylhexyl acrylate (2EHA).
- the content ratio of 2-ethylhexyl acrylate (2EHA) in all the monomer components is preferably more than 0% by weight and 48% by weight or less, more preferably 5% or more, from the viewpoint that the effect of the present invention can be further exhibited.
- the total monomer component may further contain n-butyl acrylate (BA) in a proportion higher than that of 2-ethylhexyl acrylate (2EHA).
- Other monomers may be copolymerized with the acrylic polymer as long as the effects of the present invention are not impaired.
- Other monomers can be used for the purpose of adjusting the glass transition temperature (Tg) of the acrylic polymer, adjusting the adhesive performance, and the like.
- Tg glass transition temperature
- the monomer capable of improving the cohesive force and heat resistance of the pressure-sensitive adhesive include sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl esters, aromatic vinyl compounds, and the like. Is preferred.
- Specific examples of vinyl esters include, for example, vinyl acetate (VAc), vinyl propionate, vinyl laurate and the like, with vinyl acetate (VAc) being preferred.
- the “other monomer” may be only one kind or two or more kinds.
- the content of the other monomer in all the monomer components is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 40% by weight, and further preferably 0.1% by weight to It is 10% by weight, particularly preferably 0.5% by weight to 5% by weight, and most preferably 1% by weight to 3% by weight.
- the other monomer that can introduce a functional group that can serve as a crosslinking group point into the acrylic polymer or contribute to the improvement of adhesive strength for example, a hydroxyl group (OH group)-containing monomer, a carboxy group-containing monomer, an acid anhydride group-containing monomer, an amide
- a hydroxyl group (OH group)-containing monomer for example, a hydroxyl group (OH group)-containing monomer, a carboxy group-containing monomer, an acid anhydride group-containing monomer, an amide
- examples thereof include a group-containing monomer, an amino group-containing monomer, an imide group-containing monomer, an epoxy group-containing monomer, (meth)acryloylmorpholine and vinyl ethers.
- the acrylic polymer there is an acrylic polymer in which a carboxy group-containing monomer is copolymerized as the other monomer.
- the carboxy group-containing monomer include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and isocrotonic acid.
- acrylic acid (AA) and methacrylic acid (MAA) are preferable as the carboxy group-containing monomer, from the viewpoint that the effect of the present invention can be further expressed, and acrylic acid (AA) is more preferable. is there.
- the content ratio of the other monomer in all the monomer components is preferably 0.1% by weight to 10% by weight from the viewpoint that the effect of the present invention can be further exhibited. More preferably 0.2% to 8% by weight, still more preferably 0.5% to 5% by weight, particularly preferably 0.7% to 4% by weight, most preferably 1% by weight. % To 3% by weight.
- an acrylic polymer is an acrylic polymer in which a hydroxyl group-containing monomer is copolymerized as another monomer.
- the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth).
- Hydroxyalkyl (meth)acrylates such as acrylates; polypropylene glycol mono(meth)acrylate; N-hydroxyethyl (meth)acrylamide; and the like.
- the hydroxyl group-containing monomer is preferably a hydroxyalkyl(meth)acrylate whose alkyl group is a linear chain having 2 to 4 carbon atoms, from the viewpoint of more exerting the effects of the present invention.
- Specific examples thereof include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA), and 4-hydroxybutyl acrylate (4HBA) is more preferable.
- the content ratio of the other monomer in all the monomer components is preferably 0.001% by weight to 10% by weight from the viewpoint that the effect of the present invention can be more exhibited. It is preferably 0.01% to 5% by weight, more preferably 0.02% to 2% by weight, particularly preferably 0.03% to 1% by weight, and most preferably 0.05. % By weight to 0.5% by weight.
- the Tg of the base polymer can be, for example, ⁇ 80° C. or higher in that the effect of the present invention can be further exhibited.
- the base polymer preferably an acrylic polymer
- Tg is preferably ⁇ 15° C. or lower from the viewpoint of enhancing the deformability of the pressure-sensitive adhesive layer in the shearing direction.
- the Tg of the base polymer is, for example, preferably ⁇ 25° C. or lower, more preferably ⁇ 40° C. or lower, further preferably ⁇ 50° C. or lower.
- the Tg of the base polymer is designed so that, for example, the Tg is preferably ⁇ 70° C. or higher (more preferably ⁇ 65° C. or higher, further preferably ⁇ 60° C. or higher) from the viewpoint of enhancing cohesiveness and shape recovery. Has been done.
- the Tg of the base polymer is based on the Tg of a homopolymer (homopolymer) of each monomer constituting the base polymer and the weight fraction (copolymerization ratio on a weight basis) of the monomer, and is calculated from the Fox equation. Refers to the required value.
- Tg is the glass transition temperature (unit: K) of the copolymer
- Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio on a weight basis)
- Tgi is a homopolymer of the monomer i. Represents the glass transition temperature (unit: K) of.
- Tg of the homopolymer the value described in publicly known data shall be adopted.
- Tg of the homopolymer for example, the following values can be specifically used.
- an acrylic polymer for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or the like, various polymerization methods known as a synthetic method of an acrylic polymer may be appropriately adopted. You can Among these polymerization methods, the solution polymerization method can be preferably used.
- a method of supplying a monomer when carrying out the solution polymerization a batch charging method of supplying all of the monomer components at once, a continuous supply (dropping) method, a divided supply (dropping) method and the like can be appropriately adopted.
- the polymerization temperature can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc., and is preferably 20° C. or higher, more preferably 30° C. or higher, and further preferably 40° C. Or higher, preferably 170° C. or lower, more preferably 160° C. or lower, still more preferably 140° C. or lower.
- photopolymerization typically carried out in the presence of a photopolymerization initiator
- irradiating light such as UV
- irradiation with radiation such as ⁇ ray or ⁇ ray
- active energy ray irradiation polymerization such as radiation polymerization may be employed.
- the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from any appropriate organic solvent.
- organic solvent examples thereof include aromatic compounds such as toluene (typically aromatic hydrocarbons), acetic acid esters such as ethyl acetate, and aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane.
- the initiator used for polymerization can be appropriately selected from any appropriate polymerization initiator according to the type of polymerization method. Only 1 type may be sufficient as a polymerization initiator and 2 or more types may be sufficient as it. Examples of such a polymerization initiator include azo polymerization initiators such as 2,2′-azobisisobutyronitrile (AIBN); persulfates such as potassium persulfate; benzoyl peroxide, hydrogen peroxide, etc. Peroxide-based initiators; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds; and the like. As another example of the polymerization initiator, a redox type initiator obtained by combining a peroxide and a reducing agent can be mentioned.
- AIBN 2,2′-azobisisobutyronitrile
- persulfates such as potassium persulfate
- benzoyl peroxide hydrogen peroxide, etc.
- the amount of the polymerization initiator used is preferably 0.005 to 1 part by weight, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of all the monomer components.
- the Mw of the acrylic polymer is preferably 10 ⁇ 10 4 to 500 ⁇ 10 4 , more preferably 10 ⁇ 10 4 to 150 ⁇ 10 4 , and further preferably 20 ⁇ 10 4 to 75 ⁇ 10 4 . And particularly preferably 35 ⁇ 10 4 to 65 ⁇ 10 4 .
- Mw refers to a standard polystyrene conversion value obtained by GPC (gel permeation chromatography).
- GPC device for example, a model name “HLC-8320GPC” (column: TSKgel GMH-H(S), manufactured by Tosoh Corporation) can be used.
- the acrylic pressure-sensitive adhesive may contain a tackifying resin from the viewpoint that the effect of the present invention can be further exhibited.
- the tackifying resin include rosin-based tackifying resin, terpene-based tackifying resin, hydrocarbon-based tackifying resin, epoxy-based tackifying resin, polyamide-based tackifying resin, elastomer-based tackifying resin, and phenol-based tackifying resin. , Ketone-based tackifying resins, and the like.
- the tackifying resin may be only one kind or two or more kinds.
- the amount of the tackifying resin used is preferably 5 parts by weight to 70 parts by weight, more preferably 10 parts by weight to 60 parts by weight, based on 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited.
- the tackifying resin preferably contains a tackifying resin TL having a softening point of less than 105° C. from the viewpoint that the effect of the present invention can be further exhibited.
- the tackifying resin TL can effectively contribute to improving the deformability of the pressure-sensitive adhesive layer in the surface direction (shear direction).
- the softening point of the tackifying resin used as the tackifying resin TL is preferably 50° C. to 103° C., more preferably 60° C. to 100° C., and further preferably
- the temperature is from 65°C to 95°C, particularly preferably from 70°C to 90°C, and most preferably from 75°C to 85°C.
- the softening point of the tackifying resin is defined as the value measured based on the softening point test method (ring and ball method) specified in JIS K5902 and JIS K2207. Specifically, the sample should be melted as quickly as possible and the ring placed on a flat metal plate should be carefully filled to prevent bubbles. After cooling down, cut off the raised part from the plane including the upper end of the ring with a slightly heated knife. Next, a support (ring holder) is placed in a glass container (heating bath) having a diameter of 85 mm or more and a height of 127 mm or more, and glycerin is poured until the depth becomes 90 mm or more.
- a glass container heating bath
- a steel ball (diameter: 9.5 mm, weight: 3.5 g) and a ring filled with a sample are immersed in glycerin so that they do not contact each other, and the temperature of glycerin is kept at 20°C plus or minus 5°C for 15 minutes. ..
- a steel ball is placed on the center of the surface of the sample in the ring, and this is placed in a fixed position on the support.
- keeping the distance from the upper end of the ring to the glycerin surface at 50 mm placing a thermometer, setting the position of the center of the mercury ball of the thermometer to the same height as the center of the ring, and heating the container.
- the Bunsen burner flame used for heating is placed so as to hit the center of the bottom of the container and the edge thereof so that the heating is even.
- the rate at which the bath temperature rises after reaching 40° C. after the start of heating must be 5.0 plus or minus 0.5° C. per minute.
- the temperature at which the sample gradually softens and flows down from the ring and finally comes into contact with the bottom plate is read, and this is taken as the softening point. Two or more softening points are measured at the same time, and the average value is adopted.
- the amount of the tackifying resin TL to be used is preferably 5 parts by weight to 50 parts by weight, more preferably 10 parts by weight to 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited.
- the amount is 45 parts by weight, more preferably 15 parts by weight to 40 parts by weight, particularly preferably 20 parts by weight to 35 parts by weight, and most preferably 25 parts by weight to 32 parts by weight.
- the tackifying resin TL one or two or more kinds of the tackifying resins exemplified above may be appropriately selected from those having a softening point of less than 105°C.
- the tackifying resin TL preferably contains a rosin resin.
- Rosin resins that can be preferably used as the tackifying resin TL include rosin esters such as unmodified rosin ester and modified rosin ester.
- modified rosin ester include hydrogenated rosin ester.
- the tackifying resin TL preferably contains a hydrogenated rosin ester from the viewpoint that the effect of the present invention can be further exhibited.
- the hydrogenated rosin ester has a softening point of preferably less than 105° C., more preferably 50° C. to 100° C., still more preferably 60° C. to 90° C., from the viewpoint that the effect of the present invention can be further exhibited. And particularly preferably 70° C. to 85° C., and most preferably 75° C. to 85° C.
- the tackifying resin TL may contain a non-hydrogenated rosin ester.
- the non-hydrogenated rosin ester is a concept that comprehensively refers to the above-mentioned rosin esters other than the hydrogenated rosin ester.
- Examples of the non-hydrogenated rosin ester include unmodified rosin ester, disproportionated rosin ester, and polymerized rosin ester.
- the non-hydrogenated rosin ester has a softening point of preferably less than 105° C., more preferably 50° C. to 100° C., still more preferably 60° C. to 90, from the viewpoint that the effect of the present invention can be further exhibited.
- C. particularly preferably 70 to 85.degree. C., most preferably 75 to 85.degree.
- the tackifying resin TL may contain another tackifying resin in addition to the rosin-based resin.
- the other tackifying resin among the tackifying resins exemplified above, one kind or two or more kinds appropriately selected from those having a softening point of less than 105° C. can be adopted.
- the tackifying resin TL may include, for example, a rosin resin and a terpene resin.
- the content ratio of the rosin-based resin in the entire tackifying resin TL is preferably more than 50% by weight, more preferably 55% by weight to 100% by weight, and further preferably, from the viewpoint that the effect of the present invention can be further exhibited. Is 60% to 99% by weight, particularly preferably 65% to 97% by weight, most preferably 75% to 97% by weight.
- the tackifying resin may include the tackifying resin TL in combination with the tackifying resin TH having a softening point of 105° C. or higher (preferably 105° C. to 170° C.), in that the effect of the present invention can be further exhibited. Good.
- the tackifying resin TH may include at least one selected from rosin-based tackifying resins (for example, rosin esters) and terpene-based tackifying resins (for example, terpene phenolic resins).
- the acrylic pressure-sensitive adhesive may contain a crosslinking agent.
- the cross-linking agent may be only one kind or two or more kinds. By using the crosslinking agent, it is possible to impart an appropriate cohesive force to the acrylic pressure-sensitive adhesive.
- the cross-linking agent can also help control the displacement and return distances in the retention test.
- the acrylic pressure-sensitive adhesive containing a crosslinking agent can be obtained, for example, by forming a pressure-sensitive adhesive layer using a pressure-sensitive adhesive composition containing the crosslinking agent.
- the cross-linking agent may be included in the acrylic pressure-sensitive adhesive in a form after the cross-linking reaction, a form before the cross-linking reaction, a form in which the cross-linking reaction has occurred, an intermediate or complex form of these, and the like.
- the cross-linking agent is typically contained in the acrylic pressure-sensitive adhesive exclusively in the form after the cross-linking reaction.
- the amount of the cross-linking agent used is preferably 0.005 to 10 parts by weight, more preferably 0.01 part by weight, based on 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited.
- To 7 parts by weight more preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 4 parts by weight, and most preferably 1 to 3 parts by weight.
- cross-linking agent examples include isocyanate cross-linking agents, epoxy cross-linking agents, silicone cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, silane cross-linking agents, alkyl etherified melamine cross-linking agents, and metal chelate cross-linking agents.
- a crosslinking agent such as peroxide, and the like, from the viewpoint that the effect of the present invention can be more exhibited, an isocyanate crosslinking agent and an epoxy crosslinking agent are preferable, and an isocyanate crosslinking agent is more preferable. ..
- the isocyanate-based cross-linking agent a compound having two or more isocyanate groups (including an isocyanate-regenerated functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification) can be used.
- the isocyanate-based cross-linking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate.
- isocyanate cross-linking agent examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2 Aromatic diisocyanates such as 4,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate; trimethylolpropane/tolylene diisocyanate trimer adducts (for example, manufactured by Tosoh Corporation, Trade name Coronate L), trimethylolpropane/hexamethylene diisocyanate trimer adduct (for example, Tosoh Corporation, trade name: Coronate HL), hexamethylene diisocyanate isocyanurate (for
- the amount of the isocyanate cross-linking agent used is preferably 0.005 to 10 parts by weight, and more preferably 0.01 to 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited.
- the weight ratio of isocyanate crosslinking agent/hydroxyl group-containing monomer is preferably more than 20 and less than 50 from the viewpoint that the effect of the present invention can be further exhibited. Yes, more preferably 22 to 45, further preferably 25 to 40, particularly preferably 27 to 40, and most preferably 30 to 35.
- the weight ratio of the tackifying resin TL/isocyanate cross-linking agent is preferably more than 2 from the viewpoint that the effect of the present invention can be further exhibited. Is less than 15, more preferably 5 to 13, still more preferably 7 to 12, and particularly preferably 7 to 11.
- epoxy-based cross-linking agent a polyfunctional epoxy compound having two or more epoxy groups in one molecule can be used.
- the epoxy crosslinking agent include N,N,N′,N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, penta Erythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycid
- the amount of the epoxy-based cross-linking agent used is preferably 0.005 to 10 parts by weight, more preferably 0.01 to 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited.
- Acrylic pressure-sensitive adhesives if necessary, such as leveling agents, crosslinking aids, plasticizers, softeners, fillers, antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers, etc.
- leveling agents such as leveling agents, crosslinking aids, plasticizers, softeners, fillers, antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers, etc.
- additives generally used in the field of agents may be contained. As such various additives, conventionally known ones can be used by a conventional method.
- the pressure-sensitive adhesive film of the present invention may have an antistatic layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive film of the present invention has an antistatic layer on the surface opposite to the surface having the pressure-sensitive adhesive layer of the substrate layer, whereby the charge of the pressure-sensitive adhesive film itself can be suppressed, and dust becomes difficult to be adsorbed, which is preferable. It becomes a mode.
- the antistatic layer for example, a method of applying an antistatic resin composed of an antistatic agent and a resin component, a conductive polymer, a method of applying a conductive resin containing a conductive substance, or a method of depositing or plating a conductive substance is available. Can be mentioned.
- antistatic agent contained in the antistatic resin examples include cation type antistatic agents having a cationic functional group such as quaternary ammonium salt, pyridinium salt, primary, secondary and tertiary amino groups; Anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric charges such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives Antistatic agent; nonionic antistatic agent such as amino alcohol and its derivative, glycerin and its derivative, polyethylene glycol and its derivative, etc.; polymerization or copolymerization of the above-mentioned cation type, anion type and amphoteric ion type monomer having an ion conductive group. And the like. These antistatic agents may be used alone or in combination of two or more.
- the cationic antistatic agent has, for example, a quaternary ammonium group such as an alkyltrimethylammonium salt, an acyloylamidopropyltrimethylammonium methosulfate, an alkylbenzylmethylammonium salt, an acylcholine chloride, and polydimethylaminoethylmethacrylate (meth).
- a quaternary ammonium group such as an alkyltrimethylammonium salt, an acyloylamidopropyltrimethylammonium methosulfate, an alkylbenzylmethylammonium salt, an acylcholine chloride, and polydimethylaminoethylmethacrylate (meth).
- anionic antistatic agent examples include alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfate ester salts, alkyl ethoxy sulfate ester salts, alkyl phosphate ester salts, and sulfonic acid group-containing styrene copolymers. .. These antistatic agents may be used alone or in combination of two or more.
- zwitterionic antistatic agents examples include alkyl betaines, alkyl imidazolium betaines, and carbobetaine graft copolymers. These antistatic agents may be used alone or in combination of two or more.
- nonionic antistatic agent examples include fatty acid alkylolamide, di(2-hydroxyethyl)alkylamine, polyoxyethylenealkylamine, fatty acid glycerin ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan.
- examples thereof include fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyethylene glycol, polyoxyethylene diamine, a copolymer of polyether, polyester and polyamide, and methoxy polyethylene glycol (meth)acrylate.
- These antistatic agents may be used alone or in combination of two or more.
- conductive polymers examples include polyaniline, polypyrrole, polythiophene, and the like. These conductive polymers may be used alone or in combination of two or more.
- tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, Copper iodide and alloys or mixtures thereof and the like can be mentioned. Only one kind of these conductive materials may be used, or two or more kinds thereof may be used.
- the resin component used for the antistatic resin and the conductive resin for example, general-purpose resins such as polyester resin, acrylic resin, polyvinyl resin, urethane resin, melamine resin, and epoxy resin are used.
- the resin component may not be contained.
- a cross-linking agent a methylol- or alkylol-based melamine compound, urea compound, glyoxal compound, acrylamide compound, epoxy compound, isocyanate compound, etc. may be contained as a component of the antistatic resin. Is.
- the above-mentioned antistatic resin, conductive polymer, conductive resin or the like is diluted with a solvent such as an organic solvent or water, and the coating liquid is applied to a substrate or the like and dried. It is formed by doing.
- Examples of the diluted solution used for forming the antistatic layer include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, isopropanol, water and the like. .. Only one kind of these solvents may be used, or two or more kinds thereof may be used.
- any suitable coating method is appropriately used.
- a coating method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, impregnation and curtain coating.
- Any appropriate method is appropriately used as the method for vapor deposition or plating of the conductive material. Examples of such a method include vacuum vapor deposition, sputtering, ion plating, chemical vapor deposition, spray pyrolysis, chemical plating, electroplating and the like.
- the thickness of the antistatic layer may be any appropriate thickness as long as the effect of the present invention is not impaired.
- the thickness of the antistatic layer is preferably 0.001 ⁇ m to 5 ⁇ m, and more preferably 0.005 ⁇ m to 1 ⁇ m, from the viewpoint that the effect of the present invention can be further exhibited.
- the pressure-sensitive adhesive film of the present invention may have a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer.
- the top coat layer preferably contains a binder, and more preferably contains a binder and a slip agent.
- the scratch resistance of the pressure-sensitive adhesive film is improved, which is a preferred embodiment.
- any suitable resin can be adopted as long as the effect of the present invention is not impaired.
- a resin is preferably at least one selected from the group consisting of a polyester resin and a urethane resin, from the viewpoint that the effect of the present invention can be further exhibited.
- polyester resin When the binder contains a polyester resin, the polyester resin may be only one kind or two or more kinds.
- the polyester resin is preferably a resin containing polyester as a main component.
- the content of polyester in the polyester resin is preferably more than 50% by weight, more preferably 75% by weight or more, and further preferably 90% by weight or more.
- the polyester is preferably selected from polyvalent carboxylic acids having two or more carboxyl groups in one molecule (preferably dicarboxylic acids) and derivatives thereof (anhydrides, esterified products, halides, etc. of polycarboxylic acid). At least one compound (polyvalent carboxylic acid component) and at least one compound selected from polyhydric alcohols (preferably diols) having two or more hydroxyl groups in one molecule (polyvalent) Alcohol component) and condensed structure.
- Examples of the compound that can be adopted as the polycarboxylic acid component include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, ( ⁇ )-malic acid, meso- Tartaric acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methylglutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyladipic acid, dimethyladipine Acid, tetramethyladipic acid, methyleneadipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,3,6,6-tetramethylsuberic acid, azelaic acid, se
- steers eg, alkyl esters, monoesters, diesters, etc.
- acid halides eg, dicarboxylic acid chlorides, etc.
- Preferred examples of the compound that can be used as the polycarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, and fumaric acid.
- Aromaphatic dicarboxylic acids such as acids, maleic acid, hymic acid, and 1,4-cyclohexanedicarboxylic acid, and acid anhydrides thereof; lower alkyl esters of the above dicarboxylic acids (for example, esters with monoalcohols having 1 to 3 carbon atoms) ; And the like.
- Examples of compounds that can be used as the polyhydric alcohol component include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl.
- Glycol 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3 -Propane diol, 2,2-diethyl-1,3-propane diol, 2-butyl-2-ethyl-1,3-propane diol, xylylene glycol, hydrogenated bisphenol A, bisphenol A, and other diols. ..
- Other examples include alkylene oxide adducts of these compounds (eg, ethylene oxide adducts, propylene oxide adducts, etc.).
- the polyester resin preferably contains a water-dispersible polyester, and more preferably contains a water-dispersible polyester as a main component.
- a water-dispersible polyester has, for example, a hydrophilic functional group (for example, at least one selected from hydrophilic functional groups such as metal sulfonate group, carboxyl group, ether group and phosphoric acid group) introduced into the polymer. It may be a polyester having improved water dispersibility.
- a method of introducing a hydrophilic functional group into the polymer for example, a method of copolymerizing a compound having a hydrophilic functional group, polyester or a precursor thereof (for example, polyvalent carboxylic acid component, polyhydric alcohol) Any appropriate technique such as a method of modifying components, oligomers thereof, etc.) to generate a hydrophilic functional group can be appropriately adopted.
- Preferred water-dispersible polyesters include polyesters (copolymerized polyesters) obtained by copolymerizing a compound having a hydrophilic functional group.
- the polyester resin used as the binder may be one having a saturated polyester as a main component or one having an unsaturated polyester as a main component.
- the polyester resin is preferably a saturated polyester as a main component, and more preferably a saturated polyester imparted with water dispersibility (for example, saturated copolyester).
- Such polyester resin polyester resin which may be prepared in the form of an aqueous dispersion
- the molecular weight of the polyester resin is preferably 0.5 ⁇ 10 4 to 15 ⁇ 10 4 , more preferably 1 as the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). It is from ⁇ 10 4 to 6 ⁇ 10 4 .
- the glass transition temperature (Tg) of the polyester resin is preferably 0°C to 100°C, more preferably 10°C to 80°C.
- the urethane-based resin When a urethane-based resin is contained in the binder, the urethane-based resin may be only one type or two or more types.
- the urethane resin is preferably a urethane resin obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).
- polyol (A) only one kind may be used, or two or more kinds may be used.
- any appropriate polyol can be adopted as long as it is a polyol having two or more OH groups.
- a polyol (A) include a polyol (diol) having two OH groups, a polyol (triol) having three OH groups, a polyol (tetraol) having four OH groups, and an OH group of 5
- examples thereof include a polyol having one (pentaol) and a polyol having six OH groups (hexaol).
- glycols such as ethylene glycol and propylene glycol having two or more OH groups are adopted as an essential component.
- glycol As the polyol (A), preferably, glycols such as ethylene glycol and propylene glycol having two or more OH groups are adopted as an essential component.
- glycol As the polyol (A), preferably, glycols such as ethylene glycol and propylene glycol having two or more OH groups are adopted as an essential component.
- glycol As the polyol (A), preferably, glycols such as ethylene glycol and propylene glycol having two or more OH groups are adopted as an essential component.
- the content ratio of glycol in the polyol (A) is preferably 30% by weight to 100% by weight, more preferably 50% by weight to 100% by weight, and further preferably 70% by weight to 100% by weight.
- % more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, most preferably substantially 100% by weight.
- polyol (A) examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl- 2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonane Diol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polyethylene glycol, polypropylene glycol, polyester polyol, polyether polyol
- the polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
- the acid component examples include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid , And acid anhydrides thereof.
- polyether polyol for example, water, low molecular weight polyol (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, hydroquinone, etc.), etc.
- a polyether polyol obtained by addition-polymerizing an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide can be mentioned. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
- polycaprolactone polyols examples include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ⁇ -caprolactone and ⁇ -valerolactone.
- polycarbonate polyol for example, a polycarbonate polyol obtained by polycondensing the above polyol component and phosgene; the above polyol component, dimethyl carbonate, diethyl carbonate, diprobyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonic acid, ethylene carbonate, Polycarbonate polyols obtained by transesterification condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymerized polycarbonate polyols obtained by using two or more of the above polyol components together; the above various polycarbonate polyols and carboxyl group-containing Polycarbonate polyol obtained by esterification reaction with a compound; Polycarbonate polyol obtained by etherification reaction between the above various polycarbonate polyols and hydroxyl group-containing compound; Obtained by transesterification reaction between the above various polycarbonate polyols and
- castor oil-based polyols examples include castor oil-based polyols obtained by reacting castor oil fatty acid with the above polyol component. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.
- the polyfunctional isocyanate compound (B) may be only one type, or may be two or more types.
- polyfunctional isocyanate compound (B) any suitable polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted.
- examples of such a polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate compound, and a polyfunctional aromatic isocyanate compound.
- polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4. 4-trimethylhexamethylene diisocyanate and the like can be mentioned.
- polyfunctional alicyclic isocyanate compound examples include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Examples thereof include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
- polyfunctional aromatic diisocyanate compound examples include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and , 4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.
- polyfunctional isocyanate compound (B) also include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, burettes reacted with water, trimers having an isocyanurate ring, and the like. Also, these may be used in combination.
- the content of the polyfunctional isocyanate compound (B) is preferably 5% by weight to 60% by weight, more preferably 8% by weight to 60% by weight, based on the polyol (A). %, and more preferably 10% to 60% by weight.
- the urethane resin is typically obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).
- a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).
- any appropriate other component other than the polyol (A) and the polyfunctional isocyanate compound (B) may be contained within a range not impairing the effects of the present invention.
- Such other components include, for example, catalysts, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, Examples include antiaging agents, conductive agents, antioxidants, ultraviolet absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and the like.
- the effects of the present invention such as a urethanization reaction method using bulk polymerization or solution polymerization can be obtained. Any appropriate method can be adopted within a range that does not impair the property.
- the top coat layer serves as a binder as long as it does not significantly impair the performance of the adhesive film, and as a binder, other resins (for example, acrylic resin, acrylic-styrene resin, acrylic-silicone resin, silicone resin, polysilazane). At least one resin selected from resins, fluororesins and polyolefin resins) may be further contained.
- the binder of the topcoat layer is substantially composed of at least one selected from the group consisting of polyester resin and urethane resin, and is composed of polyester resin and urethane resin in the binder.
- the proportion of at least one selected from the group is preferably 98% by weight to 100% by weight, more preferably 99% by weight to 100% by weight, and further preferably 99.5% by weight to 100% by weight. is there.
- the proportion of the binder in the entire top coat layer is preferably 15% by weight to 95% by weight, more preferably 25% by weight to 80% by weight.
- the slip agent preferably contains an ester of a higher fatty acid and a higher alcohol (hereinafter sometimes referred to as "wax ester").
- the “higher fatty acid” is preferably a carboxylic acid having 8 or more carbon atoms, and the number of carbon atoms is more preferably 10 or more, further preferably 10 to 40.
- the carboxylic acid is preferably a monovalent carboxylic acid.
- the “higher alcohol” is preferably an alcohol having 6 or more carbon atoms, and the number of carbon atoms is more preferably 10 or more, further preferably 10 to 40.
- the alcohol is preferably a monohydric or dihydric alcohol, more preferably a monohydric alcohol.
- the topcoat layer having a composition containing a combination of such a wax ester and the above-mentioned binder is unlikely to be whitened even when kept under high temperature and high humidity conditions. Therefore, the adhesive film provided with the base material having such a top coat layer can have a higher appearance quality.
- the topcoat layer having the above composition has excellent whitening resistance (for example, the property that whitening is difficult even when kept under high temperature and high humidity conditions) is achieved by the topcoat layer having the above composition. That is, it is presumed that the conventionally used silicone-based lubricant exhibits a function of imparting slipperiness to the surface of the topcoat layer by bleeding. However, in these silicone lubricants, the degree of bleeding is likely to change depending on the storage conditions (temperature, humidity, aging, etc.). Therefore, for example, when the adhesive film is kept under normal storage conditions (for example, 25° C. and 50% RH), it has a suitable slipperiness for a relatively long period (for example, about 3 months) immediately after the production of the adhesive film.
- normal storage conditions for example, 25° C. and 50% RH
- top coat layer a specific combination of wax ester as a slip agent and polyester resin as a binder is adopted. With such a combination of the slip agent and the binder, the degree of bleeding of the wax ester from the top coat layer is less likely to be affected by storage conditions. This can improve the whitening resistance of the adhesive film.
- one or more compounds represented by the general formula (W) can be preferably adopted.
- X and Y in formula (W) are each independently preferably a hydrocarbon group having 10 to 40 carbon atoms, and the number of carbon atoms is more preferably 10 to 35, and further preferably 14 To 35, particularly preferably 20 to 32. If the number of carbon atoms is too small, the effect of imparting slipperiness to the top coat layer may be insufficient.
- the above hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- the above-mentioned hydrocarbon group is preferably a saturated hydrocarbon group.
- the above hydrocarbon group may have a structure containing an aromatic ring, or may have a structure containing no aromatic ring (aliphatic hydrocarbon group), or a structure containing an aliphatic ring. May be a hydrocarbon group (alicyclic hydrocarbon group) or a chain (including straight chain and branched chain) hydrocarbon group.
- the wax ester is a compound in which X and Y in the formula (W) are each independently a chain alkyl group having 10 to 40 carbon atoms, more preferably 10 to 40 carbon atoms. It is a compound that is a linear alkyl group. Specific examples of such compounds, for example, cerotic myricyl (CH 3 (CH 2) 24 COO (CH 2) 29 CH 3), myricyl palmitate (CH 3 (CH 2) 14 COO (CH 2) 29 CH 3), cetyl palmitate (CH 3 (CH 2) 14 COO (CH 2) 15 CH 3), stearyl stearyl (CH 3 (CH 2) 16 COO (CH 2) 17 CH 3) , and the like.
- the wax ester has a melting point of preferably 50° C. or higher, more preferably 60° C. or higher, further preferably 70° C. or higher, particularly preferably 75° C. or higher. With such a wax ester, higher whitening resistance can be realized.
- the wax ester preferably has a melting point of 100° C. or lower. Since such a wax ester has a high effect of imparting slipperiness, it can form a top coat layer having higher scratch resistance. It is also preferable that the melting point of the wax ester is 100° C. or lower from the viewpoint of easily preparing an aqueous dispersion of the wax ester.
- myricyl cerotate can be preferably adopted.
- a natural wax containing such a wax ester can be used as a raw material for the top coat layer.
- the content ratio of the above-mentioned wax ester is preferably more than 50% by weight based on the nonvolatile content (NV). Most, more preferably 65% by weight or more, and further preferably 75% by weight or more.
- Examples of such a natural wax include carnauba wax (generally, containing myricyl cerotate in an amount of preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more).
- waxes such as wax; animal waxes such as beeswax and whale wax; and the like.
- the melting point of such natural wax is preferably 50° C. or higher, more preferably 60° C. or higher, further preferably 70° C. or higher, particularly preferably 75° C. or higher.
- a raw material for the top coat layer a chemically synthesized wax ester may be used, or a natural wax purified to improve the purity of the wax ester may be used. These raw materials may be only one kind or two or more kinds.
- the proportion of the slip agent in the entire top coat layer is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight. If the content of the slipping agent is too low, the scratch resistance may be lowered. If the content of the slip agent is too high, the effect of improving the whitening resistance may be insufficient.
- the top coat layer may contain other slip agent in addition to the wax ester.
- examples of other lubricants include wax esters such as petroleum wax (paraffin wax), mineral wax (montane wax etc.), higher fatty acid (cerotic acid etc.) and neutral fat (palmitic acid triglyceride etc.). Other various waxes are listed.
- a silicone lubricant, a fluorine lubricant, etc. may be contained.
- a preferred embodiment of the top coat layer is a form in which a silicone-based lubricant and a fluorine-based lubricant are not substantially contained.
- the total content of the silicone-based lubricant and the fluorine-based lubricant is preferably 0 or less. It is 0.01% by weight or less, more preferably the detection limit or less.
- the topcoat layer is an antistatic component, a cross-linking agent, an antioxidant, a colorant (pigment, dye, etc.), a fluidity adjusting agent (thixotropic agent, thickener, etc.), a film-forming aid, an interface, if necessary.
- Additives such as activators (defoaming agents, dispersants, etc.), preservatives and the like may be contained.
- a preferred embodiment of the topcoat layer contains an antistatic component.
- the antistatic component is a component capable of exhibiting the action of preventing or suppressing the charge of the adhesive film.
- the top coat layer contains an antistatic component, as the antistatic component, for example, an organic or inorganic conductive substance, various antistatic agents, etc. can be used. It is also possible to use antistatic agents which can be used in the antistatic layers mentioned above.
- organic conductive substance a quaternary ammonium salt, a pyridinium salt, a cationic antistatic agent having a cationic functional group such as a primary amino group, a secondary amino group, and a tertiary amino group; a sulfonate or a sulfate ester salt. , Phosphonate, phosphate ester and other anionic antistatic agents having anionic functional groups; alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, etc.
- zwitterionic antistatic agents amino alcohols and Nonionic antistatic agents such as derivatives thereof, glycerin and derivatives thereof, polyethylene glycol and derivatives thereof; polymerization of monomers having the above-mentioned cation-type, anion-type, and zwitterion-type ion conductive groups (for example, quaternary ammonium salt groups) or Ion conductive polymers obtained by copolymerization; conductive polymers such as polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine polymers; and the like. Only one kind of such antistatic agent may be used, or two or more kinds thereof may be used.
- the inorganic conductive substance examples include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron and cobalt. , Copper iodide, ITO (indium oxide/tin oxide), ATO (antimony oxide/tin oxide), and the like. Only one kind of such inorganic conductive material may be used, or two or more kinds thereof may be used.
- antistatic agent examples include a cationic antistatic agent, an anionic antistatic agent, a zwitterionic antistatic agent, a nonionic antistatic agent, and the above-mentioned cationic, anionic, and zwitterionic ionically conductive groups.
- examples thereof include ion conductive polymers obtained by polymerizing or copolymerizing monomers.
- the antistatic component preferably contains an organic conductive substance.
- the organic conductive substance various conductive polymers can be preferably used. With such a configuration, both good antistatic properties and high scratch resistance can be achieved.
- conductive polymers examples include polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine-based polymers. Only one kind of such conductive polymer may be used, or two or more kinds thereof may be used. It may also be used in combination with other antistatic components (inorganic conductive substances, antistatic agents, etc.).
- the amount of the conductive polymer used is preferably 1 part by weight to 100 parts by weight, more preferably 2 parts by weight to 70 parts by weight, and further preferably 100 parts by weight of the binder contained in the top coat layer. It is 3 to 50 parts by weight. If the amount of the conductive polymer used is too small, the antistatic effect may be reduced. If the amount of the conductive polymer used is too large, the compatibility of the conductive polymer in the topcoat layer tends to be insufficient, and the appearance quality of the topcoat layer may deteriorate or the solvent resistance may decrease. ..
- the conductive polymer is preferably polythiophene or polyaniline.
- the polythiophene has a polystyrene-equivalent weight average molecular weight Mw of preferably 40 ⁇ 10 4 or less, more preferably 30 ⁇ 10 4 or less.
- the polyaniline has a polystyrene-equivalent weight average molecular weight Mw of preferably 50 ⁇ 10 4 or less, more preferably 30 ⁇ 10 4 or less.
- the polystyrene-equivalent weight average molecular weight Mw of the conductive polymer is preferably 0.1 ⁇ 10 4 or more, more preferably 0.5 ⁇ 10 4 or more.
- polythiophene refers to a polymer of unsubstituted or substituted thiophene. Examples of the substituted thiophene polymer include poly(3,4-ethylenedioxythiophene).
- a conductive polymer used for preparing the coating material A conductive polymer dissolved or dispersed in water (conductive polymer aqueous solution) can be preferably used.
- a conductive polymer aqueous solution is prepared by, for example, dissolving a conductive polymer having a hydrophilic functional group (a conductive polymer that can be synthesized by a method such as copolymerizing a monomer having a hydrophilic functional group in the molecule) in water. Alternatively, it can be prepared by dispersing.
- hydrophilic functional group examples include sulfo group, amino group, amide group, imino group, hydroxyl group, mercapto group, hydrazino group, carboxyl group, quaternary ammonium group, sulfuric acid ester group (—O—SO 3 H), phosphorus Examples thereof include acid ester groups (eg, —O—PO(OH) 2 ).
- Such a hydrophilic functional group may form a salt.
- examples of commercially available polythiophene aqueous solution include "Denatron” series manufactured by Nagase Chemtec Co., Ltd.
- commercial products of the polyaniline sulfonic acid aqueous solution examples include trade name “aqua-PASS” manufactured by Mitsubishi Rayon Co., Ltd.
- an aqueous polythiophene solution In the preparation of the coating material, it is preferable to use an aqueous polythiophene solution.
- a polythiophene aqueous solution containing polystyrene sulfonate (PSS) (for example, a form in which PSS is added as a dopant to polythiophene) is preferable.
- PSS polystyrene sulfonate
- Such an aqueous polythiophene solution may contain polythiophene:PSS, preferably in a mass ratio of 1:1 to 1:10.
- the total content of polythiophene and PSS in such an aqueous polythiophene solution is preferably 1% by mass to 5% by mass.
- polythiophene aqueous solution containing PSS examples include H.I. C. The trade name “Baytron” of Stark and the like can be mentioned.
- the total amount of polythiophene and PSS is preferably 5 parts by weight to 200 parts by weight, and more preferably 10 parts by weight with respect to 100 parts by weight of the binder. It is from 100 to 100 parts by weight, and more preferably from 25 to 70 parts by weight.
- the topcoat layer optionally contains a conductive polymer and one or more other antistatic components (organic conductive substances other than conductive polymers, inorganic conductive substances, antistatic agents, etc.) together. You may stay.
- the top coat layer contains substantially no antistatic component other than the conductive polymer. That is, it is preferable that the antistatic component contained in the topcoat layer consists essentially of a conductive polymer.
- the top coat layer preferably contains a crosslinking agent.
- a cross-linking agent such as a melamine-based cross-linking agent, an isocyanate-based cross-linking agent, or an epoxy-based cross-linking agent that is used for cross-linking general resins can be appropriately selected and used.
- the cross-linking agent comprises a melamine-based cross-linking agent.
- the cross-linking agent substantially consists of a melamine-based cross-linking agent (melamine-based resin) (that is, does not substantially contain a cross-linking agent other than the melamine-based cross-linking agent).
- the top coat layer when the material of the base material layer is at least one selected from polyimide and polyether ether ketone, the top coat layer contains a binder containing a urethane resin and an antistatic component. It is a mode. In this way, by using a binder containing a urethane resin as the binder of the antistatic component of the top coat layer, the top surface of the base material layer made of at least one selected from polyimide and polyether ether ketone is used. The coatability of the coat layer becomes excellent, the appearance may be good, and the excellent antistatic property may be exhibited.
- a binder containing a polyester resin is often preferable, but the material for the base material layer is at least one selected from polyimide and polyetheretherketone for a specific base material layer.
- the binder containing the polyester resin may have a low affinity, and the appearance of the topcoat layer after coating and forming may be deteriorated, or the excellent antistatic property may not be exhibited.
- the top coat layer contains a binder containing a urethane resin and an antistatic component, the coatability of the topcoat layer on the surface of the base material layer becomes excellent, the appearance may be good, and the excellent antistatic property may be exhibited.
- the topcoat layer is formed by a method including applying a liquid composition (a coating material for forming a topcoat layer) in which the above resin components and additives used as necessary are dispersed or dissolved in a suitable solvent to a substrate. It can be suitably formed. For example, a method in which the above-mentioned coating material is applied to the first surface of a base material, dried, and if necessary, a curing treatment (heat treatment, ultraviolet treatment, etc.) can be preferably adopted.
- the NV (nonvolatile content) of the coating material is preferably 5% by weight or less, more preferably 0.05% by weight to 5% by weight, further preferably 0.05% by weight to 1% by weight, Particularly preferably, it is 0.10% by weight to 1% by weight.
- the NV of the coating material is preferably 0.05% by weight to 0.50% by weight, and more preferably 0.10% by weight to 0.30% by weight. To do. By using the low NV coating material as described above, a more uniform top coat layer can be formed.
- Such a solvent may be an organic solvent, water, or a mixed solvent thereof.
- the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic carbonization such as n-hexane and cyclohexane.
- the solvent constituting the coating material for forming the topcoat layer is water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
- the thickness of the top coat layer is preferably 3 nm to 500 nm, more preferably 3 nm to 100 nm, and further preferably 3 nm to 60 nm. If the thickness of the top coat layer is too large, the transparency (light transmittance) of the pressure-sensitive adhesive film may be likely to decrease. If the thickness of the top coat layer is too small, it may be difficult to uniformly form the top coat layer, and for example, in the thickness of the top coat layer, there may be a large variation in thickness depending on the location. However, the appearance of the pressure-sensitive adhesive film may be likely to be uneven.
- the thickness of the top coat layer can be understood by observing the cross section of the top coat layer with a transmission electron microscope (TEM).
- TEM transmission electron microscope
- a target sample a base material having a top coat layer formed thereon, an adhesive film including a base material, etc.
- a heavy metal dyeing treatment is performed for the purpose of clarifying the top coat layer, followed by resin embedding.
- the result obtained by TEM observation of the cross section of the sample by the ultrathin section method can be preferably adopted as the thickness of the topcoat layer.
- a TEM model “H-7650” manufactured by Hitachi, Ltd. can be used.
- a cross-sectional image obtained under the conditions of accelerating voltage: 100 kV and magnification: 60,000 times was binarized, and then the cross-sectional area of the top coat was divided by the sample length in the visual field. By doing so, the thickness of the top coat layer (average thickness in the visual field) is measured.
- the heavy metal dyeing process may be omitted if the topcoat layer can be observed sufficiently clearly without heavy metal dyeing.
- there is a calibration curve for the correlation between the thickness grasped by the TEM and the detection result by various thickness detection devices for example, surface roughness meter, interference thickness meter, infrared spectrophotometer, various X-ray diffractometers, etc.).
- the thickness of the top coat layer may be determined by preparing the above and calculating.
- the surface resistivity measured on the surface of the top coat layer is preferably 10 12 ⁇ or less, more preferably 10 4 ⁇ to 10 12 ⁇ , further preferably 10 4 ⁇ to 10 11 ⁇ , and particularly preferably It is preferably 5 ⁇ 10 4 ⁇ to 10 10 ⁇ , and most preferably 10 4 ⁇ to 10 9 ⁇ .
- the pressure-sensitive adhesive film having such a surface resistivity can be suitably used as a pressure-sensitive adhesive film used, for example, in the processing or transportation process of articles such as liquid crystal cells and semiconductor devices that are sensitive to static electricity.
- the surface resistivity value can be calculated from the surface resistance value measured in an atmosphere of 23° C. and 50% RH using a commercially available insulation resistance measuring device.
- the friction coefficient of the top coat layer is preferably 0.4 or less.
- a load a load that causes scratches
- the power can be reduced.
- cohesive failure of the topcoat layer damage mode in which the topcoat layer breaks inside
- interface failure damage mode in which the topcoat layer peels from the back surface of the substrate
- the lower limit of the coefficient of friction is preferably 0.1 or more, more preferably 0.15 or more, in consideration of the balance with other characteristics (for example, appearance quality and printability).
- the friction coefficient for example, a value obtained by rubbing the surface of the top coat layer with a vertical load of 40 mN under a measurement environment of 23° C. and 50% RH can be adopted.
- the amount of the slip agent used may be set so that a preferable coefficient of friction is realized.
- the back surface (surface of the top coat layer) of the adhesive film has a property that it can be easily printed with an oil-based ink (for example, using an oil-based marking pen).
- an oil-based ink for example, using an oil-based marking pen.
- the identification number or the like of the adherend to be protected in the process of processing or transporting the adherend (for example, an optical component) that is performed with the pressure-sensitive adhesive film attached It is suitable for displaying and displaying. Therefore, a surface protective film having excellent printability in addition to appearance quality is preferable.
- the solvent is alcoholic and has high printability with respect to an oil-based ink of a type including a pigment.
- the pressure-sensitive adhesive film preferably has solvent resistance to the extent that when the print is corrected or erased, the print is wiped off with alcohol (for example, ethyl alcohol) so that the appearance is not significantly changed.
- alcohol for example, ethyl alcohol
- the topcoat layer preferably contains a wax ester as a slip agent, so that the surface of the topcoat layer is subjected to further release treatment (for example, any suitable release treatment such as a silicone-based release agent or a long-chain alkyl-based release agent).
- Sufficient slipperiness (for example, the above-mentioned preferable friction coefficient) can be realized even in a mode in which the treatment of applying the agent and drying is not performed.
- the embodiment in which the surface of the top coat layer is not further subjected to the peeling treatment can prevent the whitening (for example, the whitening due to the storage under the heating and humidifying conditions) caused by the peeling treatment agent. It is preferable in terms. It is also advantageous in terms of solvent resistance.
- the pressure-sensitive adhesive film may be embodied in a mode including other layers in addition to the base material, the pressure-sensitive adhesive layer, and the top coat layer.
- Examples of the arrangement of the "other layer” include between the first surface (back surface) of the base material and the top coat layer, between the second surface (front surface) of the base material and the adhesive layer, and the like.
- the layer arranged between the back surface of the substrate and the topcoat layer can be, for example, a layer containing an antistatic component (antistatic layer).
- the layer arranged between the front surface of the substrate and the pressure-sensitive adhesive layer may be, for example, an undercoat layer (anchor layer) that enhances the anchoring property of the pressure-sensitive adhesive layer to the second surface, an antistatic layer, or the like.
- the pressure-sensitive adhesive film may have a structure in which an antistatic layer is disposed on the front surface of a substrate, an anchor layer is disposed on the antistatic layer, and a pressure-sensitive adhesive layer is disposed thereon.
- the pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, for example, a bendable device (a bendable device), a foldable device (a foldable device), or a rollable device (having a movable bending portion) (a bendable device). It is suitable for a rollable device).
- the pressure-sensitive adhesive film of the present invention is particularly excellent in flexibility and transparency, and thus is suitable for a foldable device (foldable device) and a rollable device (rollable device) that have been difficult to apply until now. Can be prepared for.
- the foldable device of the present invention includes the adhesive film of the present invention.
- the foldable device of the present invention may include any appropriate other member as long as it has the adhesive film of the present invention.
- the rollable device of the present invention includes the adhesive film of the present invention.
- the rollable device of the present invention may include any appropriate other member as long as it has the adhesive film of the present invention.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of the foldable device of the present invention as a representative example of one usage form of the adhesive film of the present invention.
- a foldable device 1000 of the present invention includes a cover film 10, an adhesive layer 20, a polarizing plate 30, an adhesive layer 40, a touch sensor 50, an adhesive layer 60, an OLED 70, and an adhesive film 100 of the present invention.
- the adhesive film 100 of the present invention is composed of an adhesive layer 80 and a base material layer 90 in FIG.
- the pressure-sensitive adhesive layer 20, the pressure-sensitive adhesive layer 40, and the pressure-sensitive adhesive layer 60 is composed of an adhesive layer 80 and a base material layer 90 in FIG.
- the pressure-sensitive adhesive layer 20 the pressure-sensitive adhesive layer 40, and the pressure-sensitive adhesive layer 60.
- It may be a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive having the same composition as the pressure-sensitive adhesive layer 80 constituting the pressure-sensitive adhesive film 100 of the present invention, or may be a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive having a different composition.
- FIG. 1 is a diagram provided on a back surface (a surface opposite to a display surface) of a foldable device (a foldable device).
- ⁇ tan ⁇ > The viscoelasticity measuring device "RSA-G2" (manufactured by TA Instruments Japan Co., Ltd.) was used in the tensile mode to measure the sample size width 5 mm x distance 15 mm and axial force 100 g.
- the frequency is 1 Hz
- the measurement temperature is 90° C.
- the immersion time is 60 seconds
- the strain measurement range is set from 0.01% to 1.0%
- the strain is measured during that period. I went.
- the value of tan ⁇ at each strain was graphed, and the tan ⁇ of 0.1% strain and 0.7% strain was obtained from the graph.
- the flat pressure-sensitive adhesive film is fixed in a state of being sandwiched between the silicone-treated surfaces of the silicone-treated separator with the pressure-sensitive adhesive film bent at 6 ⁇ so that the temperature is 90° C. For 48 hours. After that, the bending was released, and the film was allowed to stand at 23° C. and 50% RH for 24 hours, and then the angle of the bent film was measured. The case where it completely returned to the original state was set to 180 degrees, and the case where the bent state in the first fixing was maintained as it was was set to 0 degree.
- Adhesive film was attached to a PET film (Toray, S10) with a thickness of 50 ⁇ m, and the adhesive film was bent so that the adhesive film was on the inside as shown in FIG. 3 and kept at 90° C. for 48 hours, and then fixed. Was released, and peeling of the adhesive film from the PET film was visually observed.
- the evaluation was performed according to the following criteria. Good: Peeling from the PET film is not seen. X: Peeling from the PET film is seen.
- Haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd.
- haze (%) (Td/Tt) ⁇ 100 (Td: diffuse transmittance, Tt: Total light transmittance) was calculated.
- the total light transmittance was measured according to JIS-K-7316.
- the sample piece was cut into a strip shape with a width of 10 mm, and the strip-shaped sample piece was pulled in a longitudinal direction at a chuck distance of 100 mm with a universal tensile compression tester (Tensilon) under a temperature environment of 25° C. to measure, Young's modulus was determined from the obtained SS (Strain-Strength) curve.
- the measurement conditions were a pulling speed of 200 mm/min and a chuck gap of 50 mm.
- the Young's modulus was calculated from the SS curve by drawing a graph of the SS curve, drawing a tangent line (linear equation) on the graph in the displacement range of 1 mm to 2 mm, and calculating from the slope of the tangent line.
- the adhesive film was cut into a width of 25 mm and a length of 150 mm to obtain a sample for evaluation.
- the surface of the pressure-sensitive adhesive layer of the sample for evaluation was attached to a glass plate (Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) by reciprocating a 2.0 kg roller once. I attached it. After curing for 30 minutes in an atmosphere of a temperature of 23° C.
- ⁇ Applicability> The number of circular irregularities in the applied top coat layer (including the antistatic layer) is counted. Two sheets of A4 size were prepared and the average number was calculated. 2 or less were judged to be good, and 3 or more were judged to be defective.
- the circular uneven part is a part where the thickness of the top coat layer is thin and it is a defect in appearance, and the one that could not be applied at all because it repelled the antistatic agent was “Hajiki” And
- Example 8 ⁇ Surface resistance value (for Example 8)> The layer on which the antistatic treatment layer was formed in Example 8 was measured with a volume resistance meter Model 152-1 152P-2P probe (manufactured by Trek Japan KK) at a voltage of 10V.
- ⁇ Surface resistivity for Examples 9 to 17 and Comparative Examples 6 to 9>
- a resistivity meter manufactured by Mitsubishi Chemical Analytic, “HIRESTA UP MCP-HT450 type” was used to bring the URS probe into contact with the surface without the adhesive layer of the adhesive film.
- the surface resistivity was measured under conditions of an applied voltage of 100 V and a voltage application time of 10 seconds.
- an isocyanate-based crosslinking agent trade name "Takenate D110N", manufactured by Mitsui Chemicals, Inc.
- the pressure-sensitive adhesive composition A was prepared by adding 1 part by weight in terms of conversion.
- Polymerization reaction was carried out for 6 hours while maintaining the liquid temperature in the flask at around 60°C to prepare a solution (40% by weight) of the acrylic polymer (b).
- the weight average molecular weight of the acrylic polymer (b) was 540,000.
- the acrylic polymer (b) solution (40% by weight) was diluted to 25% by weight with ethyl acetate, and 400 parts by weight of this solution (solid content 100 parts by weight) was added with a trifunctional isocyanate compound as a crosslinking agent.
- Example 1 A commercially available release liner (DIAFOIL MRF-38", manufactured by Mitsubishi Plastics, Inc.) was prepared.
- the pressure-sensitive adhesive composition A was applied to one surface (release surface) of the release liner so that the thickness after drying was 25 ⁇ m, and dried at 130° C. for 3 minutes. In this way, a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m and composed of the acrylic pressure-sensitive adhesive A corresponding to the pressure-sensitive adhesive composition A was formed on the release surface of the release liner.
- a polyimide base material (trade name “Kapton”, manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 ⁇ m was prepared.
- the pressure-sensitive adhesive layer formed on the release liner was attached to one surface of the base material layer.
- the release liner was left as it was on the pressure-sensitive adhesive layer and used to protect the surface of the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer surface).
- the obtained structure was passed once through a laminator at 80° C. (0.3 MPa, speed 0.5 m/min), and then aged in an oven at 50° C. for 1 day. Thus, the adhesive film (1) was obtained. The results are shown in Table 1.
- Example 2 An adhesive film (2) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 ⁇ m (trade name “UPILEX-50S”, manufactured by Ube Industries, Ltd.) was used as the substrate layer. The results are shown in Table 1.
- Example 3 An adhesive film (3) was obtained in the same manner as in Example 1 except that a polyimide base material having a thickness of 50 ⁇ m (trade name “Pixio BP”, manufactured by Kaneka Corporation) was used as the base material layer. The results are shown in Table 1.
- Example 4 An adhesive film (4) was obtained in the same manner as in Example 1 except that a polyimide base material having a thickness of 50 ⁇ m (trade name “UPILEX-50RN”, manufactured by Ube Industries, Ltd.) was used as the base material layer. The results are shown in Table 1.
- Example 5 Examples except that a 50 ⁇ m thick polyetheretherketone (PEEK)-based substrate (trade name “Shin-Etsu Sepla Film”, non-stretched film-forming high crystal, manufactured by Shin-Etsu Polymer Co., Ltd.) was used as the substrate layer The same procedure as in 1 was carried out to obtain an adhesive film (5). The results are shown in Table 1.
- PEEK polyetheretherketone
- Example 6 An adhesive film (6) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 ⁇ m (trade name “Neoprim S100”, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used as the substrate layer. The results are shown in Table 1.
- Example 7 An adhesive film (7) was obtained in the same manner as in Example 1 except that a 25 ⁇ m-thick polyetheretherketone (PEEK) base material (trade name “Expeak”, manufactured by Kurabo Industries) was used as the base material layer. It was The results are shown in Table 1.
- PEEK polyetheretherketone
- Example 1 An adhesive film (C1) was obtained in the same manner as in Example 1 except that a 25 ⁇ m-thick polyester base material (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer. The results are shown in Table 1.
- Example 2 An adhesive film (C2) was obtained in the same manner as in Example 1 except that a 50 ⁇ m-thick polyester base material (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer. The results are shown in Table 1.
- Example 3 Same as Example 1 except that the pressure-sensitive adhesive composition B was used in place of the pressure-sensitive adhesive composition A, and a polyester base material having a thickness of 50 ⁇ m (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer. Then, an adhesive film (C3) was obtained. The results are shown in Table 1.
- antistatic agent Microsolver RMd-142, manufactured by Solvex Co., containing tin oxide and polyester resin as main components
- An antistatic agent solution was prepared by diluting with 70 parts by weight of a mixed solvent.
- Example 8 An adhesive film (8) was obtained in the same manner as in Example 1 except that the antistatic-treated polyimide film A was used as the substrate.
- the surface resistance value was 5 ⁇ 10 6 ⁇ .
- slipper dispersion (hereinafter also referred to as “slipper dispersion”) was prepared. Further, an aqueous solution containing 0.5% by weight of poly(3,4-dioxythiophene) (PEDOT) and 0.8% by weight of polystyrene sulfonate (number average molecular weight 150,000) (PSS) as a conductive polymer (H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution”) was prepared.
- PEDOT poly(3,4-dioxythiophene)
- PSS polystyrene sulfonate
- H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution” was prepared.
- coating material B having an NV of about 0.15% by weight was prepared.
- top coat layer forming polyimide film B ⁇ Preparation of top coat layer forming polyimide film B>
- the coating material B is applied by a bar coater on a polyimide base material (trade name "Kapton", manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 ⁇ m, which is a base material, and dried by heating at 130° C. for 2 minutes.
- a base material (topcoat layer forming polyimide film B) having a transparent topcoat layer having a thickness of 10 nm on one surface of the polyimide base material was produced.
- an aqueous dispersion of carnauba wax (manufactured by Nippon Wax Co., Ltd., trade name “Purified Carnauba Waxus No. 2 powder”) (hereinafter also referred to as “slipper dispersion”) was prepared. Further, an aqueous solution containing 0.5% by weight of poly(3,4-dioxythiophene) (PEDOT) and 0.8% by weight of polystyrene sulfonate (number average molecular weight 150,000) (PSS) as a conductive polymer (H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution”) was prepared.
- PEDOT poly(3,4-dioxythiophene)
- PSS polystyrene sulfonate
- H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution” was prepared.
- an aqueous solution containing 10% by weight of polyethylene glycol (PEG) alkyl ether and 10% by weight of polyvinyl alcohol was prepared as a dispersant.
- a mixed solvent of water and ethanol weight ratio 50:50
- 40 parts by weight of the binder dispersion liquid in solid content 5 parts by weight of the slip agent dispersion liquid in solid content, and the conductive polymer aqueous solution.
- 8 parts by weight of solid content, 40 parts by weight of the above dispersant, and 7 parts by weight of melamine-based cross-linking agent were added, and the mixture was stirred for about 20 minutes and mixed sufficiently.
- coating material C having an NV of about 0.30% by weight was prepared.
- top coat layer forming polyimide film C ⁇ Preparation of top coat layer forming polyimide film C>
- the coating material C is applied with a bar coater onto a polyimide base material (trade name "Kapton", manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 ⁇ m, which is a base material, and heated at 130° C. for 2 minutes to dry. Let In this way, a base material (topcoat layer forming polyimide film C) having a transparent topcoat layer having a thickness of 50 nm on one surface of the polyimide base material was produced.
- a base material topcoat layer forming polyimide film C having a transparent topcoat layer having a thickness of 50 nm on one surface of the polyimide base material was produced.
- Example 9 An adhesive film (9) was obtained in the same manner as in Example 1 except that the top coat layer-forming polyimide film B was used as the substrate. The results are shown in Table 2.
- Example 10 An adhesive film (10) was obtained in the same manner as in Example 2 except that the top coat layer-forming polyimide film B was used as the substrate. The results are shown in Table 2.
- Example 11 An adhesive film (11) was obtained in the same manner as in Example 4, except that the top coat layer-forming polyimide film B was used as the substrate. The results are shown in Table 2.
- Example 12 An adhesive film (12) was obtained in the same manner as in Example 7 except that the top coat layer-forming polyimide film B was used as the substrate. The results are shown in Table 2.
- Example 13 An adhesive film (13) was obtained in the same manner as in Example 1 except that the top coat layer-forming polyimide film C was used as the substrate. The results are shown in Table 2.
- Example 14 An adhesive film (14) was obtained in the same manner as in Example 2 except that the top coat layer-forming polyimide film C was used as the substrate. The results are shown in Table 2.
- Example 15 An adhesive film (15) was obtained in the same manner as in Example 3 except that the top coat layer-forming polyimide film C was used as the substrate. The results are shown in Table 2.
- Example 16 An adhesive film (16) was obtained in the same manner as in Example 4, except that the top coat layer-forming polyimide film C was used as the substrate. The results are shown in Table 2.
- Example 17 An adhesive film (17) was obtained in the same manner as in Example 7, except that the top coat layer-forming polyimide film C was used as the substrate. The results are shown in Table 2.
- the pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, for example, a bendable device (a bendable device), a foldable device (a foldable device), or a rollable device (having a movable bending portion) (a bendable device). It is suitable for a rollable device).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Provided is an adhesive film having excellent bendability and transparency. Also provided are a foldable device and a rollable device having excellent bendability. This adhesive film has a substrate layer and an adhesive layer, tan δ(0.7%) at a strain of 0.7% of the adhesive film measured in the tension mode of a viscoelasticity measurement device being 0.1 or less. This adhesive film has a substrate layer and an adhesive layer, the difference (tan δ(0.7%) – tan δ(0.1%)) between tan δ(0.7%) at a strain of 0.7% and tan δ(0.1%) at a strain of 0.1% of the adhesive film measured in the tension mode of a viscoelasticity measurement device being 0.05 or less.
Description
本発明は、粘着フィルムに関する。本発明は、また、そのような粘着フィルムを備えたフォルダブルデバイス、および、そのような粘着フィルムを備えたローラブルデバイスに関する。
The present invention relates to an adhesive film. The present invention also relates to a foldable device provided with such an adhesive film and a rollable device provided with such an adhesive film.
粘着フィルムは、様々な形状の部材の補強や表面保護等に用いられている。
Adhesive films are used for reinforcement of various shaped members and surface protection.
例えば、半導体素子の基板(例えば、TFT基板など)に集積回路(IC)やフレキシブルプリント回路基板(FPC)を接合する場合、通常、異方性導電フィルム(ACF)によって熱圧着を行う。このような熱圧着を行う際に、予め、半導体素子の基板の裏側に粘着フィルムを貼り合せて補強しておく場合がある(例えば、特許文献1)。
For example, when an integrated circuit (IC) or a flexible printed circuit board (FPC) is bonded to a semiconductor element substrate (for example, a TFT substrate), thermocompression bonding is usually performed with an anisotropic conductive film (ACF). When such thermocompression bonding is performed, an adhesive film may be bonded and reinforced in advance on the back side of the substrate of the semiconductor element (for example, Patent Document 1).
また、近年開発が進みつつあるフレキシブルデバイスやローラブルデバイスの製造方法としては、一般的には、ガラス等の支持基板上に、剥離層とフレキシブルあるいはローラブルなフィルム基板を形成し、そのフィルム基板上にTFT基板、さらにその上に、有機EL層を形成する。そして、支持基板を剥離し、フレキシブルデバイスやローラブルデバイスを製造するのであるが、フレキシブル表示層やローラブル表示層が非常に薄いため、取扱い等によってデバイスに不具合が生じる。このため、裏側に粘着フィルムを貼り合せて補強しておく場合がある(例えば、特許文献2)。
In addition, as a method of manufacturing a flexible device or a rollable device that has been developed in recent years, generally, a peeling layer and a flexible or rollable film substrate are formed on a supporting substrate such as glass, and the film substrate Then, a TFT substrate is formed, and an organic EL layer is formed thereon. Then, the supporting substrate is peeled off to manufacture a flexible device or a rollable device. However, since the flexible display layer or the rollable display layer is very thin, the device may be defective due to handling or the like. Therefore, an adhesive film may be attached to the back side to reinforce (for example, Patent Document 2).
半導体素子の基板やフレキシブルデバイスやローラブルデバイスは、繰り返し屈曲される場合があり、基板の裏側に貼り合せた粘着フィルムの屈曲特性が悪いと、屈曲後の回復性が悪化したり、最悪は繰り返し屈曲により破断してしまったりする場合がある。具体的には、屈曲部(例えば、折り畳み部材の可動屈曲部など)に粘着フィルムを貼り合わせようとすると、例えば、下記のような問題が生じる。
A semiconductor device substrate, flexible device, or rollable device may be repeatedly bent, and if the adhesive film attached to the back side of the substrate has poor bending properties, the recoverability after bending may deteriorate, and at worst, it may be repeated. It may break due to bending. Specifically, when an adhesive film is attached to a bent portion (for example, a movable bent portion of a folding member), the following problems occur, for example.
粘着フィルムが角度を持って曲げられた場合、曲げられた内径側には圧縮させる力が働くために、その力を緩和させようとして粘着フィルム自体の変形が起こる。具体的には、例えば、しわが入りやすくなる。
When the adhesive film is bent at an angle, a compressing force acts on the bent inner diameter side, so the adhesive film itself deforms in an attempt to alleviate the force. Specifically, for example, wrinkles easily occur.
粘着フィルムが角度を持って曲げられた場合、曲げられた外径側には引っ張られる応力が働く。このため、その応力が緩和される際に、被着体からの浮きが発生する。
When the adhesive film is bent at an angle, tensile stress acts on the bent outer diameter side. Therefore, when the stress is relieved, the floating from the adherend occurs.
粘着フィルムが角度を持って曲げられた場合、粘着フィルムの曲げられる箇所や引っ張られる箇所の厚みが大きく変化してしまい、このような状態においても、しわが入りやすくなったり、浮きが発生したりする。例えば、粘着フィルムが引っ張られた場合に、粘着フィルムの厚みが大幅に薄くなってしまい、被着体からの浮きが発生しやすくなる。
If the pressure-sensitive adhesive film is bent at an angle, the thickness of the bendable part or the stretched part of the pressure-sensitive adhesive film will change greatly, and even in such a state, wrinkles are likely to occur and floating may occur. To do. For example, when the pressure-sensitive adhesive film is pulled, the thickness of the pressure-sensitive adhesive film is significantly reduced, and the adhesive film is apt to float from the adherend.
このように、従来の粘着フィルムにおいては、角部や屈曲部への凹凸追従が十分に達成できていない。
In this way, conventional pressure-sensitive adhesive films have not been able to achieve sufficient conformity to the corners and bends.
特に、可動屈曲部に粘着フィルムを貼り合わせた場合、屈曲が繰り返されるため、可動屈曲部上において、粘着フィルムに折れ跡(いわゆる「クセ」)が付いた状態になってしまう。
In particular, when an adhesive film is attached to the movable bending part, the bending is repeated, so that the adhesive film has a nick (so-called “habit”) on the movable bending part.
また、集積回路(IC)やフレキシブルプリント回路基板(FPC)を半導体素子の基板(例えば、TFT基板など)に熱圧着を行って接合する際に、基板の裏側から接合する位置を確認して圧着を行う。このため、基板の裏側に貼り合わせる粘着フィルムには、透明性が要求される。
In addition, when an integrated circuit (IC) or a flexible printed circuit board (FPC) is bonded to a semiconductor element substrate (for example, a TFT substrate) by thermocompression bonding, the bonding position is confirmed from the back side of the substrate to perform pressure bonding. I do. Therefore, the pressure-sensitive adhesive film attached to the back side of the substrate is required to have transparency.
本発明の課題は、屈曲性および透明性に優れた粘着フィルムを提供することにある。本発明の課題は、また、屈曲性に優れたフォルダブルデバイスおよびローラブルデバイスを提供することにある。
An object of the present invention is to provide an adhesive film having excellent flexibility and transparency. Another object of the present invention is to provide a foldable device and a rollable device having excellent flexibility.
本発明の粘着フィルムは、
基材層と粘着剤層を有する粘着フィルムであって、
粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)が0.1以下である。 The adhesive film of the present invention,
An adhesive film having a base material layer and an adhesive layer,
The tan δ (0.7%) at a strain of 0.7% measured in the tensile mode of the viscoelasticity measuring device is 0.1 or less.
基材層と粘着剤層を有する粘着フィルムであって、
粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)が0.1以下である。 The adhesive film of the present invention,
An adhesive film having a base material layer and an adhesive layer,
The tan δ (0.7%) at a strain of 0.7% measured in the tensile mode of the viscoelasticity measuring device is 0.1 or less.
本発明の粘着フィルムは、
基材層と粘着剤層を有する粘着フィルムであって、
粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)と歪み0.1%におけるtanδ(0.1%)との差(tanδ(0.7%)-tanδ(0.1%))が0.05以下である。 The adhesive film of the present invention,
An adhesive film having a base material layer and an adhesive layer,
The difference between tan δ (0.7%) at a strain of 0.7% and tan δ (0.1%) at a strain of 0.1% measured in the tensile mode of the viscoelasticity measuring device (tan δ (0.7%)-tan δ (0.1%)) is 0.05 or less.
基材層と粘着剤層を有する粘着フィルムであって、
粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)と歪み0.1%におけるtanδ(0.1%)との差(tanδ(0.7%)-tanδ(0.1%))が0.05以下である。 The adhesive film of the present invention,
An adhesive film having a base material layer and an adhesive layer,
The difference between tan δ (0.7%) at a strain of 0.7% and tan δ (0.1%) at a strain of 0.1% measured in the tensile mode of the viscoelasticity measuring device (tan δ (0.7%)-tan δ (0.1%)) is 0.05 or less.
一つの実施形態においては、本発明の粘着フィルムは、6Φで屈曲させて90℃にて48時間保持させた後に、該屈曲を解放し、23℃、50%RHにて24時間放置させた後の屈曲角度が60度~180度である。
In one embodiment, the pressure-sensitive adhesive film of the present invention is bent at 6Φ and held at 90° C. for 48 hours, after which the bending is released and left at 23° C. and 50% RH for 24 hours. Has a bending angle of 60 to 180 degrees.
一つの実施形態においては、本発明の粘着フィルムは、上記基材層の上記粘着剤層を有する面と反対側の面にトップコート層を有する。
In one embodiment, the pressure-sensitive adhesive film of the present invention has a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer.
一つの実施形態においては、上記トップコート層が、ポリエステル樹脂およびウレタン系樹脂から選ばれる少なくとも1種を含むバインダを含有する。
In one embodiment, the top coat layer contains a binder containing at least one selected from polyester resins and urethane resins.
一つの実施形態においては、上記バインダがウレタン系樹脂を含む。
In one embodiment, the binder contains urethane resin.
一つの実施形態においては、上記トップコート層が帯電防止成分を含有する。
In one embodiment, the top coat layer contains an antistatic component.
一つの実施形態においては、上記基材層の23℃におけるヤング率が6.0×107Pa以上である。
In one embodiment, the base material layer has a Young's modulus at 23° C. of 6.0×10 7 Pa or more.
一つの実施形態においては、上記基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種である。
In one embodiment, the material of the base material layer is at least one selected from polyimide and polyether ether ketone.
一つの実施形態においては、本発明の粘着フィルムは、上記基材層の上記粘着剤層を有する面と反対側の面にトップコート層を有し、該トップコート層がウレタン系樹脂を含むバインダおよび帯電防止成分を含有し、上記基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種である。
In one embodiment, the pressure-sensitive adhesive film of the present invention has a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer, and the topcoat layer contains a binder containing a urethane resin. And an antistatic component, and the material of the base material layer is at least one selected from polyimide and polyether ether ketone.
一つの実施形態においては、本発明の粘着フィルムは、全光線透過率が20%以上である。
In one embodiment, the adhesive film of the present invention has a total light transmittance of 20% or more.
一つの実施形態においては、本発明の粘着フィルムは、ヘイズが15%以下である。
In one embodiment, the adhesive film of the present invention has a haze of 15% or less.
一つの実施形態においては、上記粘着剤層の、23℃における、引張速度300mm/分、180度ピールでの、SUS板に対する粘着力が1N/25mm以上である。
In one embodiment, the pressure-sensitive adhesive layer has an adhesive force of 1 N/25 mm or more with respect to a SUS plate at a pulling speed of 300 mm/min and a peel of 180 degrees at 23°C.
一つの実施形態においては、上記粘着剤層がアクリル系粘着剤を含む。
In one embodiment, the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive.
一つの実施形態においては、本発明の粘着フィルムは、フォルダブル部材に貼り付けられる。
In one embodiment, the adhesive film of the present invention is attached to a foldable member.
一つの実施形態においては、上記フォルダブル部材がOLEDである。
In one embodiment, the foldable member is an OLED.
一つの実施形態においては、本発明の粘着フィルムは、ローラブル部材に貼り付けられる。
In one embodiment, the adhesive film of the present invention is attached to a rollable member.
一つの実施形態においては、上記ローラブル部材がOLEDである。
In one embodiment, the rollable member is an OLED.
本発明のフォルダブルデバイスは、上記粘着フィルムを備える。
The foldable device of the present invention includes the above-mentioned adhesive film.
本発明のローラブルデバイスは、上記粘着フィルムを備える。
The rollable device of the present invention includes the above adhesive film.
本発明によれば、屈曲性および透明性に優れた粘着フィルムを提供することができる。本発明によれば、また、屈曲性に優れたフォルダブルデバイスおよびローラブルデバイスを提供することができる。
According to the present invention, an adhesive film having excellent flexibility and transparency can be provided. According to the present invention, it is also possible to provide a foldable device and a rollable device having excellent flexibility.
≪≪粘着フィルム≫≫
本発明の粘着フィルムは、基材層と粘着剤層を有する。すなわち、本発明の粘着フィルムは、基材層と粘着剤層を有すれば、本発明の効果を損なわない範囲で、任意の適切な他の層を有していてもよい。 ≪≪Adhesive film≫≫
The adhesive film of the present invention has a base material layer and an adhesive layer. That is, the pressure-sensitive adhesive film of the present invention may have any appropriate other layer as long as it has a base material layer and a pressure-sensitive adhesive layer, as long as the effects of the present invention are not impaired.
本発明の粘着フィルムは、基材層と粘着剤層を有する。すなわち、本発明の粘着フィルムは、基材層と粘着剤層を有すれば、本発明の効果を損なわない範囲で、任意の適切な他の層を有していてもよい。 ≪≪Adhesive film≫≫
The adhesive film of the present invention has a base material layer and an adhesive layer. That is, the pressure-sensitive adhesive film of the present invention may have any appropriate other layer as long as it has a base material layer and a pressure-sensitive adhesive layer, as long as the effects of the present invention are not impaired.
基材層は、1層であってもよいし、2層以上であってもよい。基材層は、本発明の効果をより発現させ得る点で、好ましくは1層である。
The base material layer may be one layer or two or more layers. The base material layer is preferably one layer from the viewpoint that the effect of the present invention can be further exhibited.
粘着剤層は、1層であってもよいし、2層以上であってもよい。粘着剤層は、本発明の効果をより発現させ得る点で、好ましくは1層である。
The pressure-sensitive adhesive layer may be one layer or two or more layers. The pressure-sensitive adhesive layer is preferably one layer from the viewpoint that the effect of the present invention can be further exhibited.
本発明の粘着フィルムは、粘着剤層の基材層の反対側の表面に、使用するまでの保護等のために、任意の適切な剥離ライナーが備えられていてもよい。
The pressure-sensitive adhesive film of the present invention may be provided with any suitable release liner on the surface of the pressure-sensitive adhesive layer on the side opposite to the base material layer for protection before use.
剥離ライナーとしては、例えば、紙やプラスチックフィルム等の基材(ライナー基材)の表面がシリコーン処理された剥離ライナー、紙やプラスチックフィルム等の基材(ライナー基材)の表面がポリオレフィン系樹脂によりラミネートされた剥離ライナーなどが挙げられる。ライナー基材としてのプラスチックフィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン-酢酸ビニル共重合体フィルムなどが挙げられる。
Examples of the release liner include a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicone, or a surface of a base material (liner base material) such as paper or plastic film is formed of a polyolefin resin. Examples include laminated release liners. The plastic film as the liner substrate, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Examples thereof include a polyurethane film and an ethylene-vinyl acetate copolymer film.
剥離ライナーの厚みは、好ましくは1μm~500μmであり、より好ましくは3μm~450μmであり、さらに好ましくは5μm~400μmであり、特に好ましくは10μm~300μmである。
The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, further preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm.
本発明の粘着フィルムは、総厚みdが、好ましくは1μm~500μmであり、より好ましくは5μm~200μmであり、さらに好ましくは10μm~150μmであり、特に好ましくは20μm~100μmであり、最も好ましくは30μm~80μmである。本発明の粘着フィルムの総厚みdが上記範囲内にあれば、本発明の効果がより発現し得る。
The adhesive film of the present invention has a total thickness d of preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm, further preferably 10 μm to 150 μm, particularly preferably 20 μm to 100 μm, and most preferably It is 30 μm to 80 μm. When the total thickness d of the adhesive film of the present invention is within the above range, the effect of the present invention can be more exhibited.
本発明の粘着フィルムは、粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)が、0.1以下であり、好ましくは0.09以下であり、より好ましくは0.08以下であり、さらに好ましくは0.07以下であり、特に好ましくは0.06以下である。本発明の粘着フィルムの、粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)が、上記範囲内にあれば、本発明の効果がより発現し得る。
The adhesive film of the present invention has a tan δ (0.7%) at a strain of 0.7% measured in a tension mode of a viscoelasticity measuring device of 0.1 or less, preferably 0.09 or less, and more preferably Is 0.08 or less, more preferably 0.07 or less, and particularly preferably 0.06 or less. If the tan δ (0.7%) at a strain of 0.7% of the pressure-sensitive adhesive film of the present invention measured in a tension mode of a viscoelasticity measuring device is within the above range, the effect of the present invention can be more exhibited.
粘着フィルムの、粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)は、粘着フィルムを大きく屈曲させた際の損失正接を示す指標である。本発明を完成させるに至っては、この値が上記範囲内にあれば本発明の効果がより発現し得ることを、種々の実験データに基づいて見出した。粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)の測定方法については、後に詳述する。
Tan δ (0.7%) at a strain of 0.7% measured in the tension mode of the viscoelasticity measuring device of the adhesive film is an index showing the loss tangent when the adhesive film is largely bent. Upon completion of the present invention, it was found based on various experimental data that the effect of the present invention can be more exhibited if this value is within the above range. The method for measuring tan δ (0.7%) at a strain of 0.7% measured in the tensile mode of the viscoelasticity measuring device will be described in detail later.
本発明の粘着フィルムは、粘弾性測定装置の引張モードにおいて測定した歪み0.1%におけるtanδ(0.1%)が、好ましくは0.1以下であり、より好ましくは0.08以下であり、さらに好ましくは0.06以下であり、特に好ましくは0.05以下である。本発明の粘着フィルムの、粘弾性測定装置の引張モードにおいて測定した歪み0.1%におけるtanδ(0.1%)が、上記範囲内にあれば、本発明の効果がより発現し得る。
The adhesive film of the present invention has a tan δ (0.1%) at a strain of 0.1% measured in a tensile mode of a viscoelasticity measuring device of preferably 0.1 or less, more preferably 0.08 or less. , More preferably 0.06 or less, and particularly preferably 0.05 or less. If the tan δ (0.1%) at a strain of 0.1% measured in the tensile mode of the viscoelasticity measuring device of the pressure-sensitive adhesive film of the present invention is within the above range, the effect of the present invention can be more exhibited.
粘着フィルムの、粘弾性測定装置の引張モードにおいて測定した歪み0.1%におけるtanδ(0.1%)は、粘着フィルムを小さく屈曲させた際の損失正接を示す指標である。本発明を完成させるに至っては、この値が上記範囲内にあれば本発明の効果がより発現し得ることを、種々の実験データに基づいて見出した。粘弾性測定装置の引張モードにおいて測定した歪み0.1%におけるtanδ(0.1%)の測定方法については、後に詳述する。
Tan δ (0.1%) at a strain of 0.1% measured in the tension mode of the viscoelasticity measuring device of the adhesive film is an index showing the loss tangent when the adhesive film is bent slightly. Upon completion of the present invention, it was found based on various experimental data that the effect of the present invention can be more exhibited if this value is within the above range. A method for measuring tan δ (0.1%) at a strain of 0.1% measured in the tensile mode of the viscoelasticity measuring device will be described in detail later.
本発明の粘着フィルムは、粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)と歪み0.1%におけるtanδ(0.1%)との差(tanδ(0.7%)-tanδ(0.1%))が、好ましくは0.05以下であり、より好ましくは0.04以下であり、さらに好ましくは0.03以下である。本発明の粘着フィルムの、粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)と歪み0.1%におけるtanδ(0.1%)との差(tanδ(0.7%)-tanδ(0.1%))が、上記範囲内にあれば、本発明の効果がより発現し得る。
The pressure-sensitive adhesive film of the present invention has a difference (tan δ (tan δ (0.1%) between a tan δ (0.7%) at a strain of 0.7% and a tan δ (0.1%) at a strain of 0.1% measured in a tensile mode of a viscoelasticity measuring device. 0.7%)-tan δ(0.1%)) is preferably 0.05 or less, more preferably 0.04 or less, still more preferably 0.03 or less. The difference (tan δ (tan δ (0.1%) between the tan δ (0.7%) at a strain of 0.7% and the tan δ (0.1%) at a strain of 0.7% of the pressure-sensitive adhesive film of the present invention measured in a tensile mode of a viscoelasticity measuring apparatus. If the ratio (0.7%)-tan δ(0.1%)) is within the above range, the effect of the present invention can be more exerted.
粘着フィルムの、粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)と歪み0.1%におけるtanδ(0.1%)との差(tanδ(0.7%)-tanδ(0.1%))は、粘着フィルムを大きく屈曲させた際の損失正接と粘着フィルムを小さく屈曲させた際の損失正接の差を示す指標である。本発明を完成させるに至っては、この値が上記範囲内にあれば本発明の効果がより発現し得ることを、種々の実験データに基づいて見出した。
The difference (tan δ (0.7%) between tan δ (0.7%) at a strain of 0.7% and tan δ (0.1%) at a strain of 0.7%, which was measured in a tensile mode of a viscoelasticity measuring device, of the adhesive film. %)-Tan δ (0.1%)) is an index showing the difference between the loss tangent when the pressure-sensitive adhesive film is largely bent and the loss tangent when the pressure-sensitive adhesive film is slightly bent. Upon completion of the present invention, it was found based on various experimental data that the effect of the present invention can be more exhibited if this value is within the above range.
本発明の粘着フィルムは、6Φで屈曲させて90℃にて48時間保持させた後に、該屈曲を解放し、23℃、50%RHにて24時間放置させた後の屈曲角度が、好ましくは60度~180度であり、より好ましくは80度~180度であり、さらに好ましくは100度~180度であり、特に好ましくは120度~180度であり、最も好ましくは150度~180度である。本発明の粘着フィルムの、6Φで屈曲させて90℃にて48時間保持させた後に、該屈曲を解放し、23℃、50%RHにて24時間放置させた後の屈曲角度が、上記範囲内にあれば、本発明の効果がより発現し得る。
The pressure-sensitive adhesive film of the present invention is preferably bent at 6Φ and held at 90° C. for 48 hours, then released from the bending, and allowed to stand at 23° C. and 50% RH for 24 hours. It is 60 to 180 degrees, more preferably 80 to 180 degrees, further preferably 100 to 180 degrees, particularly preferably 120 to 180 degrees, and most preferably 150 to 180 degrees. is there. The bending angle of the pressure-sensitive adhesive film of the present invention after being bent at 6Φ and held at 90° C. for 48 hours, then released, and allowed to stand at 23° C. and 50% RH for 24 hours is within the above range. Within the range, the effect of the present invention can be more exerted.
粘着フィルムの、6Φで屈曲させて90℃にて48時間保持させた後に、該屈曲を解放し、23℃、50%RHにて24時間放置させた後の屈曲角度は、屈曲後の回復性を示す指標である。6Φで屈曲させて90℃にて48時間保持させた後に、該屈曲を解放し、23℃、50%RHにて24時間放置させた後の屈曲角度の測定方法については、後に詳述する。
The bending angle of the pressure-sensitive adhesive film after being bent at 6Φ and held at 90° C. for 48 hours, then released, and allowed to stand at 23° C. and 50% RH for 24 hours is the recoverability after bending. Is an index indicating. The method of measuring the bending angle after bending at 6Φ and holding at 90° C. for 48 hours, releasing the bending, and leaving at 23° C. and 50% RH for 24 hours will be described in detail later.
本発明の粘着フィルムは、全光線透過率が、好ましくは20%以上であり、より好ましくは30%以上であり、さらに好ましくは40%以上であり、特に好ましくは50%以上であり、最も好ましくは60%以上である。本発明の粘着フィルムの全光線透過率が上記範囲内にあれば、優れた透明性がより発現し得る。
The adhesive film of the present invention has a total light transmittance of preferably 20% or more, more preferably 30% or more, further preferably 40% or more, particularly preferably 50% or more, most preferably Is 60% or more. When the total light transmittance of the pressure-sensitive adhesive film of the present invention is within the above range, excellent transparency can be further exhibited.
本発明の粘着フィルムは、ヘイズが、好ましくは15%以下であり、より好ましくは13%以下であり、さらに好ましくは10%以下であり、特に好ましくは8%以下であり、最も好ましくは6%以下である。本発明の粘着フィルムのヘイズが上記範囲内にあれば、優れた透明性がより発現し得る。
The adhesive film of the present invention has a haze of preferably 15% or less, more preferably 13% or less, further preferably 10% or less, particularly preferably 8% or less, and most preferably 6%. It is below. When the haze of the pressure-sensitive adhesive film of the present invention is within the above range, excellent transparency can be more exhibited.
本発明の粘着フィルムは、屈曲性および透明性に優れるので、好ましくは、フォルダブル部材に貼り付けられる。フォルダブル部材としては、繰り返しの屈曲が可能な部材であれば、任意の適切な部材を採用し得る。このようなフォルダブル部材としては、例えば、フォルダブルな光学部材、フォルダブルな電子部材などが挙げられ、代表的には、フォルダブルなOLEDが挙げられる。
Since the adhesive film of the present invention has excellent flexibility and transparency, it is preferably attached to a foldable member. Any appropriate member can be adopted as the foldable member as long as it can be repeatedly bent. Examples of such a foldable member include a foldable optical member, a foldable electronic member, and the like. Typically, a foldable OLED is used.
本発明の粘着フィルムは、屈曲性および透明性に優れるので、好ましくは、ローラブル部材に貼り付けられる。ローラブル部材としては、繰り返しの巻き取りと巻き戻しが可能な部材であれば、任意の適切な部材を採用し得る。このようなローラブル部材としては、例えば、ローラブルな光学部材、ローラブルな電子部材などが挙げられ、代表的には、ローラブルなOLEDが挙げられる。
The pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, and thus is preferably attached to a rollable member. Any appropriate member can be adopted as the rollable member as long as it can be repeatedly wound and unwound. Examples of such a rollable member include a rollable optical member and a rollable electronic member, and typically, a rollable OLED is used.
≪基材層≫
基材層の厚みは、好ましくは1μm~500μmであり、より好ましくは5μm~300μmであり、さらに好ましくは10μm~100μmであり、特に好ましくは15μm~80μmであり、最も好ましくは20μm~60μmである。基材層の厚みが上記範囲内にあれば、本発明の効果がより発現し得る。 ≪Base material layer≫
The thickness of the base material layer is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, further preferably 10 μm to 100 μm, particularly preferably 15 μm to 80 μm, and most preferably 20 μm to 60 μm. .. When the thickness of the base material layer is within the above range, the effect of the present invention can be more exhibited.
基材層の厚みは、好ましくは1μm~500μmであり、より好ましくは5μm~300μmであり、さらに好ましくは10μm~100μmであり、特に好ましくは15μm~80μmであり、最も好ましくは20μm~60μmである。基材層の厚みが上記範囲内にあれば、本発明の効果がより発現し得る。 ≪Base material layer≫
The thickness of the base material layer is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, further preferably 10 μm to 100 μm, particularly preferably 15 μm to 80 μm, and most preferably 20 μm to 60 μm. .. When the thickness of the base material layer is within the above range, the effect of the present invention can be more exhibited.
基材層は、23℃におけるヤング率が、好ましくは6.0×107Pa以上であり、より好ましくは1.0×108Pa以上であり、さらに好ましくは5.0×108Pa以上であり、特に好ましくは8.0×108Pa以上であり、最も好ましくは1.0×109Pa以上である。基材層の23℃におけるヤング率の上限は、代表的には、好ましくは1.0×1011Pa以下である。基材層の23℃におけるヤング率が上記範囲内にあれば、本発明の効果がより発現し得る。基材層の23℃におけるヤング率が低すぎると、粘着フィルムが角度を持って曲げられると、内径側の圧縮に対して外径側の引張が十分に保持できないおそれがあり、厚みが変化しやすくなり、被着体からの浮きが発生しやすくなるおそれがある。基材層の23℃におけるヤング率が高すぎると、粘着フィルムを容易に変形することができないおそれがある。ヤング率の測定方法については、後に詳述する。
The Young's modulus of the base material layer at 23° C. is preferably 6.0×10 7 Pa or higher, more preferably 1.0×10 8 Pa or higher, and further preferably 5.0×10 8 Pa or higher. And particularly preferably 8.0×10 8 Pa or higher, and most preferably 1.0×10 9 Pa or higher. The upper limit of the Young's modulus of the base material layer at 23° C. is typically and preferably 1.0×10 11 Pa or less. When the Young's modulus at 23° C. of the base material layer is within the above range, the effect of the present invention can be more exhibited. If the Young's modulus of the base material layer at 23° C. is too low, if the adhesive film is bent at an angle, the tension on the outer diameter side may not be sufficiently retained against the compression on the inner diameter side, and the thickness may change. There is a possibility that it will be easy to float from the adherend. If the Young's modulus at 23° C. of the base material layer is too high, the pressure-sensitive adhesive film may not be easily deformed. The method of measuring Young's modulus will be described in detail later.
基材層の材料としては、本発明の効果を損なわない範囲で、任意の適切な材料を採用し得る。このような基材層の材料としては、代表的には樹脂材料が挙げられる。
As the material of the base material layer, any appropriate material can be adopted as long as the effect of the present invention is not impaired. As a material of such a base material layer, a resin material is typically mentioned.
基材層の材料としての樹脂材料としては、例えば、ポリイミド(PI)、ポリエーテルエーテルケトン(PEEK)、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)、ポリメチルメタクリレート(PMMA)等のアクリル系樹脂、ポリカーボネート、トリアセチルセルロース(TAC)、ポリサルフォン、ポリアリレート、ポリエチレン(PE)、ポリプロピレン(PP)、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体(EVA)、ポリアミド(ナイロン)、全芳香族ポリアミド(アラミド)、ポリ塩化ビニル(PVC)、ポリ酢酸ビニル、ポリフェニレンサルファイド(PPS)、フッ素系樹脂、環状オレフィン系ポリマーなどが挙げられる。
Examples of the resin material as the material of the base material layer include polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polymethyl methacrylate. Acrylic resin such as (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) , Polyamide (nylon), wholly aromatic polyamide (aramid), polyvinyl chloride (PVC), polyvinyl acetate, polyphenylene sulfide (PPS), fluorine resin, cyclic olefin polymer, and the like.
基材層の材料としての樹脂材料としては、本発明の効果をより発現させ得る点で、好ましくは、ポリイミド(PI)、ポリエーテルエーテルケトン(PEEK)、環状オレフィン系ポリマーから選ばれる少なくとも1種が挙げられ、より好ましくは、ポリイミド(PI)およびポリエーテルエーテルケトン(PEEK)から選ばれる少なくとも1種が挙げられる。
The resin material as the material of the base material layer is preferably at least one selected from polyimide (PI), polyether ether ketone (PEEK), and cyclic olefin-based polymer from the viewpoint that the effect of the present invention can be further exhibited. And more preferably at least one selected from polyimide (PI) and polyether ether ketone (PEEK).
≪粘着剤層≫
粘着剤層の厚みは、好ましくは1μm~500μmであり、より好ましくは5μm~300μmであり、さらに好ましくは10μm~100μmであり、特に好ましくは15μm~80μmであり、最も好ましくは20μm~60μmである。粘着剤層の厚みが上記範囲内にあれば、本発明の効果がより発現し得る。 <<Adhesive layer>>
The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, further preferably 10 μm to 100 μm, particularly preferably 15 μm to 80 μm, and most preferably 20 μm to 60 μm. .. When the thickness of the pressure-sensitive adhesive layer is within the above range, the effect of the present invention can be more exhibited.
粘着剤層の厚みは、好ましくは1μm~500μmであり、より好ましくは5μm~300μmであり、さらに好ましくは10μm~100μmであり、特に好ましくは15μm~80μmであり、最も好ましくは20μm~60μmである。粘着剤層の厚みが上記範囲内にあれば、本発明の効果がより発現し得る。 <<Adhesive layer>>
The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, further preferably 10 μm to 100 μm, particularly preferably 15 μm to 80 μm, and most preferably 20 μm to 60 μm. .. When the thickness of the pressure-sensitive adhesive layer is within the above range, the effect of the present invention can be more exhibited.
粘着剤層の、23℃における、引張速度300mm/分、180度ピールでの、ガラス板に対する粘着力は、好ましくは1N/25mm以上であり、より好ましくは5N/25mm以上であり、さらに好ましくは10N/25mm以上であり、特に好ましくは12N/25mm以上であり、最も好ましくは15N/25mm以上である。粘着剤層の、23℃における、引張速度300mm/分、180度ピールでの、ガラス板に対する粘着力の上限は、代表的には、好ましくは1000N/25mm以下であり、より好ましくは5000N/25mm以下であり、さらに好ましくは300N/25mm以下であり、特に好ましくは200N/25mm以下であり、最も好ましくは100N/25mm以下である。粘着剤層の、23℃における、引張速度300mm/分、180度ピールでの、ガラス板に対する粘着力が上記範囲内にあれば、本発明の効果をより発現させ得る。
The adhesive force of the pressure-sensitive adhesive layer to the glass plate at a pulling speed of 300 mm/min and a peel of 180 degrees at 23° C. is preferably 1 N/25 mm or more, more preferably 5 N/25 mm or more, and further preferably It is 10 N/25 mm or more, particularly preferably 12 N/25 mm or more, and most preferably 15 N/25 mm or more. The upper limit of the adhesive force of the pressure-sensitive adhesive layer to the glass plate at a tensile rate of 300 mm/min and 180 degree peeling at 23° C. is typically preferably 1000 N/25 mm or less, more preferably 5000 N/25 mm. Or less, more preferably 300 N/25 mm or less, particularly preferably 200 N/25 mm or less, and most preferably 100 N/25 mm or less. If the adhesive strength of the pressure-sensitive adhesive layer to the glass plate at a tensile rate of 300 mm/min at 180° peel at 23° C. is within the above range, the effect of the present invention can be further exhibited.
粘着剤層は、ベースポリマーを含む。ベースポリマーは、1種のみであってもよいし、2種以上であってもよい。粘着剤層中のベースポリマーの含有割合は、本発明の効果をより発現させ得る点で、好ましくは20重量%~100重量%であり、より好ましくは30重量%~95重量%であり、さらに好ましくは40重量%~90重量%であり、特に好ましくは45重量%~85重量%であり、最も好ましくは50重量%~80重量%である。
The adhesive layer contains a base polymer. The base polymer may be only one type, or may be two or more types. The content ratio of the base polymer in the pressure-sensitive adhesive layer is preferably 20% by weight to 100% by weight, more preferably 30% by weight to 95% by weight, from the viewpoint that the effect of the present invention can be further exhibited. It is preferably 40% by weight to 90% by weight, particularly preferably 45% by weight to 85% by weight, and most preferably 50% by weight to 80% by weight.
ベースポリマーとしては、本発明の効果を損なわない範囲で任意の適切なポリマーを採用し得る。本発明の効果をより発現させ得る点で、ベースポリマーとしては、好ましくは、アクリル系ポリマー、ゴム系ポリマー、シリコーン系ポリマー、ウレタン系ポリマーから選ばれる少なくとも1種が挙げられる。すなわち、粘着剤層は、好ましくは、アクリル系ポリマーを含むアクリル系粘着剤、ゴム系ポリマーを含むゴム系粘着剤、シリコーン系ポリマーを含むシリコーン系粘着剤、ウレタン系ポリマーを含むウレタン系粘着剤から選ばれる少なくとも1種を含む。本発明の効果をより一層発現させ得る点で、粘着剤層は、好ましくは、アクリル系粘着剤を含む。以下、粘着剤層に含まれ得る粘着剤の代表例として、アクリル系粘着剤について詳述する。
As the base polymer, any suitable polymer can be adopted as long as the effect of the present invention is not impaired. The base polymer is preferably at least one selected from acrylic polymers, rubber polymers, silicone polymers, and urethane polymers from the viewpoint that the effects of the present invention can be further exhibited. That is, the pressure-sensitive adhesive layer is preferably composed of an acrylic pressure-sensitive adhesive containing an acrylic polymer, a rubber-based pressure-sensitive adhesive containing a rubber-based polymer, a silicone-based pressure-sensitive adhesive containing a silicone-based polymer, and a urethane-based pressure-sensitive adhesive containing a urethane-based polymer. At least one selected is included. From the viewpoint that the effects of the present invention can be further exhibited, the pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive. Hereinafter, an acrylic pressure-sensitive adhesive will be described in detail as a typical example of the pressure-sensitive adhesive that can be contained in the pressure-sensitive adhesive layer.
<アクリル系粘着剤>
アクリル系粘着剤は、ベースポリマーとしてアクリル系ポリマーを含む。アクリル系粘着剤は、粘着付与樹脂を含んでいてもよい。アクリル系粘着剤は、架橋剤を含んでいてもよい。 <Acrylic adhesive>
The acrylic pressure-sensitive adhesive contains an acrylic polymer as a base polymer. The acrylic adhesive may contain a tackifying resin. The acrylic pressure-sensitive adhesive may contain a crosslinking agent.
アクリル系粘着剤は、ベースポリマーとしてアクリル系ポリマーを含む。アクリル系粘着剤は、粘着付与樹脂を含んでいてもよい。アクリル系粘着剤は、架橋剤を含んでいてもよい。 <Acrylic adhesive>
The acrylic pressure-sensitive adhesive contains an acrylic polymer as a base polymer. The acrylic adhesive may contain a tackifying resin. The acrylic pressure-sensitive adhesive may contain a crosslinking agent.
アクリル系粘着剤が、アクリル系ポリマーと粘着付与樹脂と架橋剤とを含む場合、アクリル系粘着剤の全量に対する、アクリル系ポリマーと粘着付与樹脂と架橋剤の合計量の含有割合は、本発明の効果をより発現させ得る点で、好ましくは95重量%以上であり、より好ましくは97重量%以上であり、さらに好ましくは99重量%以上である。
When the acrylic pressure-sensitive adhesive contains an acrylic polymer, a tackifying resin, and a crosslinking agent, the content ratio of the total amount of the acrylic polymer, the tackifying resin, and the crosslinking agent with respect to the total amount of the acrylic pressure-sensitive adhesive is From the viewpoint that the effect can be further exhibited, it is preferably 95% by weight or more, more preferably 97% by weight or more, and further preferably 99% by weight or more.
(アクリル系ポリマー)
アクリル系ポリマーとしては、例えば、アルキル(メタ)アクリレートを主モノマーとして含み、該主モノマーと共重合性を有する副モノマーをさらに含み得るモノマー成分の重合物が好ましい。ここで主モノマーとは、モノマー成分全体の50重量%超を占める成分をいう。 (Acrylic polymer)
As the acrylic polymer, for example, a polymer of a monomer component containing an alkyl (meth)acrylate as a main monomer and further containing a sub-monomer copolymerizable with the main monomer is preferable. Here, the main monomer means a component which accounts for more than 50% by weight of the whole monomer component.
アクリル系ポリマーとしては、例えば、アルキル(メタ)アクリレートを主モノマーとして含み、該主モノマーと共重合性を有する副モノマーをさらに含み得るモノマー成分の重合物が好ましい。ここで主モノマーとは、モノマー成分全体の50重量%超を占める成分をいう。 (Acrylic polymer)
As the acrylic polymer, for example, a polymer of a monomer component containing an alkyl (meth)acrylate as a main monomer and further containing a sub-monomer copolymerizable with the main monomer is preferable. Here, the main monomer means a component which accounts for more than 50% by weight of the whole monomer component.
アルキル(メタ)アクリレートとしては、例えば、下記式(1)で表される化合物を好適に用いることができる。
CH2=C(R1)COOR2 (1) As the alkyl (meth)acrylate, for example, a compound represented by the following formula (1) can be preferably used.
CH 2 =C(R 1 )COOR 2 (1)
CH2=C(R1)COOR2 (1) As the alkyl (meth)acrylate, for example, a compound represented by the following formula (1) can be preferably used.
CH 2 =C(R 1 )COOR 2 (1)
ここで、上記式(1)中のR1は水素原子またはメチル基であり、R2は炭素原子数1~20の鎖状アルキル基(以下、このような炭素原子数の範囲を「C1-20」と表すことがある)である。粘着剤層の貯蔵弾性率等の観点から、R2は、好ましくはC1-14の鎖状アルキル基であり、より好ましくはC2-10の鎖状アルキル基であり、さらに好ましくはC4-8の鎖状アルキル基である。ここで鎖状とは、直鎖状および分岐状を包含する意味である。
Here, R 1 in the above formula (1) is a hydrogen atom or a methyl group, and R 2 is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms is referred to as “C1- 20"). From the viewpoint of the storage elastic modulus of the pressure-sensitive adhesive layer, R 2 is preferably a C1-14 chain alkyl group, more preferably a C2-10 chain alkyl group, and further preferably a C4-8 chain alkyl group. It is a chain alkyl group. Here, the term “chain” means a straight chain and a branched chain.
R2がC1-20の鎖状アルキル基であるアルキル(メタ)アクリレートとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、s-ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、テトラデシル(メタ)アクリレート、ペンタデシル(メタ)アクリレート、ヘキサデシル(メタ)アクリレート、ヘプタデシル(メタ)アクリレート、オクタデシル(メタ)アクリレート、イソステアリル(メタ)アクリレート、ノナデシル(メタ)アクリレート、エイコシル(メタ)アクリレートなどが挙げられる。これらアルキル(メタ)アクリレートは、1種のみであってもよいし、2種以上であってもよい。
Examples of the alkyl(meth)acrylate in which R 2 is a C1-20 chain alkyl group include, for example, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl. (Meth)acrylate, isobutyl(meth)acrylate, s-butyl(meth)acrylate, pentyl(meth)acrylate, isopentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, 2-ethylhexyl(meth)acrylate , Octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (Meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl ( Examples thereof include (meth)acrylate. These alkyl (meth)acrylates may be only one kind or two or more kinds.
アルキル(メタ)アクリレートとしては、本発明の効果をより発現させ得る点で、好ましくは、n-ブチルアクリレート(BA)、2-エチルヘキシルアクリレート(2EHA)が挙げられる。
The alkyl (meth)acrylate is preferably n-butyl acrylate (BA) or 2-ethylhexyl acrylate (2EHA) from the viewpoint that the effect of the present invention can be further exhibited.
アクリル系ポリマーの合成に用いられる全モノマー成分に占めるアルキル(メタ)アクリレートの含有割合は、本発明の効果をより発現させ得る点で、好ましくは70重量%以上であり、より好ましくは85重量%以上であり、さらに好ましくは90重量%以上である。アルキル(メタ)アクリレートの含有割合の上限は、好ましくは99.5重量%以下であり、より好ましくは99重量%以下である。しかしながら、アクリル系ポリマーは、実質的にアルキル(メタ)アクリレートのみを重合して得られたものであってもよい。
The content ratio of the alkyl (meth)acrylate in all the monomer components used for the synthesis of the acrylic polymer is preferably 70% by weight or more, more preferably 85% by weight, from the viewpoint that the effect of the present invention can be further exhibited. It is above, and more preferably 90% by weight or more. The upper limit of the content ratio of the alkyl (meth)acrylate is preferably 99.5% by weight or less, more preferably 99% by weight or less. However, the acrylic polymer may be obtained by polymerizing substantially only alkyl (meth)acrylate.
R2がC4-8の鎖状アルキル基であるアルキル(メタ)アクリレートを使用する場合、モノマー成分中に含まれるアルキル(メタ)アクリレートのうちR2がC4-8の鎖状アルキル基であるアルキル(メタ)アクリレートの割合は、本発明の効果をより発現させ得る点で、好ましくは50重量%以上であり、より好ましくは70重量%以上であり、さらに好ましくは90重量%以上であり、特に好ましくは95重量%以上であり、最も好ましくは99重量%~100重量%である。
When R 2 using the alkyl (meth) acrylate is a linear alkyl group of C4-8, alkyl R 2 is a linear alkyl group of C4-8 among alkyl (meth) acrylates contained in the monomer components The ratio of (meth)acrylate is preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 90% by weight or more, particularly from the viewpoint that the effect of the present invention can be further exhibited. It is preferably 95% by weight or more, and most preferably 99% by weight to 100% by weight.
アクリル系ポリマーの一つの実施形態として、全モノマー成分の50重量%以上がn-ブチルアクリレート(BA)であるアクリル系ポリマーが挙げられる。この場合、全モノマー成分中のn-ブチルアクリレート(BA)の含有割合は、本発明の効果をより発現させ得る点で、好ましくは50重量%を超え100重量%以下であり、より好ましくは55重量%~95重量%であり、さらに好ましくは60重量%~90重量%であり、特に好ましくは63重量%~85重量%であり、最も好ましくは65重量%~80重量%である。全モノマー成分は、n-ブチルアクリレート(BA)より少ない割合で2-エチルヘキシルアクリレート(2EHA)をさらに含んでいてもよい。
As one embodiment of the acrylic polymer, an acrylic polymer in which 50% by weight or more of all monomer components is n-butyl acrylate (BA) can be mentioned. In this case, the content ratio of n-butyl acrylate (BA) in all the monomer components is preferably more than 50% by weight and 100% by weight or less, and more preferably 55% by weight, from the viewpoint that the effect of the present invention can be further exhibited. % To 95% by weight, more preferably 60 to 90% by weight, particularly preferably 63 to 85% by weight, most preferably 65 to 80% by weight. The total monomer component may further include 2-ethylhexyl acrylate (2EHA) in a proportion smaller than n-butyl acrylate (BA).
アクリル系ポリマーの一つの実施形態として、全モノマー成分の50重量%未満が2-エチルヘキシルアクリレート(2EHA)であるアクリル系ポリマーが挙げられる。この場合、全モノマー成分中の2-エチルヘキシルアクリレート(2EHA)の含有割合は、本発明の効果をより発現させ得る点で、好ましくは0重量%を超え48重量%以下であり、より好ましくは5重量%~45重量%であり、さらに好ましくは10重量%~43重量%であり、特に好ましくは15重量%~40重量%であり、最も好ましくは20重量%~35重量%である。全モノマー成分は、2-エチルヘキシルアクリレート(2EHA)より多い割合でさらにn-ブチルアクリレート(BA)を含んでいてもよい。
One embodiment of an acrylic polymer is an acrylic polymer in which less than 50% by weight of all monomer components is 2-ethylhexyl acrylate (2EHA). In this case, the content ratio of 2-ethylhexyl acrylate (2EHA) in all the monomer components is preferably more than 0% by weight and 48% by weight or less, more preferably 5% or more, from the viewpoint that the effect of the present invention can be further exhibited. % By weight to 45% by weight, more preferably 10% by weight to 43% by weight, particularly preferably 15% by weight to 40% by weight, most preferably 20% by weight to 35% by weight. The total monomer component may further contain n-butyl acrylate (BA) in a proportion higher than that of 2-ethylhexyl acrylate (2EHA).
アクリル系ポリマーには、本発明の効果を損なわない範囲で、その他モノマーが共重合されていてもよい。その他モノマーは、例えば、アクリル系ポリマーのガラス転移温度(Tg)の調整、粘着性能の調整等の目的で使用することができる。例えば、粘着剤の凝集力や耐熱性を向上させ得るモノマーとして、スルホン酸基含有モノマー、リン酸基含有モノマー、シアノ基含有モノマー、ビニルエステル類、芳香族ビニル化合物などが挙げられ、ビニルエステル類が好ましい。ビニルエステル類の具体例としては、例えば、酢酸ビニル(VAc)、プロピオン酸ビニル、ラウリン酸ビニルなどが挙げられ、酢酸ビニル(VAc)が好ましい。
Other monomers may be copolymerized with the acrylic polymer as long as the effects of the present invention are not impaired. Other monomers can be used for the purpose of adjusting the glass transition temperature (Tg) of the acrylic polymer, adjusting the adhesive performance, and the like. Examples of the monomer capable of improving the cohesive force and heat resistance of the pressure-sensitive adhesive include sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl esters, aromatic vinyl compounds, and the like. Is preferred. Specific examples of vinyl esters include, for example, vinyl acetate (VAc), vinyl propionate, vinyl laurate and the like, with vinyl acetate (VAc) being preferred.
「その他モノマー」は、1種のみであってもよいし、2種以上であってもよい。全モノマー成分中のその他モノマーの含有割合は、好ましくは0.001重量%~40重量%であり、より好ましくは0.01重量%~40重量%であり、さらに好ましくは0.1重量%~10重量%であり、特に好ましくは0.5重量%~5重量%であり、最も好ましくは1重量%~3重量%である。
The “other monomer” may be only one kind or two or more kinds. The content of the other monomer in all the monomer components is preferably 0.001% by weight to 40% by weight, more preferably 0.01% by weight to 40% by weight, and further preferably 0.1% by weight to It is 10% by weight, particularly preferably 0.5% by weight to 5% by weight, and most preferably 1% by weight to 3% by weight.
アクリル系ポリマーに架橋基点となり得る官能基を導入し、あるいは接着力の向上に寄与し得るその他モノマーとして、例えば、水酸基(OH基)含有モノマー、カルボキシ基含有モノマー、酸無水物基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、イミド基含有モノマー、エポキシ基含有モノマー、(メタ)アクリロイルモルホリン、ビニルエーテル類などが挙げられる。
As the other monomer that can introduce a functional group that can serve as a crosslinking group point into the acrylic polymer or contribute to the improvement of adhesive strength, for example, a hydroxyl group (OH group)-containing monomer, a carboxy group-containing monomer, an acid anhydride group-containing monomer, an amide Examples thereof include a group-containing monomer, an amino group-containing monomer, an imide group-containing monomer, an epoxy group-containing monomer, (meth)acryloylmorpholine and vinyl ethers.
アクリル系ポリマーの一つの実施形態として、その他モノマーとしてカルボキシ基含有モノマーが共重合されたアクリル系ポリマーが挙げられる。カルボキシ基含有モノマーとしては、例えば、アクリル酸(AA)、メタクリル酸(MAA)、カルボキシエチル(メタ)アクリレート、カルボキシペンチル(メタ)アクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸などが挙げられる。これらの中でも、本発明の効果をより発現させ得る点で、カルボキシ基含有モノマーとして、好ましくは、アクリル酸(AA)、メタクリル酸(MAA)が挙げられ、より好ましくは、アクリル酸(AA)である。
As one embodiment of the acrylic polymer, there is an acrylic polymer in which a carboxy group-containing monomer is copolymerized as the other monomer. Examples of the carboxy group-containing monomer include acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and isocrotonic acid. Is mentioned. Among these, acrylic acid (AA) and methacrylic acid (MAA) are preferable as the carboxy group-containing monomer, from the viewpoint that the effect of the present invention can be further expressed, and acrylic acid (AA) is more preferable. is there.
その他モノマーとしてカルボキシ基含有モノマーを採用する場合、全モノマー成分中のその他モノマーの含有割合は、本発明の効果をより発現させ得る点で、好ましくは0.1重量%~10重量%であり、より好ましくは0.2重量%~8重量%であり、さらに好ましくは0.5重量%~5重量%であり、特に好ましくは0.7重量%~4重量%であり、最も好ましくは1重量%~3重量%である。
When a carboxy group-containing monomer is used as the other monomer, the content ratio of the other monomer in all the monomer components is preferably 0.1% by weight to 10% by weight from the viewpoint that the effect of the present invention can be further exhibited. More preferably 0.2% to 8% by weight, still more preferably 0.5% to 5% by weight, particularly preferably 0.7% to 4% by weight, most preferably 1% by weight. % To 3% by weight.
アクリル系ポリマーの一つの実施形態として、その他モノマーとして水酸基含有モノマーが共重合されたアクリル系ポリマーが挙げられる。水酸基含有モノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート;ポリプロピレングリコールモノ(メタ)アクリレート;N-ヒドロキシエチル(メタ)アクリルアミド;などが挙げられる。これらの中でも、水酸基含有モノマーとして、本発明の効果をより発現させ得る点で、好ましくは、アルキル基が炭素原子数2~4の直鎖状であるヒドロキシアルキル(メタ)アクリレートが挙げられ、具体的には、例えば、2-ヒドロキシエチルアクリレート(HEA)、4-ヒドロキシブチルアクリレート(4HBA)が挙げられ、より好ましくは、4-ヒドロキシブチルアクリレート(4HBA)である。
One example of an acrylic polymer is an acrylic polymer in which a hydroxyl group-containing monomer is copolymerized as another monomer. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth). ) Hydroxyalkyl (meth)acrylates such as acrylates; polypropylene glycol mono(meth)acrylate; N-hydroxyethyl (meth)acrylamide; and the like. Among these, the hydroxyl group-containing monomer is preferably a hydroxyalkyl(meth)acrylate whose alkyl group is a linear chain having 2 to 4 carbon atoms, from the viewpoint of more exerting the effects of the present invention. Specific examples thereof include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA), and 4-hydroxybutyl acrylate (4HBA) is more preferable.
その他モノマーとして水酸基含有モノマーを採用する場合、全モノマー成分中のその他モノマーの含有割合は、本発明の効果をより発現させ得る点で、好ましくは0.001重量%~10重量%であり、より好ましくは0.01重量%~5重量%であり、さらに好ましくは0.02重量%~2重量%であり、特に好ましくは0.03重量%~1重量%であり、最も好ましくは0.05重量%~0.5重量%である。
When a hydroxyl group-containing monomer is used as the other monomer, the content ratio of the other monomer in all the monomer components is preferably 0.001% by weight to 10% by weight from the viewpoint that the effect of the present invention can be more exhibited. It is preferably 0.01% to 5% by weight, more preferably 0.02% to 2% by weight, particularly preferably 0.03% to 1% by weight, and most preferably 0.05. % By weight to 0.5% by weight.
ベースポリマーのTgは、本発明の効果をより発現させ得る点で、例えば、-80℃以上であり得る。ベースポリマー(好適にはアクリル系ポリマー)は、せん断方向に対する粘着剤層の変形性を高める観点から、Tgが、好ましくは-15℃以下となるように設計されている。いくつかの実施形態においては、ベースポリマーのTgは、例えば、好ましくは-25℃以下であり、より好ましくは-40℃以下であり、さらに好ましくは-50℃以下である。ベースポリマーのTgは、凝集性や形状復元性を高める観点から、例えば、Tgが、好ましくは-70℃以上(より好ましくは-65℃以上、さらに好ましくは-60℃以上)となるように設計されている。
The Tg of the base polymer can be, for example, −80° C. or higher in that the effect of the present invention can be further exhibited. The base polymer (preferably an acrylic polymer) is designed so that Tg is preferably −15° C. or lower from the viewpoint of enhancing the deformability of the pressure-sensitive adhesive layer in the shearing direction. In some embodiments, the Tg of the base polymer is, for example, preferably −25° C. or lower, more preferably −40° C. or lower, further preferably −50° C. or lower. The Tg of the base polymer is designed so that, for example, the Tg is preferably −70° C. or higher (more preferably −65° C. or higher, further preferably −60° C. or higher) from the viewpoint of enhancing cohesiveness and shape recovery. Has been done.
ベースポリマーのTgとは、ベースポリマーを構成する各モノマーの単独重合体(ホモポリマー)のTgおよび該モノマーの重量分率(重量基準の共重合割合)に基づいて、フォックス(Fox)の式から求められる値をいう。Foxの式とは、以下に示すように、共重合体のTgと、該共重合体を構成するモノマーのそれぞれを単独重合したホモポリマーのガラス転移温度Tgiとの関係式である。
1/Tg=Σ(Wi/Tgi) The Tg of the base polymer is based on the Tg of a homopolymer (homopolymer) of each monomer constituting the base polymer and the weight fraction (copolymerization ratio on a weight basis) of the monomer, and is calculated from the Fox equation. Refers to the required value. The Fox equation is a relational expression between Tg of a copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
1/Tg=Σ(Wi/Tgi)
1/Tg=Σ(Wi/Tgi) The Tg of the base polymer is based on the Tg of a homopolymer (homopolymer) of each monomer constituting the base polymer and the weight fraction (copolymerization ratio on a weight basis) of the monomer, and is calculated from the Fox equation. Refers to the required value. The Fox equation is a relational expression between Tg of a copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
1/Tg=Σ(Wi/Tgi)
上記Foxの式において、Tgは共重合体のガラス転移温度(単位:K)、Wiは該共重合体におけるモノマーiの重量分率(重量基準の共重合割合)、Tgiはモノマーiのホモポリマーのガラス転移温度(単位:K)を表す。ホモポリマーのTgとしては、公知資料に記載の値を採用するものとする。
In the above Fox equation, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi is a homopolymer of the monomer i. Represents the glass transition temperature (unit: K) of. As the Tg of the homopolymer, the value described in publicly known data shall be adopted.
ホモポリマーのTgとして、例えば、具体的には以下の値を用い得る。
2-エチルヘキシルアクリレート -70℃
n-ブチルアクリレート -55℃
アクリル酸 106℃
2-ヒドロキシエチルアクリレート -15℃
4-ヒドロキシブチルアクリレート -40℃ As the Tg of the homopolymer, for example, the following values can be specifically used.
2-Ethylhexyl acrylate-70℃
n-Butyl acrylate -55°C
Acrylic acid 106℃
2-hydroxyethyl acrylate -15℃
4-hydroxybutyl acrylate -40°C
2-エチルヘキシルアクリレート -70℃
n-ブチルアクリレート -55℃
アクリル酸 106℃
2-ヒドロキシエチルアクリレート -15℃
4-ヒドロキシブチルアクリレート -40℃ As the Tg of the homopolymer, for example, the following values can be specifically used.
2-Ethylhexyl acrylate-70℃
n-Butyl acrylate -55°C
Acrylic acid 106℃
2-hydroxyethyl acrylate -15℃
4-hydroxybutyl acrylate -40°C
上記で例示した以外のホモポリマーのTgについては、「Polymer Handbook」(第3版、John Wiley & Sons, Inc., 1989)に記載の数値を用いることができる。上記「Polymer Handbook」に複数の数値が記載されている場合は、conventionalの値を採用する。上記「Polymer Handbook」に記載のないモノマーについては、モノマー製造企業のカタログ値を採用する。上記「Polymer Handbook」に記載がなく、モノマー製造企業のカタログ値も提供されていないモノマーのホモポリマーのTgとしては、特開2007-51271号公報に記載の測定方法により得られる値を用いるものとする。
Regarding the Tg of homopolymers other than those exemplified above, the values described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) can be used. If more than one numerical value is described in the above "Polymer Handbook", the value of "conventional" is adopted. For monomers not mentioned in the above "Polymer Handbook", the catalog values of the monomer manufacturing companies shall be adopted. As the Tg of the homopolymer of the monomer, which is not described in the above "Polymer Handbook" and the catalog value of the monomer manufacturing company is not provided, the value obtained by the measuring method described in JP2007-51271A is used. To do.
アクリル系ポリマーを得る方法としては、例えば、溶液重合法、乳化重合法、塊状重合法、懸濁重合法等の、アクリル系ポリマーの合成手法として知られている各種の重合方法を適宜採用することができる。これらの重合方法の中でも、溶液重合法を好ましく用いることができる。溶液重合を行う際のモノマー供給方法としては、モノマー成分の全量を一度に供給する一括仕込み方式、連続供給(滴下)方式、分割供給(滴下)方式等を適宜採用することができる。重合温度は、使用するモノマーおよび溶媒の種類、重合開始剤の種類等に応じて適宜選択することができ、好ましくは20℃以上であり、より好ましくは30℃以上であり、さらに好ましくは40℃以上であり、好ましくは170℃以下であり、より好ましくは160℃以下であり、さらに好ましくは140℃以下である。アクリル系ポリマーを得る方法としては、UV等の光を照射して行う光重合(典型的には、光重合開始剤の存在下で行われる)や、β線、γ線等の放射線を照射して行う放射線重合等の活性エネルギー線照射重合を採用してもよい。
As a method for obtaining an acrylic polymer, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or the like, various polymerization methods known as a synthetic method of an acrylic polymer may be appropriately adopted. You can Among these polymerization methods, the solution polymerization method can be preferably used. As a method of supplying a monomer when carrying out the solution polymerization, a batch charging method of supplying all of the monomer components at once, a continuous supply (dropping) method, a divided supply (dropping) method and the like can be appropriately adopted. The polymerization temperature can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc., and is preferably 20° C. or higher, more preferably 30° C. or higher, and further preferably 40° C. Or higher, preferably 170° C. or lower, more preferably 160° C. or lower, still more preferably 140° C. or lower. As a method for obtaining an acrylic polymer, photopolymerization (typically carried out in the presence of a photopolymerization initiator) performed by irradiating light such as UV, or irradiation with radiation such as β ray or γ ray is performed. Alternatively, active energy ray irradiation polymerization such as radiation polymerization may be employed.
溶液重合に用いる溶媒(重合溶媒)としては、任意の適切な有機溶媒から適宜選択することができる。例えば、トルエン等の芳香族化合物類(典型的には、芳香族炭化水素類)、酢酸エチル等の酢酸エステル類、ヘキサンやシクロヘキサン等の脂肪族または脂環式炭化水素類などが挙げられる。
The solvent (polymerization solvent) used for solution polymerization can be appropriately selected from any appropriate organic solvent. Examples thereof include aromatic compounds such as toluene (typically aromatic hydrocarbons), acetic acid esters such as ethyl acetate, and aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane.
重合に用いる開始剤(重合開始剤)は、重合方法の種類に応じて、任意の適切な重合開始剤から適宜選択することができる。重合開始剤は、1種のみであってもよいし、2種以上であってもよい。このような重合開始剤としては、例えば、2,2’-アゾビスイソブチロニトリル(AIBN)等のアゾ系重合開始剤;過硫酸カリウム等の過硫酸塩;ベンゾイルパーオキサイド、過酸化水素等の過酸化物系開始剤;フェニル置換エタン等の置換エタン系開始剤;芳香族カルボニル化合物;などが挙げられる。重合開始剤の他の例としては、過酸化物と還元剤との組合せによるレドックス系開始剤が挙げられる。
The initiator used for polymerization (polymerization initiator) can be appropriately selected from any appropriate polymerization initiator according to the type of polymerization method. Only 1 type may be sufficient as a polymerization initiator and 2 or more types may be sufficient as it. Examples of such a polymerization initiator include azo polymerization initiators such as 2,2′-azobisisobutyronitrile (AIBN); persulfates such as potassium persulfate; benzoyl peroxide, hydrogen peroxide, etc. Peroxide-based initiators; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds; and the like. As another example of the polymerization initiator, a redox type initiator obtained by combining a peroxide and a reducing agent can be mentioned.
重合開始剤の使用量は、全モノマー成分100重量部に対して、好ましくは0.005重量部~1重量部であり、より好ましくは0.01重量部~1重量部である。
The amount of the polymerization initiator used is preferably 0.005 to 1 part by weight, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of all the monomer components.
アクリル系ポリマーのMwは、好ましくは10×104~500×104であり、より好ましくは10×104~150×104であり、さらに好ましくは20×104~75×104であり、特に好ましくは35×104~65×104である。ここでMwとは、GPC(ゲルパーミエーションクロマトグラフィ)により得られた標準ポリスチレン換算の値をいう。GPC装置としては、例えば機種名「HLC-8320GPC」(カラム:TSKgel GMH-H(S)、東ソー社製)を用いることができる。
The Mw of the acrylic polymer is preferably 10×10 4 to 500×10 4 , more preferably 10×10 4 to 150×10 4 , and further preferably 20×10 4 to 75×10 4 . And particularly preferably 35×10 4 to 65×10 4 . Here, Mw refers to a standard polystyrene conversion value obtained by GPC (gel permeation chromatography). As the GPC device, for example, a model name “HLC-8320GPC” (column: TSKgel GMH-H(S), manufactured by Tosoh Corporation) can be used.
(粘着付与樹脂)
アクリル系粘着剤は、本発明の効果をより発現させ得る点で、粘着付与樹脂を含み得る。粘着付与樹脂としては、例えば、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂、炭化水素系粘着付与樹脂、エポキシ系粘着付与樹脂、ポリアミド系粘着付与樹脂、エラストマー系粘着付与樹脂、フェノール系粘着付与樹脂、ケトン系粘着付与樹脂などが挙げられる。粘着付与樹脂は、1種のみであってもよいし、2種以上であってもよい。 (Tackifying resin)
The acrylic pressure-sensitive adhesive may contain a tackifying resin from the viewpoint that the effect of the present invention can be further exhibited. Examples of the tackifying resin include rosin-based tackifying resin, terpene-based tackifying resin, hydrocarbon-based tackifying resin, epoxy-based tackifying resin, polyamide-based tackifying resin, elastomer-based tackifying resin, and phenol-based tackifying resin. , Ketone-based tackifying resins, and the like. The tackifying resin may be only one kind or two or more kinds.
アクリル系粘着剤は、本発明の効果をより発現させ得る点で、粘着付与樹脂を含み得る。粘着付与樹脂としては、例えば、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂、炭化水素系粘着付与樹脂、エポキシ系粘着付与樹脂、ポリアミド系粘着付与樹脂、エラストマー系粘着付与樹脂、フェノール系粘着付与樹脂、ケトン系粘着付与樹脂などが挙げられる。粘着付与樹脂は、1種のみであってもよいし、2種以上であってもよい。 (Tackifying resin)
The acrylic pressure-sensitive adhesive may contain a tackifying resin from the viewpoint that the effect of the present invention can be further exhibited. Examples of the tackifying resin include rosin-based tackifying resin, terpene-based tackifying resin, hydrocarbon-based tackifying resin, epoxy-based tackifying resin, polyamide-based tackifying resin, elastomer-based tackifying resin, and phenol-based tackifying resin. , Ketone-based tackifying resins, and the like. The tackifying resin may be only one kind or two or more kinds.
粘着付与樹脂の使用量は、本発明の効果をより発現させ得る点で、ベースポリマー100重量部に対して、好ましくは5重量部~70重量部であり、より好ましくは10重量部~60重量部であり、さらに好ましくは15重量部~50重量部であり、さらに好ましくは20重量部~45重量部であり、特に好ましくは25重量部~40重量部であり、最も好ましくは25重量部~35重量部である。
The amount of the tackifying resin used is preferably 5 parts by weight to 70 parts by weight, more preferably 10 parts by weight to 60 parts by weight, based on 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited. Parts, more preferably 15 parts by weight to 50 parts by weight, further preferably 20 parts by weight to 45 parts by weight, particularly preferably 25 parts by weight to 40 parts by weight, most preferably 25 parts by weight to 35 parts by weight.
粘着付与樹脂は、本発明の効果をより発現させ得る点で、軟化点が105℃未満の粘着付与樹脂TLを含むことが好ましい。粘着付与樹脂TLは、粘着剤層の面方向(せん断方向)への変形性の向上に効果的に寄与し得る。より高い変形性向上効果を得る観点から、粘着付与樹脂TLとして用いられる粘着付与樹脂の軟化点は、好ましくは50℃~103℃であり、より好ましくは60℃~100℃であり、さらに好ましくは65℃~95℃であり、特に好ましくは70℃~90℃であり、最も好ましくは75℃~85℃である。
The tackifying resin preferably contains a tackifying resin TL having a softening point of less than 105° C. from the viewpoint that the effect of the present invention can be further exhibited. The tackifying resin TL can effectively contribute to improving the deformability of the pressure-sensitive adhesive layer in the surface direction (shear direction). From the viewpoint of obtaining a higher effect of improving the deformability, the softening point of the tackifying resin used as the tackifying resin TL is preferably 50° C. to 103° C., more preferably 60° C. to 100° C., and further preferably The temperature is from 65°C to 95°C, particularly preferably from 70°C to 90°C, and most preferably from 75°C to 85°C.
粘着付与樹脂の軟化点は、JIS K5902およびJIS K2207に規定する軟化点試験方法(環球法)に基づいて測定された値として定義される。具体的には、試料をできるだけ低温ですみやかに融解し、これを平らな金属板の上に置いた環の中に、泡ができないように注意して満たす。冷えたのち、少し加熱した小刀で環の上端を含む平面から盛り上がった部分を切り去る。つぎに、径85mm以上、高さ127mm以上のガラス容器(加熱浴)の中に支持器(環台)を入れ、グリセリンを深さ90mm以上となるまで注ぐ。つぎに、鋼球(径9.5mm、重量3.5g)と、試料を満たした環とを互いに接触しないようにしてグリセリン中に浸し、グリセリンの温度を20℃プラスマイナス5℃に15分間保つ。つぎに、環中の試料の表面の中央に鋼球をのせ、これを支持器の上の定位置に置く。つぎに、環の上端からグリセリン面までの距離を50mmに保ち、温度計を置き、温度計の水銀球の中心の位置を環の中心と同じ高さとし、容器を加熱する。加熱に用いるブンゼンバーナーの炎は、容器の底の中心と縁との中間にあたるようにし、加熱を均等にする。なお、加熱が始まってから40℃に達したのちの浴温の上昇する割合は、毎分5.0プラスマイナス0.5℃でなければならない。試料がしだいに軟化して環から流れ落ち、ついに底板に接触したときの温度を読み、これを軟化点とする。軟化点の測定は、同時に2個以上行い、その平均値を採用する。
The softening point of the tackifying resin is defined as the value measured based on the softening point test method (ring and ball method) specified in JIS K5902 and JIS K2207. Specifically, the sample should be melted as quickly as possible and the ring placed on a flat metal plate should be carefully filled to prevent bubbles. After cooling down, cut off the raised part from the plane including the upper end of the ring with a slightly heated knife. Next, a support (ring holder) is placed in a glass container (heating bath) having a diameter of 85 mm or more and a height of 127 mm or more, and glycerin is poured until the depth becomes 90 mm or more. Next, a steel ball (diameter: 9.5 mm, weight: 3.5 g) and a ring filled with a sample are immersed in glycerin so that they do not contact each other, and the temperature of glycerin is kept at 20°C plus or minus 5°C for 15 minutes. .. Next, a steel ball is placed on the center of the surface of the sample in the ring, and this is placed in a fixed position on the support. Next, keeping the distance from the upper end of the ring to the glycerin surface at 50 mm, placing a thermometer, setting the position of the center of the mercury ball of the thermometer to the same height as the center of the ring, and heating the container. The Bunsen burner flame used for heating is placed so as to hit the center of the bottom of the container and the edge thereof so that the heating is even. The rate at which the bath temperature rises after reaching 40° C. after the start of heating must be 5.0 plus or minus 0.5° C. per minute. The temperature at which the sample gradually softens and flows down from the ring and finally comes into contact with the bottom plate is read, and this is taken as the softening point. Two or more softening points are measured at the same time, and the average value is adopted.
粘着付与樹脂TLの使用量としては、本発明の効果をより発現させ得る点で、ベースポリマー100重量部に対して、好ましくは5重量部~50重量部であり、より好ましくは10重量部~45重量部であり、さらに好ましくは15重量部~40重量部であり、特に好ましくは20重量部~35重量部であり、最も好ましくは25重量部~32重量部である。
The amount of the tackifying resin TL to be used is preferably 5 parts by weight to 50 parts by weight, more preferably 10 parts by weight to 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited. The amount is 45 parts by weight, more preferably 15 parts by weight to 40 parts by weight, particularly preferably 20 parts by weight to 35 parts by weight, and most preferably 25 parts by weight to 32 parts by weight.
粘着付与樹脂TLとしては、上記で例示した粘着付与樹脂のうち、軟化点が105℃未満のものから適宜選択される1種または2種以上を採用し得る。粘着付与樹脂TLは、好ましくはロジン系樹脂を含む。
As the tackifying resin TL, one or two or more kinds of the tackifying resins exemplified above may be appropriately selected from those having a softening point of less than 105°C. The tackifying resin TL preferably contains a rosin resin.
粘着付与樹脂TLとして好ましく採用し得るロジン系樹脂としては、例えば、未変性ロジンエステルや変性ロジンエステル等のロジンエステル類などが挙げられる。変性ロジンエステルとしては、例えば、水素添加ロジンエステルが挙げられる。
Rosin resins that can be preferably used as the tackifying resin TL include rosin esters such as unmodified rosin ester and modified rosin ester. Examples of the modified rosin ester include hydrogenated rosin ester.
粘着付与樹脂TLは、本発明の効果をより発現させ得る点で、好ましくは、水素添加ロジンエステルを含む。水素添加ロジンエステルとしては、軟化点が、本発明の効果をより発現させ得る点で、好ましくは105℃未満であり、より好ましくは50℃~100℃であり、さらに好ましくは60℃~90℃であり、特に好ましくは70℃~85℃であり、最も好ましくは75℃~85℃である。
The tackifying resin TL preferably contains a hydrogenated rosin ester from the viewpoint that the effect of the present invention can be further exhibited. The hydrogenated rosin ester has a softening point of preferably less than 105° C., more preferably 50° C. to 100° C., still more preferably 60° C. to 90° C., from the viewpoint that the effect of the present invention can be further exhibited. And particularly preferably 70° C. to 85° C., and most preferably 75° C. to 85° C.
粘着付与樹脂TLは、非水素添加ロジンエステルを含んでいてもよい。ここで非水素添加ロジンエステルとは、上述したロジンエステル類のうち水素添加ロジンエステル以外のものを包括的に指す概念である。非水素添加ロジンエステルとしては、未変性ロジンエステル、不均化ロジンエステル、重合ロジンエステルなどが挙げられる。
The tackifying resin TL may contain a non-hydrogenated rosin ester. Here, the non-hydrogenated rosin ester is a concept that comprehensively refers to the above-mentioned rosin esters other than the hydrogenated rosin ester. Examples of the non-hydrogenated rosin ester include unmodified rosin ester, disproportionated rosin ester, and polymerized rosin ester.
非水素添加ロジンエステルとしては、軟化点が、本発明の効果をより発現させ得る点で、好ましくは105℃未満であり、より好ましくは50℃~100℃であり、さらに好ましくは60℃~90℃であり、特に好ましくは70℃~85℃であり、最も好ましくは75℃~85℃である。
The non-hydrogenated rosin ester has a softening point of preferably less than 105° C., more preferably 50° C. to 100° C., still more preferably 60° C. to 90, from the viewpoint that the effect of the present invention can be further exhibited. C., particularly preferably 70 to 85.degree. C., most preferably 75 to 85.degree.
粘着付与樹脂TLは、ロジン系樹脂に加えて他の粘着付与樹脂を含んでいてもよい。他の粘着付与樹脂としては、上記で例示した粘着付与樹脂のうち、軟化点が105℃未満のものから適宜選択される1種または2種以上を採用し得る。粘着付与樹脂TLは、例えば、ロジン系樹脂とテルペン樹脂を含んでいてもよい。
The tackifying resin TL may contain another tackifying resin in addition to the rosin-based resin. As the other tackifying resin, among the tackifying resins exemplified above, one kind or two or more kinds appropriately selected from those having a softening point of less than 105° C. can be adopted. The tackifying resin TL may include, for example, a rosin resin and a terpene resin.
粘着付与樹脂TL全体に占めるロジン系樹脂の含有割合は、本発明の効果をより発現させ得る点で、好ましくは50重量%を超え、より好ましくは55重量%~100重量%であり、さらに好ましくは60重量%~99重量%であり、特に好ましくは65重量%~97重量%であり、最も好ましくは75重量%~97重量%である。
The content ratio of the rosin-based resin in the entire tackifying resin TL is preferably more than 50% by weight, more preferably 55% by weight to 100% by weight, and further preferably, from the viewpoint that the effect of the present invention can be further exhibited. Is 60% to 99% by weight, particularly preferably 65% to 97% by weight, most preferably 75% to 97% by weight.
粘着付与樹脂は、本発明の効果をより発現させ得る点で、粘着付与樹脂TLと、軟化点が105℃以上(好ましくは105℃~170℃)の粘着付与樹脂THを組み合わせて含んでいてもよい。
The tackifying resin may include the tackifying resin TL in combination with the tackifying resin TH having a softening point of 105° C. or higher (preferably 105° C. to 170° C.), in that the effect of the present invention can be further exhibited. Good.
粘着付与樹脂THとしては、上記で例示した粘着付与樹脂のうち軟化点が105℃以上のものから適宜選択される1種または2種以上を採用し得る。粘着付与樹脂THは、ロジン系粘着付与樹脂(例えば、ロジンエステル類)およびテルペン系粘着付与樹脂(例えば、テルペンフェノール樹脂)から選ばれる少なくとも1種を含み得る。
As the tackifying resin TH, one kind or two or more kinds of the tackifying resins exemplified above, which are appropriately selected from those having a softening point of 105° C. or higher, can be adopted. The tackifying resin TH may include at least one selected from rosin-based tackifying resins (for example, rosin esters) and terpene-based tackifying resins (for example, terpene phenolic resins).
(架橋剤)
アクリル系粘着剤には架橋剤を含有させることができる。架橋剤は、1種のみであってもよいし、2種以上であてもよい。架橋剤の使用により、アクリル系粘着剤に適度な凝集力を付与することができる。架橋剤は、保持力試験におけるズレ距離および戻り距離の調節にも役立ち得る。架橋剤を含有するアクリル系粘着剤は、例えば、該架橋剤を含む粘着剤組成物を用いて粘着剤層を形成することにより得ることができる。架橋剤は、架橋反応後の形態、架橋反応前の形態、部分的に架橋反応した形態、これらの中間的または複合的な形態等でアクリル系粘着剤に含まれ得る。架橋剤は、典型的には、もっぱら架橋反応後の形態でアクリル系粘着剤に含まれている。 (Crosslinking agent)
The acrylic pressure-sensitive adhesive may contain a crosslinking agent. The cross-linking agent may be only one kind or two or more kinds. By using the crosslinking agent, it is possible to impart an appropriate cohesive force to the acrylic pressure-sensitive adhesive. The cross-linking agent can also help control the displacement and return distances in the retention test. The acrylic pressure-sensitive adhesive containing a crosslinking agent can be obtained, for example, by forming a pressure-sensitive adhesive layer using a pressure-sensitive adhesive composition containing the crosslinking agent. The cross-linking agent may be included in the acrylic pressure-sensitive adhesive in a form after the cross-linking reaction, a form before the cross-linking reaction, a form in which the cross-linking reaction has occurred, an intermediate or complex form of these, and the like. The cross-linking agent is typically contained in the acrylic pressure-sensitive adhesive exclusively in the form after the cross-linking reaction.
アクリル系粘着剤には架橋剤を含有させることができる。架橋剤は、1種のみであってもよいし、2種以上であてもよい。架橋剤の使用により、アクリル系粘着剤に適度な凝集力を付与することができる。架橋剤は、保持力試験におけるズレ距離および戻り距離の調節にも役立ち得る。架橋剤を含有するアクリル系粘着剤は、例えば、該架橋剤を含む粘着剤組成物を用いて粘着剤層を形成することにより得ることができる。架橋剤は、架橋反応後の形態、架橋反応前の形態、部分的に架橋反応した形態、これらの中間的または複合的な形態等でアクリル系粘着剤に含まれ得る。架橋剤は、典型的には、もっぱら架橋反応後の形態でアクリル系粘着剤に含まれている。 (Crosslinking agent)
The acrylic pressure-sensitive adhesive may contain a crosslinking agent. The cross-linking agent may be only one kind or two or more kinds. By using the crosslinking agent, it is possible to impart an appropriate cohesive force to the acrylic pressure-sensitive adhesive. The cross-linking agent can also help control the displacement and return distances in the retention test. The acrylic pressure-sensitive adhesive containing a crosslinking agent can be obtained, for example, by forming a pressure-sensitive adhesive layer using a pressure-sensitive adhesive composition containing the crosslinking agent. The cross-linking agent may be included in the acrylic pressure-sensitive adhesive in a form after the cross-linking reaction, a form before the cross-linking reaction, a form in which the cross-linking reaction has occurred, an intermediate or complex form of these, and the like. The cross-linking agent is typically contained in the acrylic pressure-sensitive adhesive exclusively in the form after the cross-linking reaction.
架橋剤の使用量は、本発明の効果をより発現させ得る点で、ベースポリマー100重量部に対して、好ましくは0.005重量部~10重量部であり、より好ましくは0.01重量部~7重量部であり、さらに好ましくは0.05重量部~5重量部であり、特に好ましくは0.1重量部~4重量部であり、最も好ましくは1重量部~3重量部である。
The amount of the cross-linking agent used is preferably 0.005 to 10 parts by weight, more preferably 0.01 part by weight, based on 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited. To 7 parts by weight, more preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 4 parts by weight, and most preferably 1 to 3 parts by weight.
架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤、過酸化物等の架橋剤などが挙げられ、本発明の効果をより発現させ得る点で、好ましくは、イソシアネート系架橋剤、エポキシ系架橋剤であり、より好ましくは、イソシアネート系架橋剤である。
Examples of the cross-linking agent include isocyanate cross-linking agents, epoxy cross-linking agents, silicone cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, silane cross-linking agents, alkyl etherified melamine cross-linking agents, and metal chelate cross-linking agents. , A crosslinking agent such as peroxide, and the like, from the viewpoint that the effect of the present invention can be more exhibited, an isocyanate crosslinking agent and an epoxy crosslinking agent are preferable, and an isocyanate crosslinking agent is more preferable. ..
イソシアネート系架橋剤は、イソシアネート基(イソシアネート基をブロック剤または数量体化等により一時的に保護したイソシアネート再生型官能基を含む)を1分子中に2つ以上有する化合物を用いることができる。イソシアネート系架橋剤としては、例えば、トリレンジイソシアネート、キシレンジイソシアネート等の芳香族イソシアネート;イソホロンジイソシアネート等の脂環族イソシアネート;ヘキサメチレンジイソシアネート等の脂肪族イソシアネート;などが挙げられる。
As the isocyanate-based cross-linking agent, a compound having two or more isocyanate groups (including an isocyanate-regenerated functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification) can be used. Examples of the isocyanate-based cross-linking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate.
イソシアネート系架橋剤としては、より具体的には、例えば、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類;シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート類;2,4-トリレンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、ポリメチレンポリフェニルイソシアネート等の芳香族ジイソシアネート類;トリメチロールプロパン/トリレンジイソシアネート3量体付加物(例えば、東ソー社製、商品名コロネートL)、トリメチロールプロパン/ヘキサメチレンジイソシアネート3量体付加物(例えば、東ソー社製、商品名:コロネートHL)、ヘキサメチレンジイソシアネートのイソシアヌレート体(例えば、東ソー社製、商品名:コロネートHX)等のイソシアネート付加物;キシリレンジイソシアネートのトリメチロールプロパン付加物(例えば、三井化学社製、商品名:タケネートD110N)、キシリレンジイソシアネートのトリメチロールプロパン付加物(例えば、三井化学社製、商品名:タケネートD120N)、イソホロンジイソシアネートのトリメチロールプロパン付加物(例えば、三井化学社製、商品名:タケネートD140N)、ヘキサメチレンジイソシアネートのトリメチロールプロパン付加物(例えば、三井化学社製、商品名:タケネートD160N);ポリエーテルポリイソシアネート、ポリエステルポリイソシアネート、ならびにこれらと各種のポリオールとの付加物;イソシアヌレート結合、ビューレット結合、アロファネート結合等で多官能化したポリイソシアネート;などが挙げられる。これらの中でも、変形性と凝集力とをバランスよく両立し得る点で、芳香族イソシアネート、脂環式イソシアネートが好ましい。
Specific examples of the isocyanate cross-linking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2 Aromatic diisocyanates such as 4,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate; trimethylolpropane/tolylene diisocyanate trimer adducts (for example, manufactured by Tosoh Corporation, Trade name Coronate L), trimethylolpropane/hexamethylene diisocyanate trimer adduct (for example, Tosoh Corporation, trade name: Coronate HL), hexamethylene diisocyanate isocyanurate (for example, Tosoh Corporation, trade name: Coronate) HX) and other isocyanate adducts; trimethylolpropane adduct of xylylene diisocyanate (for example, Mitsui Chemicals, Inc., trade name: Takenate D110N), trimethylolpropane adduct of xylylene diisocyanate (for example, Mitsui Chemicals, product Name: Takenate D120N), trimethylolpropane adduct of isophorone diisocyanate (for example, Mitsui Chemicals, trade name: Takenate D140N), hexamethylene diisocyanate trimethylolpropane adduct (for example, Mitsui Chemicals, trade name: Takenate) D160N); polyether polyisocyanates, polyester polyisocyanates, and adducts of these with various polyols; polyisocyanates polyfunctionalized with isocyanurate bonds, burette bonds, allophanate bonds and the like; Among these, aromatic isocyanates and alicyclic isocyanates are preferable in terms of achieving good balance between deformability and cohesive force.
イソシアネート系架橋剤の使用量は、本発明の効果をより発現させ得る点で、ベースポリマー100重量部に対して、好ましくは0.005重量部~10重量部であり、より好ましくは0.01重量部~7重量部であり、さらに好ましくは0.05重量部~5重量部であり、特に好ましくは0.1重量部~4重量部であり、最も好ましくは1重量部~3重量部である。
The amount of the isocyanate cross-linking agent used is preferably 0.005 to 10 parts by weight, and more preferably 0.01 to 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited. Parts by weight to 7 parts by weight, more preferably 0.05 parts by weight to 5 parts by weight, particularly preferably 0.1 parts by weight to 4 parts by weight, most preferably 1 part by weight to 3 parts by weight. is there.
アクリル系ポリマーを構成するモノマー成分が水酸基含有モノマーを含む場合、本発明の効果をより発現させ得る点で、イソシアネート系架橋剤/水酸基含有モノマーの重量比が、好ましくは20を超えて50未満であり、より好ましくは22~45であり、さらに好ましくは25~40であり、特に好ましくは27~40であり、最も好ましくは30~35である。
When the monomer component constituting the acrylic polymer contains a hydroxyl group-containing monomer, the weight ratio of isocyanate crosslinking agent/hydroxyl group-containing monomer is preferably more than 20 and less than 50 from the viewpoint that the effect of the present invention can be further exhibited. Yes, more preferably 22 to 45, further preferably 25 to 40, particularly preferably 27 to 40, and most preferably 30 to 35.
アクリル系粘着剤が軟化点105℃以下の粘着付与樹脂TLを含む場合、本発明の効果をより発現させ得る点で、粘着付与樹脂TL/イソシアネート系架橋剤の重量比は、好ましくは2を超えて15未満であり、より好ましくは5~13であり、さらに好ましくは7~12であり、特に好ましくは7~11である。
When the acrylic pressure-sensitive adhesive contains the tackifying resin TL having a softening point of 105° C. or lower, the weight ratio of the tackifying resin TL/isocyanate cross-linking agent is preferably more than 2 from the viewpoint that the effect of the present invention can be further exhibited. Is less than 15, more preferably 5 to 13, still more preferably 7 to 12, and particularly preferably 7 to 11.
エポキシ系架橋剤としては、エポキシ基を1分子中に2つ以上有する多官能エポキシ化合物を用いることができる。エポキシ系架橋剤としては、例えば、N,N,N’,N’-テトラグリシジル-m-キシレンジアミン、ジグリシジルアニリン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、1,6-ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、アジピン酸ジグリシジルエステル、o-フタル酸ジグリシジルエステル、トリグリシジル-トリス(2-ヒドロキシエチル)イソシアヌレート、レゾルシンジグリシジルエーテル、ビスフェノール-S-ジグリシジルエーテル、分子内にエポキシ基を2つ以上有するエポキシ系樹脂などが挙げられる。エポキシ系架橋剤の市販品としては、例えば、三菱ガス化学社製の商品名「テトラッドC」、「テトラッドX」などが挙げられる。
As the epoxy-based cross-linking agent, a polyfunctional epoxy compound having two or more epoxy groups in one molecule can be used. Examples of the epoxy crosslinking agent include N,N,N′,N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, penta Erythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2-hydroxyethyl) isocyanurate, Examples thereof include resorcin diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule. Examples of commercially available products of the epoxy-based cross-linking agent include trade names “Tetrad C” and “Tetrad X” manufactured by Mitsubishi Gas Chemical Company.
エポキシ系架橋剤の使用量は、本発明の効果をより発現させ得る点で、ベースポリマー100重量部に対して、好ましくは0.005重量部~10重量部であり、より好ましくは0.01重量部~5重量部であり、さらに好ましくは0.015重量部~1重量部であり、特に好ましくは0.15重量部~0.5重量部であり、最も好ましくは0.015重量部~0.3重量部である。
The amount of the epoxy-based cross-linking agent used is preferably 0.005 to 10 parts by weight, more preferably 0.01 to 100 parts by weight of the base polymer, from the viewpoint that the effect of the present invention can be further exhibited. Parts by weight to 5 parts by weight, more preferably 0.015 parts by weight to 1 part by weight, particularly preferably 0.15 parts by weight to 0.5 parts by weight, most preferably 0.015 parts by weight to 0.3 parts by weight.
(その他成分)
アクリル系粘着剤は、必要に応じて、レベリング剤、架橋助剤、可塑剤、軟化剤、充填剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤等の、粘着剤の分野において一般的な各種の添加剤を含有してもよい。このような各種添加剤については、従来公知のものを常法により使用することができる。 (Other ingredients)
Acrylic pressure-sensitive adhesives, if necessary, such as leveling agents, crosslinking aids, plasticizers, softeners, fillers, antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers, etc. Various additives generally used in the field of agents may be contained. As such various additives, conventionally known ones can be used by a conventional method.
アクリル系粘着剤は、必要に応じて、レベリング剤、架橋助剤、可塑剤、軟化剤、充填剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤等の、粘着剤の分野において一般的な各種の添加剤を含有してもよい。このような各種添加剤については、従来公知のものを常法により使用することができる。 (Other ingredients)
Acrylic pressure-sensitive adhesives, if necessary, such as leveling agents, crosslinking aids, plasticizers, softeners, fillers, antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers, etc. Various additives generally used in the field of agents may be contained. As such various additives, conventionally known ones can be used by a conventional method.
≪帯電防止層≫
本発明の粘着フィルムは、基材層の粘着剤層を有する面と反対側の面に帯電防止層を有していてもよい。本発明の粘着フィルムが、基材層の粘着剤層を有する面と反対側の面に帯電防止層を有することにより、粘着フィルム自体の帯電を抑えることができ、塵埃が吸着しにくくなり、好ましい態様となる。 << Antistatic layer >>
The pressure-sensitive adhesive film of the present invention may have an antistatic layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer. The pressure-sensitive adhesive film of the present invention has an antistatic layer on the surface opposite to the surface having the pressure-sensitive adhesive layer of the substrate layer, whereby the charge of the pressure-sensitive adhesive film itself can be suppressed, and dust becomes difficult to be adsorbed, which is preferable. It becomes a mode.
本発明の粘着フィルムは、基材層の粘着剤層を有する面と反対側の面に帯電防止層を有していてもよい。本発明の粘着フィルムが、基材層の粘着剤層を有する面と反対側の面に帯電防止層を有することにより、粘着フィルム自体の帯電を抑えることができ、塵埃が吸着しにくくなり、好ましい態様となる。 << Antistatic layer >>
The pressure-sensitive adhesive film of the present invention may have an antistatic layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer. The pressure-sensitive adhesive film of the present invention has an antistatic layer on the surface opposite to the surface having the pressure-sensitive adhesive layer of the substrate layer, whereby the charge of the pressure-sensitive adhesive film itself can be suppressed, and dust becomes difficult to be adsorbed, which is preferable. It becomes a mode.
帯電防止層としては、例えば、帯電防止剤と樹脂成分からなる帯電防止性樹脂や導電性ポリマー、導電性物質を含有する導電性樹脂を塗布する方法や、導電性物質を蒸着あるいはメッキする方法が挙げられる。
As the antistatic layer, for example, a method of applying an antistatic resin composed of an antistatic agent and a resin component, a conductive polymer, a method of applying a conductive resin containing a conductive substance, or a method of depositing or plating a conductive substance is available. Can be mentioned.
帯電防止性樹脂に含有される帯電防止剤としては、例えば、第4級アンモニウム塩、ピリジニウム塩、第1、第2、第3アミノ基などのカチオン性官能基を有すカチオン型帯電防止剤;スルホン酸塩、硫酸エステル塩、ホスホン酸塩、リン酸エステル塩などのアニオン性官能基を有するアニオン型帯電防止剤;アルキルベタインおよびその誘導体、イミダゾリンおよびその誘導体、アラニンおよびその誘導体などの両性型帯電防止剤;アミノアルコールおよびその誘導体、グリセリンおよびその誘導体、ポリエチレングリコールおよびその誘導体などのノニオン型帯電防止剤;上記カチオン型、アニオン型、両性イオン型のイオン導電性基を有するモノマーを重合もしくは共重合して得られたイオン導電性重合体;などがあげられる。これらの帯電防止剤は、1種のみであってもよいし、2種以上であってもよい。
Examples of the antistatic agent contained in the antistatic resin include cation type antistatic agents having a cationic functional group such as quaternary ammonium salt, pyridinium salt, primary, secondary and tertiary amino groups; Anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric charges such as alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives Antistatic agent; nonionic antistatic agent such as amino alcohol and its derivative, glycerin and its derivative, polyethylene glycol and its derivative, etc.; polymerization or copolymerization of the above-mentioned cation type, anion type and amphoteric ion type monomer having an ion conductive group. And the like. These antistatic agents may be used alone or in combination of two or more.
カチオン型の帯電防止剤としては、例えば、アルキルトリメチルアンモニウム塩、アシロイルアミドプロピルトリメチルアンモニウムメトサルフェート、アルキルベンジルメチルアンモニウム塩、アシル塩化コリン、ポリジメチルアミノエチルメタクリレートなどの4級アンモニウム基を有する(メタ)アクリレート共重合体;ポリビニルベンジルトリメチルアンモニウムクロライドなどの4級アンモニウム基を有するスチレン共重合体;ポリジアリルジメチルアンモニウムクロライドなどの4級アンモニウム基を有するジアリルアミン共重合体;などが挙げられる。これらの帯電防止剤は、1種のみであってもよいし、2種以上であってもよい。
The cationic antistatic agent has, for example, a quaternary ammonium group such as an alkyltrimethylammonium salt, an acyloylamidopropyltrimethylammonium methosulfate, an alkylbenzylmethylammonium salt, an acylcholine chloride, and polydimethylaminoethylmethacrylate (meth). ) Acrylate copolymers; styrene copolymers having quaternary ammonium groups such as polyvinylbenzyltrimethylammonium chloride; diallylamine copolymers having quaternary ammonium groups such as polydiallyldimethylammonium chloride; These antistatic agents may be used alone or in combination of two or more.
アニオン型の帯電防止剤としては、例えば、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩、アルキルエトキシ硫酸エステル塩、アルキルリン酸エステル塩、スルホン酸基含有スチレン共重合体などが挙げられる。これらの帯電防止剤は、1種のみであってもよいし、2種以上であってもよい。
Examples of the anionic antistatic agent include alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfate ester salts, alkyl ethoxy sulfate ester salts, alkyl phosphate ester salts, and sulfonic acid group-containing styrene copolymers. .. These antistatic agents may be used alone or in combination of two or more.
両性イオン型の帯電防止剤としては、例えば、アルキルベタイン、アルキルイミダゾリウムベタイン、カルボベタイングラフト共重合などが挙げられる。これらの帯電防止剤は、1種のみであってもよいし、2種以上であってもよい。
Examples of zwitterionic antistatic agents include alkyl betaines, alkyl imidazolium betaines, and carbobetaine graft copolymers. These antistatic agents may be used alone or in combination of two or more.
ノニオン型の帯電防止剤としては、例えば、脂肪酸アルキロールアミド、ジ(2-ヒドロキシエチル)アルキルアミン、ポリオキシエチレンアルキルアミン、脂肪酸グリセリンエステル、ポリオキシエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシソルビタン脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリエチレングリコール、ポリオキシエチレンジアミン、ポリエーテルとポリエステルとポリアミドからなる共重合体、メトキシポリエチレングリコール(メタ)アクリレートなどが挙げられる。これらの帯電防止剤は、1種のみであってもよいし、2種以上であってもよい。
Examples of the nonionic antistatic agent include fatty acid alkylolamide, di(2-hydroxyethyl)alkylamine, polyoxyethylenealkylamine, fatty acid glycerin ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan. Examples thereof include fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyethylene glycol, polyoxyethylene diamine, a copolymer of polyether, polyester and polyamide, and methoxy polyethylene glycol (meth)acrylate. These antistatic agents may be used alone or in combination of two or more.
導電性ポリマーとしては、例えば、ポリアニリン、ポリピロール、ポリチオフェンなどが挙げられる。これらの導電性ポリマーは、1種のみであってもよいし、2種以上であってもよい。
Examples of conductive polymers include polyaniline, polypyrrole, polythiophene, and the like. These conductive polymers may be used alone or in combination of two or more.
導電性物質としては、例えば、酸化錫、酸化アンチモン、酸化インジウム、酸化カドミウム、酸化チタン、酸化亜鉛、インジウム、錫、アンチモン、金、銀、銅、アルミニウム、ニッケル、クロム、チタン、鉄、コバルト、ヨウ化銅、およびそれらの合金または混合物などが挙げられる。これらの導電性物質は、1種のみであってもよいし、2種以上であってもよい。
As the conductive substance, for example, tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, Copper iodide and alloys or mixtures thereof and the like can be mentioned. Only one kind of these conductive materials may be used, or two or more kinds thereof may be used.
帯電防止性樹脂および導電性樹脂に用いられる樹脂成分としては、例えば、ポリエステル樹脂、アクリル樹脂、ポリビニル樹脂、ウレタン樹脂、メラミン樹脂、エポキシ樹脂などの汎用樹脂が用いられる。なお、高分子型帯電防止剤の場合には、樹脂成分を含有させなくてもよい。また、帯電防止性樹脂の成分として、架橋剤として、メチロール化あるいはアルキロール化したメラミン系化合物、尿素系化合物、グリオキザール系化合物、アクリルアミド系化合物;エポキシ化合物;イソシアネート化合物;などを含有させることも可能である。
As the resin component used for the antistatic resin and the conductive resin, for example, general-purpose resins such as polyester resin, acrylic resin, polyvinyl resin, urethane resin, melamine resin, and epoxy resin are used. Incidentally, in the case of the polymer type antistatic agent, the resin component may not be contained. Further, as a cross-linking agent, a methylol- or alkylol-based melamine compound, urea compound, glyoxal compound, acrylamide compound, epoxy compound, isocyanate compound, etc. may be contained as a component of the antistatic resin. Is.
帯電防止層の形成方法としては、例えば、上述の帯電防止性樹脂、導電性ポリマー、導電性樹脂などを、有機溶剤もしくは水などの溶媒で希釈し、この塗液を基材などに塗布、乾燥することで形成される。
As a method for forming the antistatic layer, for example, the above-mentioned antistatic resin, conductive polymer, conductive resin or the like is diluted with a solvent such as an organic solvent or water, and the coating liquid is applied to a substrate or the like and dried. It is formed by doing.
帯電防止層の形成に用いる希釈溶液としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサノン、n-ヘキサン、トルエン、キシレン、メタノール、エタノール、n-プロパノール、イソプロパノール、水などが挙げられる。これらの溶剤は、1種のみであってもよいし、2種以上であってもよい。
Examples of the diluted solution used for forming the antistatic layer include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-propanol, isopropanol, water and the like. .. Only one kind of these solvents may be used, or two or more kinds thereof may be used.
帯電防止層の形成における塗布方法については、任意の適切な塗布方法が適宜用いられる。このような塗布方法としては、例えば、ロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、エアーナイフコート、含浸、カーテンコートなどが挙げられる。
Regarding the coating method for forming the antistatic layer, any suitable coating method is appropriately used. Examples of such a coating method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, impregnation and curtain coating.
導電性物質の蒸着あるいはメッキの方法としては、任意の適切な方法が適宜用いられる。このような方法としては、例えば、真空蒸着、スパッタリング、イオンプレーティング、化学蒸着、スプレー熱分解、化学メッキ、電気メッキ法などが挙げられる。
Any appropriate method is appropriately used as the method for vapor deposition or plating of the conductive material. Examples of such a method include vacuum vapor deposition, sputtering, ion plating, chemical vapor deposition, spray pyrolysis, chemical plating, electroplating and the like.
帯電防止層の厚みは、本発明の効果を損なわない範囲で、任意の適切な厚みを採用し得る。本発明の効果をより発現させ得る点で、帯電防止層の厚みは、好ましくは0.001μm~5μmであり、より好ましくは0.005μm~1μmである。
The thickness of the antistatic layer may be any appropriate thickness as long as the effect of the present invention is not impaired. The thickness of the antistatic layer is preferably 0.001 μm to 5 μm, and more preferably 0.005 μm to 1 μm, from the viewpoint that the effect of the present invention can be further exhibited.
≪トップコート層≫
本発明の粘着フィルムは、基材層の粘着剤層を有する面と反対側の面にトップコート層を有していてもよい。トップコート層は、好ましくは、バインダを含有し、より好ましくは、バインダと滑り剤を含有する。本発明の粘着フィルムがトップコート層を有することにより、粘着フィルムの耐スクラッチ性が向上し、好ましい態様となる。 ≪Top coat layer≫
The pressure-sensitive adhesive film of the present invention may have a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer. The top coat layer preferably contains a binder, and more preferably contains a binder and a slip agent. When the pressure-sensitive adhesive film of the present invention has the top coat layer, the scratch resistance of the pressure-sensitive adhesive film is improved, which is a preferred embodiment.
本発明の粘着フィルムは、基材層の粘着剤層を有する面と反対側の面にトップコート層を有していてもよい。トップコート層は、好ましくは、バインダを含有し、より好ましくは、バインダと滑り剤を含有する。本発明の粘着フィルムがトップコート層を有することにより、粘着フィルムの耐スクラッチ性が向上し、好ましい態様となる。 ≪Top coat layer≫
The pressure-sensitive adhesive film of the present invention may have a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer. The top coat layer preferably contains a binder, and more preferably contains a binder and a slip agent. When the pressure-sensitive adhesive film of the present invention has the top coat layer, the scratch resistance of the pressure-sensitive adhesive film is improved, which is a preferred embodiment.
<バインダ>
バインダは、本発明の効果を損なわない範囲で任意の適切な樹脂を採用し得る。このような樹脂としては、本発明の効果をより発現させ得る点で、好ましくは、ポリエステル樹脂およびウレタン系樹脂からなる群から選択される少なくとも1種である。 <Binder>
As the binder, any suitable resin can be adopted as long as the effect of the present invention is not impaired. Such a resin is preferably at least one selected from the group consisting of a polyester resin and a urethane resin, from the viewpoint that the effect of the present invention can be further exhibited.
バインダは、本発明の効果を損なわない範囲で任意の適切な樹脂を採用し得る。このような樹脂としては、本発明の効果をより発現させ得る点で、好ましくは、ポリエステル樹脂およびウレタン系樹脂からなる群から選択される少なくとも1種である。 <Binder>
As the binder, any suitable resin can be adopted as long as the effect of the present invention is not impaired. Such a resin is preferably at least one selected from the group consisting of a polyester resin and a urethane resin, from the viewpoint that the effect of the present invention can be further exhibited.
(ポリエステル樹脂)
バインダ中にポリエステル樹脂が含まれる場合、該ポリエステル樹脂は、1種のみであってもよいし、2種以上であってもよい。 (Polyester resin)
When the binder contains a polyester resin, the polyester resin may be only one kind or two or more kinds.
バインダ中にポリエステル樹脂が含まれる場合、該ポリエステル樹脂は、1種のみであってもよいし、2種以上であってもよい。 (Polyester resin)
When the binder contains a polyester resin, the polyester resin may be only one kind or two or more kinds.
ポリエステル樹脂は、好ましくは、ポリエステルを主成分として含む樹脂である。ポリエステル樹脂中のポリエステルの含有割合は、好ましくは50重量%超であり、より好ましくは75重量%以上であり、さらに好ましくは90重量%以上である。
The polyester resin is preferably a resin containing polyester as a main component. The content of polyester in the polyester resin is preferably more than 50% by weight, more preferably 75% by weight or more, and further preferably 90% by weight or more.
ポリエステルは、好ましくは、1分子中に2個以上のカルボキシル基を有する多価カルボン酸類(好ましくは、ジカルボン酸類)およびその誘導体(多価カルボン酸の無水物、エステル化物、ハロゲン化物等)から選択される少なくとも1種の化合物(多価カルボン酸成分)と、1分子中に2個以上の水酸基を有する多価アルコール類(好ましくは、ジオール類)から選択される少なくとも1種の化合物(多価アルコール成分)とが縮合した構造を有する。
The polyester is preferably selected from polyvalent carboxylic acids having two or more carboxyl groups in one molecule (preferably dicarboxylic acids) and derivatives thereof (anhydrides, esterified products, halides, etc. of polycarboxylic acid). At least one compound (polyvalent carboxylic acid component) and at least one compound selected from polyhydric alcohols (preferably diols) having two or more hydroxyl groups in one molecule (polyvalent) Alcohol component) and condensed structure.
多価カルボン酸成分として採用し得る化合物としては、例えば、シュウ酸、マロン酸、ジフルオロマロン酸、アルキルマロン酸、コハク酸、テトラフルオロコハク酸、アルキルコハク酸、(±)-リンゴ酸、meso-酒石酸、イタコン酸、マレイン酸、メチルマレイン酸、フマル酸、メチルフマル酸、アセチレンジカルボン酸、グルタル酸、ヘキサフルオログルタル酸、メチルグルタル酸、グルタコン酸、アジピン酸、ジチオアジピン酸、メチルアジピン酸、ジメチルアジピン酸、テトラメチルアジピン酸、メチレンアジピン酸、ムコン酸、ガラクタル酸、ピメリン酸、スベリン酸、パーフルオロスベリン酸、3,3,6,6-テトラメチルスベリン酸、アゼライン酸、セバシン酸、パーフルオロセバシン酸、ブラシル酸、ドデシルジカルボン酸、トリデシルジカルボン酸、テトラデシルジカルボン酸などの脂肪族ジカルボン酸類;シクロアルキルジカルボン酸(例えば、1,4-シクロヘキサンジカルボン酸、1,2-シクロヘキサンジカルボン酸)、1,4-(2-ノルボルネン)ジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸(ハイミック酸)、アダマンタンジカルボン酸、スピロヘプタンジカルボン酸などの脂環式ジカルボン酸類;フタル酸、イソフタル酸、ジチオイソフタル酸、メチルイソフタル酸、ジメチルイソフタル酸、クロロイソフタル酸、ジクロロイソフタル酸、テレフタル酸、メチルテレフタル酸、ジメチルテレフタル酸、クロロテレフタル酸、ブロモテレフタル酸、ナフタレンジカルボン酸、オキソフルオレンジカルボン酸、アントラセンジカルボン酸、ビフェニルジカルボン酸、ビフェニレンジカルボン酸、ジメチルビフェニレンジカルボン酸、4,4”-p-テレフェニレンジカルボン酸、4,4”-p-クワレルフェニルジカルボン酸、ビベンジルジカルボン酸、アゾベンゼンジカルボン酸、ホモフタル酸、フェニレン二酢酸、フェニレンジプロピオン酸、ナフタレンジカルボン酸、ナフタレンジプロピオン酸、ビフェニル二酢酸、ビフェニルジプロピオン酸、3,3'-[4,4’-(メチレンジ-p-ビフェニレン)ジプロピオン酸、4,4’-ビベンジル二酢酸、3,3’(4,4’-ビベンジル)ジプロピオン酸、オキシジ-p-フェニレン二酢酸などの芳香族ジカルボン酸類;上述したいずれかの多価カルボン酸の酸無水物;上述したいずれかの多価カルボン酸のエステル(例えば、アルキルエステル、モノエステル、ジエステル等);上述したいずれかの多価カルボン酸に対応する酸ハロゲン化物(例えば、ジカルボン酸クロリド等);などが挙げられる。
Examples of the compound that can be adopted as the polycarboxylic acid component include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±)-malic acid, meso- Tartaric acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methylglutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyladipic acid, dimethyladipine Acid, tetramethyladipic acid, methyleneadipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid, perfluorosebacine Aliphatic dicarboxylic acids such as acids, brassylic acid, dodecyldicarboxylic acid, tridecyldicarboxylic acid, and tetradecyldicarboxylic acid; cycloalkyldicarboxylic acids (eg, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid), 1 Alicyclic dicarboxylic acids such as 4-(2-norbornene)dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid (hymic acid), adamantanedicarboxylic acid, spiroheptanedicarboxylic acid; phthalic acid, isophthalic acid, dithioisophthalic acid Acid, methylisophthalic acid, dimethylisophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methylterephthalic acid, dimethylterephthalic acid, chloroterephthalic acid, bromoterephthalic acid, naphthalenedicarboxylic acid, oxofluorangecarboxylic acid, anthracenedicarboxylic acid, Biphenyldicarboxylic acid, biphenylenedicarboxylic acid, dimethylbiphenylenedicarboxylic acid, 4,4"-p-terephenylenedicarboxylic acid, 4,4"-p-quarrelphenyldicarboxylic acid, bibenzyldicarboxylic acid, azobenzenedicarboxylic acid, homophthalic acid, Phenylenediacetic acid, phenylenedipropionic acid, naphthalenedicarboxylic acid, naphthalenedipropionic acid, biphenyldiacetic acid, biphenyldipropionic acid, 3,3'-[4,4'-(methylenedi-p-biphenylene)dipropionic acid, 4 ,4'-bibenzyldiacetic acid, 3,3'(4,4'-bibenzyl)dipropionic acid, oxydi-p-phenylenediacetic acid and other aromatic dicarboxylic acids; acid anhydride of any of the above-mentioned polycarboxylic acids A polycarboxylic acid of any of the above. Examples thereof include steers (eg, alkyl esters, monoesters, diesters, etc.); acid halides (eg, dicarboxylic acid chlorides, etc.) corresponding to any of the polyvalent carboxylic acids described above, and the like.
多価カルボン酸成分として採用し得る化合物の好適例としては、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸類およびその酸無水物;アジピン酸、セバシン酸、アゼライン酸、コハク酸、フマル酸、マレイン酸、ハイミック酸、1,4-シクロヘキサンジカルボン酸等の脂肪族ジカルボン酸類およびその酸無水物;上記ジカルボン酸類の低級アルキルエステル(例えば、炭素原子数1~3のモノアルコールとのエステル);などが挙げられる。
Preferred examples of the compound that can be used as the polycarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, and fumaric acid. Aliphatic dicarboxylic acids such as acids, maleic acid, hymic acid, and 1,4-cyclohexanedicarboxylic acid, and acid anhydrides thereof; lower alkyl esters of the above dicarboxylic acids (for example, esters with monoalcohols having 1 to 3 carbon atoms) ; And the like.
多価アルコール成分として採用し得る化合物としては、例えば、エチレングリコール、プロピレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ネオペンチルグリコール、1,5-ペンタンジオール、1,6-ヘキサンジオール、3-メチルペンタンジオール、ジエチレングリコール、1,4-シクロヘキサンジメタノール、3-メチル-1,5-ペンタンジオール、2-メチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、キシリレングリコール、水添ビスフェノールA、ビスフェノールA等のジオール類が挙げられる。他の例としては、これらの化合物のアルキレンオキサイド付加物(例えば、エチレンオキサイド付加物、プロピレンオキサイド付加物等)が挙げられる。
Examples of compounds that can be used as the polyhydric alcohol component include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl. Glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3 -Propane diol, 2,2-diethyl-1,3-propane diol, 2-butyl-2-ethyl-1,3-propane diol, xylylene glycol, hydrogenated bisphenol A, bisphenol A, and other diols. .. Other examples include alkylene oxide adducts of these compounds (eg, ethylene oxide adducts, propylene oxide adducts, etc.).
ポリエステル樹脂は、好ましくは、水分散性ポリエステルを含み、より好ましくは、水分散性ポリエステルを主成分として含む。このような水分散性ポリエステルは、例えば、ポリマー中に親水性官能基(例えば、スルホン酸金属塩基、カルボキシル基、エーテル基、リン酸基などの親水性官能基から選ばれる少なくとも1種)を導入することにより水分散性を高めたポリエステルであり得る。このように、ポリマー中に親水性官能基を導入する手法としては、例えば、親水性官能基を有する化合物を共重合させる方法、ポリエステルまたはその前駆体(例えば、多価カルボン酸成分、多価アルコール成分、それらのオリゴマーなど)を変性して親水性官能基を生じさせる方法、などの、任意の適切な手法を適宜採用することができる。好ましい水分散性ポリエステルとしては、親水性官能基を有する化合物が共重合されたポリエステル(共重合ポリエステル)が挙げられる。
The polyester resin preferably contains a water-dispersible polyester, and more preferably contains a water-dispersible polyester as a main component. Such a water-dispersible polyester has, for example, a hydrophilic functional group (for example, at least one selected from hydrophilic functional groups such as metal sulfonate group, carboxyl group, ether group and phosphoric acid group) introduced into the polymer. It may be a polyester having improved water dispersibility. As described above, as a method of introducing a hydrophilic functional group into the polymer, for example, a method of copolymerizing a compound having a hydrophilic functional group, polyester or a precursor thereof (for example, polyvalent carboxylic acid component, polyhydric alcohol) Any appropriate technique such as a method of modifying components, oligomers thereof, etc.) to generate a hydrophilic functional group can be appropriately adopted. Preferred water-dispersible polyesters include polyesters (copolymerized polyesters) obtained by copolymerizing a compound having a hydrophilic functional group.
バインダとして用いられるポリエステル樹脂は、飽和ポリエステルを主成分とするものであってもよく、不飽和ポリエステルを主成分とするものであってもよい。ポリエステル樹脂は、好ましくは、その主成分が飽和ポリエステルであり、より好ましくは、水分散性が付与された飽和ポリエステル(例えば、飽和共重合ポリエステル)である。このようなポリエステル樹脂(水分散液の形態に調製されたものであり得るポリエステル樹脂)は、任意の適切な方法によって合成することができ、あるいは、市販品を容易に入手することができる。
The polyester resin used as the binder may be one having a saturated polyester as a main component or one having an unsaturated polyester as a main component. The polyester resin is preferably a saturated polyester as a main component, and more preferably a saturated polyester imparted with water dispersibility (for example, saturated copolyester). Such polyester resin (polyester resin which may be prepared in the form of an aqueous dispersion) can be synthesized by any appropriate method, or a commercially available product can be easily obtained.
ポリエステル樹脂の分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定される標準ポリスチレン換算の重量平均分子量(Mw)として、好ましくは0.5×104~15×104であり、より好ましくは1×104~6×104である。
The molecular weight of the polyester resin is preferably 0.5×10 4 to 15×10 4 , more preferably 1 as the weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). It is from ×10 4 to 6×10 4 .
ポリエステル樹脂のガラス転移温度(Tg)は、好ましくは0℃~100℃であり、より好ましくは10℃~80℃である。
The glass transition temperature (Tg) of the polyester resin is preferably 0°C to 100°C, more preferably 10°C to 80°C.
(ウレタン系樹脂)
バインダ中にウレタン系樹脂が含まれる場合、該ウレタン系樹脂は、1種のみであってもよいし、2種以上であってもよい。 (Urethane resin)
When a urethane-based resin is contained in the binder, the urethane-based resin may be only one type or two or more types.
バインダ中にウレタン系樹脂が含まれる場合、該ウレタン系樹脂は、1種のみであってもよいし、2種以上であってもよい。 (Urethane resin)
When a urethane-based resin is contained in the binder, the urethane-based resin may be only one type or two or more types.
ウレタン系樹脂としては、好ましくは、ポリオール(A)と多官能イソシアネート化合物(B)を含有する組成物を硬化させて得られるウレタン系樹脂である。
The urethane resin is preferably a urethane resin obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).
ポリオール(A)としては、1種のみであってもよいし、2種以上であってもよい。
As the polyol (A), only one kind may be used, or two or more kinds may be used.
ポリオール(A)としては、OH基を2個以上有するポリオールであれば、任意の適切なポリオールを採用し得る。このようなポリオール(A)としては、例えば、OH基を2個有するポリオール(ジオール)、OH基を3個有するポリオール(トリオール)、OH基を4個有するポリオール(テトラオール)、OH基を5個有するポリオール(ペンタオール)、OH基を6個有するポリオール(ヘキサオール)などが挙げられる。
As the polyol (A), any appropriate polyol can be adopted as long as it is a polyol having two or more OH groups. Examples of such a polyol (A) include a polyol (diol) having two OH groups, a polyol (triol) having three OH groups, a polyol (tetraol) having four OH groups, and an OH group of 5 Examples thereof include a polyol having one (pentaol) and a polyol having six OH groups (hexaol).
ポリオール(A)として、好ましくは、OH基を2個以上有するエチレングリコールやプロピレングリコールなどのグリコールを必須成分として採用する。このようにグリコールを必須成分として採用すると、例えば、硬化後の塗膜の強度に優れ、基材との密着性や添加物質の保持性に優れた、ウレタン系硬化樹脂を提供することができる。ポリオール(A)中の、グリコールの含有割合は、好ましくは30重量%~100重量%であり、より好ましくは50重量%~100重量%であり、さらに好ましくは70重量%~100重量%であり、さらに好ましくは90重量%~100重量%であり、特に好ましくは95重量%~100重量%であり、最も好ましくは実質的に100重量%である。
As the polyol (A), preferably, glycols such as ethylene glycol and propylene glycol having two or more OH groups are adopted as an essential component. By adopting glycol as an essential component in this way, it is possible to provide a urethane-based cured resin having excellent strength of a coating film after curing, excellent adhesion to a substrate and excellent retention of an added substance. The content ratio of glycol in the polyol (A) is preferably 30% by weight to 100% by weight, more preferably 50% by weight to 100% by weight, and further preferably 70% by weight to 100% by weight. %, more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, most preferably substantially 100% by weight.
ポリオール(A)としては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、ネオペンチルグリコール、3-メチル-1,5-ペンタンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、2,4-ジエチル-1,5-ペンタンジオール、1,2-ヘキサンジオール、1,6-ヘキサンジオール、1,8-オクタンジオール、1,9-ノナンジオール、2-メチル-1,8-オクタンジオール、1,8-デカンジオール、オクタデカンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ヘキサントリオール、ポリエチレングリコール、ポリプロピレングリコール、ポリエステルポリオール、ポリエーテルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ひまし油系ポリオールなどが挙げられる。
Examples of the polyol (A) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl- 2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonane Diol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polyethylene glycol, polypropylene glycol, polyester polyol, polyether polyol, polycaprolactone Examples include polyols, polycarbonate polyols, castor oil-based polyols, and the like.
ポリエステルポリオールとしては、例えば、ポリオール成分と酸成分とのエステル化反応によって得ることができる。
The polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
酸成分としては、例えば、コハク酸、メチルコハク酸、アジピン酸、ピメリック酸、アゼライン酸、セバシン酸、1,12-ドデカン二酸、1,14-テトラデカン二酸、ダイマー酸、2-メチル-1,4-シクロヘキサンジカルボン酸、2-エチル-1,4-シクロヘキサンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、イソフタル酸、テレフタル酸、1,4-ナフタレンジカルボン酸、4,4’-ビフェエルジカルボン酸、これらの酸無水物などが挙げられる。
Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid , And acid anhydrides thereof.
ポリエーテルポリオールとしては、例えば、水、低分子ポリオール(プロピレングリコール、エチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトールなど)、ビスフェノール類(ビスフェノールAなど)、ジヒドロキシベンゼン(カテコール、レゾルシン、ハイドロキノンなど)などを開始剤として、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどのアルキレンオキサイドを付加重合させることによって得られるポリエーテルポリオールが挙げられる。具体的には、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどが挙げられる。
As the polyether polyol, for example, water, low molecular weight polyol (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, hydroquinone, etc.), etc. As the initiator, a polyether polyol obtained by addition-polymerizing an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide can be mentioned. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
ポリカプロラクトンポリオールとしては、例えば、ε-カプロラクトン、σ-バレーロラクトンなどの環状エステルモノマーの開環重合により得られるカプロラクトン系ポリエステルジオールなどが挙げられる。
Examples of polycaprolactone polyols include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.
ポリカーボネートポリオールとしては、例えば、上記ポリオール成分とホスゲンとを重縮合反応させて得られるポリカーボネートポリオール;上記ポリオール成分と、炭酸ジメチル、炭酸ジエチル、炭酸ジプロビル、炭酸ジイソプロピル、炭酸ジブチル、エチルブチル炭酸、エチレンカーボネート、プロピレンカーボネート、炭酸ジフェニル、炭酸ジベンジル等の炭酸ジエステル類とをエステル交換縮合させて得られるポリカーボネートポリオール;上記ポリオール成分を2種以上併用して得られる共重合ポリカーボネートポリオール;上記各種ポリカーボネートポリオールとカルボキシル基含有化合物とをエステル化反応させて得られるポリカーボネートポリオール;上記各種ポリカーボネートポリオールとヒドロキシル基含有化合物とをエーテル化反応させて得られるポリカーボネートポリオール;上記各種ポリカーボネートポリオールとエステル化合物とをエステル交換反応させて得られるポリカーボネートポリオール;上記各種ポリカーボネートポリオールとヒドロキシル基含有化合物とをエステル交換反応させて得られるポリカーボネートポリオール;上記各種ポリカーボネートポリオールとジカルボン酸化合物とを重縮合反応させて得られるポリエステル系ポリカーボネートポリオール;上記各種ポリカーボネートポリオールとアルキレンオキサイドとを共重合させて得られる共重合ポリエーテル系ポリカーボネートポリオール;などが挙げられる。
As the polycarbonate polyol, for example, a polycarbonate polyol obtained by polycondensing the above polyol component and phosgene; the above polyol component, dimethyl carbonate, diethyl carbonate, diprobyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonic acid, ethylene carbonate, Polycarbonate polyols obtained by transesterification condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymerized polycarbonate polyols obtained by using two or more of the above polyol components together; the above various polycarbonate polyols and carboxyl group-containing Polycarbonate polyol obtained by esterification reaction with a compound; Polycarbonate polyol obtained by etherification reaction between the above various polycarbonate polyols and hydroxyl group-containing compound; Obtained by transesterification reaction between the above various polycarbonate polyols and ester compound Polycarbonate polyol; Polycarbonate polyol obtained by transesterification of the above-mentioned various polycarbonate polyols and hydroxyl group-containing compounds; Polyester-based polycarbonate polyol obtained by polycondensation reaction of the above-mentioned various polycarbonate polyols and dicarboxylic acid compounds; And a alkylene oxide copolymerized polyether-based polycarbonate polyol;
ひまし油系ポリオールとしては、例えば、ひまし油脂肪酸と上記ポリオール成分とを反応させて得られるひまし油系ポリオールが挙げられる。具体的には、例えば、ひまし油脂肪酸とポリプロピレングリコールとを反応させて得られるひまし油系ポリオールが挙げられる。
Examples of castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acid with the above polyol component. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.
多官能イソシアネート化合物(B)は、1種のみであってもよいし、2種以上であってもよい。
The polyfunctional isocyanate compound (B) may be only one type, or may be two or more types.
多官能イソシアネート化合物(B)としては、ウレタン化反応に用い得る任意の適切な多官能イソシアネート化合物を採用し得る。このような多官能イソシアネート化合物(B)としては、例えば、多官能脂肪族系イソシアネート化合物、多官能脂環族系イソシアネート、多官能芳香族系イソシアネート化合物などが挙げられる。
As the polyfunctional isocyanate compound (B), any suitable polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted. Examples of such a polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate compound, and a polyfunctional aromatic isocyanate compound.
多官能脂肪族系イソシアネート化合物としては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、1,2-プロピレンジイソシアネート、1,3-ブチレンジイソシアネート、ドデカメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネートなどが挙げられる。
Examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4. 4-trimethylhexamethylene diisocyanate and the like can be mentioned.
多官能脂環族系イソシアネート化合物としては、例えば、1,3-シクロペンテンジイソシアネート、1,3-シクロへキサンジイソシアネート、1,4-シクロヘキサンジイソシアネート、イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加キシリレンジイソシアネート、水素添加トリレンジイソシアネート、水素添加テトラメチルキシリレンジイソシアネートなどが挙げられる。
Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Examples thereof include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
多官能芳香族系ジイソシアネート化合物としては、例えば、フェニレンジイソシアネート、2,4-トリレンジイソソアネート、2,6-トリレンジイソシアネート、2,2’一ジフェニルメタンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、4,4’-トルイジンジイソシアネート、4,4’-ジフェニルエーテルジイソシアネート、4,4’-ジフェニルジイソシアネート、1,5-ナフタレンジイソシアネート、キシリレンジイソシアネートなどが挙げられる。
Examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and , 4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.
多官能イソシアネート化合物(B)としては、上記のような各種多官能イソシアネート化合物のトリメチロールプロパンアダクト体、水と反応したビュウレット体、イソシアヌレート環を有する3量体なども挙げられる。また、これらを併用しても良い。
Examples of the polyfunctional isocyanate compound (B) also include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, burettes reacted with water, trimers having an isocyanurate ring, and the like. Also, these may be used in combination.
多官能イソシアネート化合物(B)の含有割合は、ポリオール(A)に対して、多官能イソシアネート化合物(B)が、好ましくは5重量%~60重量%であり、より好ましくは8重量%~60重量%であり、さらに好ましくは10重量%~60重量%である。多官能イソシアネート化合物(B)の含有割合を上記範囲内に調整することにより、本発明の効果をより一層発現し得る。
The content of the polyfunctional isocyanate compound (B) is preferably 5% by weight to 60% by weight, more preferably 8% by weight to 60% by weight, based on the polyol (A). %, and more preferably 10% to 60% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the effect of the present invention can be further exhibited.
ウレタン系樹脂は、代表的には、ポリオール(A)と多官能イソシアネート化合物(B)を含有する組成物を硬化させて得られる。このような組成物中には、本発明の効果を損なわない範囲で、ポリオール(A)および多官能イソシアネート化合物(B)以外の任意の適切なその他の成分を含み得る。このようなその他の成分としては、例えば、触媒、ポリウレタン系樹脂以外の他の樹脂成分、粘着付与剤、無機充填剤、有機充填剤、金属粉、顔料、箔状物、軟化剤、可塑剤、老化防止剤、導電剤、酸化防止剤、紫外線吸収剤、光安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤などが挙げられる。
The urethane resin is typically obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B). In such a composition, any appropriate other component other than the polyol (A) and the polyfunctional isocyanate compound (B) may be contained within a range not impairing the effects of the present invention. Such other components include, for example, catalysts, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, Examples include antiaging agents, conductive agents, antioxidants, ultraviolet absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and the like.
ポリオール(A)と多官能イソシアネート化合物(B)を含有する組成物を硬化させてウレタン系樹脂を得る方法としては、塊状重合や溶液重合などを用いたウレタン化反応方法など、本発明の効果を損なわない範囲で任意の適切な方法を採用し得る。
As a method for curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) to obtain a urethane-based resin, the effects of the present invention such as a urethanization reaction method using bulk polymerization or solution polymerization can be obtained. Any appropriate method can be adopted within a range that does not impair the property.
(その他の樹脂)
トップコート層は、粘着フィルムの性能を大きく損なわない限度で、バインダとして、ポリエステル樹脂およびウレタン系樹脂以外のその他の樹脂(例えば、アクリル樹脂、アクリル-スチレン樹脂、アクリル-シリコーン樹脂、シリコーン樹脂、ポリシラザン樹脂、フッ素樹脂、ポリオレフィン樹脂から選択される少なくとも1種の樹脂)をさらに含有し得る。トップコート層の好ましい実施態様としては、トップコート層のバインダが実質的にポリエステル樹脂およびウレタン系樹脂からなる群から選択される少なくとも1種のみからなり、バインダに占めるポリエステル樹脂およびウレタン系樹脂からなる群から選択される少なくとも1種の割合が、好ましくは98重量%~100重量%であり、より好ましくは99重量%~100重量%であり、さらに好ましくは99.5重量%~100重量%である。トップコート層全体に占めるバインダの割合は、好ましくは15重量%~95重量%であり、より好ましくは25重量%~80重量%である。 (Other resins)
The top coat layer serves as a binder as long as it does not significantly impair the performance of the adhesive film, and as a binder, other resins (for example, acrylic resin, acrylic-styrene resin, acrylic-silicone resin, silicone resin, polysilazane). At least one resin selected from resins, fluororesins and polyolefin resins) may be further contained. In a preferred embodiment of the topcoat layer, the binder of the topcoat layer is substantially composed of at least one selected from the group consisting of polyester resin and urethane resin, and is composed of polyester resin and urethane resin in the binder. The proportion of at least one selected from the group is preferably 98% by weight to 100% by weight, more preferably 99% by weight to 100% by weight, and further preferably 99.5% by weight to 100% by weight. is there. The proportion of the binder in the entire top coat layer is preferably 15% by weight to 95% by weight, more preferably 25% by weight to 80% by weight.
トップコート層は、粘着フィルムの性能を大きく損なわない限度で、バインダとして、ポリエステル樹脂およびウレタン系樹脂以外のその他の樹脂(例えば、アクリル樹脂、アクリル-スチレン樹脂、アクリル-シリコーン樹脂、シリコーン樹脂、ポリシラザン樹脂、フッ素樹脂、ポリオレフィン樹脂から選択される少なくとも1種の樹脂)をさらに含有し得る。トップコート層の好ましい実施態様としては、トップコート層のバインダが実質的にポリエステル樹脂およびウレタン系樹脂からなる群から選択される少なくとも1種のみからなり、バインダに占めるポリエステル樹脂およびウレタン系樹脂からなる群から選択される少なくとも1種の割合が、好ましくは98重量%~100重量%であり、より好ましくは99重量%~100重量%であり、さらに好ましくは99.5重量%~100重量%である。トップコート層全体に占めるバインダの割合は、好ましくは15重量%~95重量%であり、より好ましくは25重量%~80重量%である。 (Other resins)
The top coat layer serves as a binder as long as it does not significantly impair the performance of the adhesive film, and as a binder, other resins (for example, acrylic resin, acrylic-styrene resin, acrylic-silicone resin, silicone resin, polysilazane). At least one resin selected from resins, fluororesins and polyolefin resins) may be further contained. In a preferred embodiment of the topcoat layer, the binder of the topcoat layer is substantially composed of at least one selected from the group consisting of polyester resin and urethane resin, and is composed of polyester resin and urethane resin in the binder. The proportion of at least one selected from the group is preferably 98% by weight to 100% by weight, more preferably 99% by weight to 100% by weight, and further preferably 99.5% by weight to 100% by weight. is there. The proportion of the binder in the entire top coat layer is preferably 15% by weight to 95% by weight, more preferably 25% by weight to 80% by weight.
<滑り剤>
滑り剤としては、高級脂肪酸と高級アルコールとのエステル(以下「ワックスエステル」と称することがある。)を含むことが好ましい。 <Slip agent>
The slip agent preferably contains an ester of a higher fatty acid and a higher alcohol (hereinafter sometimes referred to as "wax ester").
滑り剤としては、高級脂肪酸と高級アルコールとのエステル(以下「ワックスエステル」と称することがある。)を含むことが好ましい。 <Slip agent>
The slip agent preferably contains an ester of a higher fatty acid and a higher alcohol (hereinafter sometimes referred to as "wax ester").
「高級脂肪酸」とは、好ましくは、炭素原子数が8以上のカルボン酸であり、その炭素原子数は、より好ましくは10以上であり、さらに好ましくは10~40である。カルボン酸は、好ましくは、1価のカルボン酸である。
The “higher fatty acid” is preferably a carboxylic acid having 8 or more carbon atoms, and the number of carbon atoms is more preferably 10 or more, further preferably 10 to 40. The carboxylic acid is preferably a monovalent carboxylic acid.
「高級アルコール」とは、好ましくは、炭素原子数が6以上のアルコールであり、その炭素原子数は、より好ましくは10以上であり、さらに好ましくは10~40である。アルコールは、好ましくは、1価または2価のアルコールであり、より好ましくは、1価のアルコールである。
The “higher alcohol” is preferably an alcohol having 6 or more carbon atoms, and the number of carbon atoms is more preferably 10 or more, further preferably 10 to 40. The alcohol is preferably a monohydric or dihydric alcohol, more preferably a monohydric alcohol.
このようなワックスエステルと前述のバインダとを組み合わせて含む組成のトップコート層は、高温多湿条件に保持されても白化しにくい。したがって、このようなトップコート層を有する基材を備えた粘着フィルムは、より外観品位の高いものとなり得る。
The topcoat layer having a composition containing a combination of such a wax ester and the above-mentioned binder is unlikely to be whitened even when kept under high temperature and high humidity conditions. Therefore, the adhesive film provided with the base material having such a top coat layer can have a higher appearance quality.
上記組成のトップコート層によって優れた耐白化性(例えば、高温多湿条件に保持されても白化しにくい性質)が実現される理由としては、例えば、以下の理由が考えられる。すなわち、従来使用されているシリコーン系滑剤は、トップコート層の表面にブリードすることにより該表面に滑り性を付与する機能を発揮するものと推察される。しかし、これらシリコーン系滑剤は、保存条件(温度、湿度、経時等)の違いによってブリードの程度が変動しやすい。このため、例えば、通常の保存条件(例えば、25℃、50%RH)に保持された場合に、粘着フィルムの製造直後から比較的長期間(例えば、約3ヶ月)に亘って適度な滑り性が得られるようにシリコーン系滑剤の使用量を設定すると、この粘着フィルムが高温多湿条件(例えば、60℃、95%RH)で2週間保存された場合には、滑剤のブリードが過剰に進行してしまう。このように過剰にブリードしたシリコーン系滑剤は、トップコート層(ひいては粘着フィルム)を白化させてしまうおそれがある。
The following reasons can be considered as reasons why excellent whitening resistance (for example, the property that whitening is difficult even when kept under high temperature and high humidity conditions) is achieved by the topcoat layer having the above composition. That is, it is presumed that the conventionally used silicone-based lubricant exhibits a function of imparting slipperiness to the surface of the topcoat layer by bleeding. However, in these silicone lubricants, the degree of bleeding is likely to change depending on the storage conditions (temperature, humidity, aging, etc.). Therefore, for example, when the adhesive film is kept under normal storage conditions (for example, 25° C. and 50% RH), it has a suitable slipperiness for a relatively long period (for example, about 3 months) immediately after the production of the adhesive film. When the amount of the silicone-based lubricant used is set so that the pressure-sensitive adhesive film is obtained, when this adhesive film is stored under high temperature and high humidity conditions (for example, 60° C. and 95% RH) for 2 weeks, bleeding of the lubricant excessively proceeds. Will end up. Such excessively bleeding silicone-based lubricant may cause whitening of the top coat layer (and thus the adhesive film).
トップコート層の好ましい実施形態としては、滑り剤としてのワックスエステルとバインダとしてのポリエステル樹脂という特定の組合せを採用する。このような滑り剤とバインダとの組合せによると、ワックスエステルのトップコート層からのブリードの程度が保存条件の影響を受けにくい。このことによって、粘着フィルムの耐白化性が向上し得る。
As a preferred embodiment of the top coat layer, a specific combination of wax ester as a slip agent and polyester resin as a binder is adopted. With such a combination of the slip agent and the binder, the degree of bleeding of the wax ester from the top coat layer is less likely to be affected by storage conditions. This can improve the whitening resistance of the adhesive film.
ワックスエステルとしては、一般式(W)で表わされる化合物の1種以上を好ましく採用し得る。
X-COO-Y (W) As the wax ester, one or more compounds represented by the general formula (W) can be preferably adopted.
X-COO-Y (W)
X-COO-Y (W) As the wax ester, one or more compounds represented by the general formula (W) can be preferably adopted.
X-COO-Y (W)
式(W)中のXおよびYは、それぞれ独立に、好ましくは、炭素原子数10~40の炭化水素基であり、その炭素原子数は、より好ましくは10~35であり、さらに好ましくは14~35であり、特に好ましくは20~32である。上記の炭素原子数が小さすぎると、トップコート層に滑り性を付与する効果が不足するおそれがある。上記の炭化水素基は、飽和炭化水素基であってもおいし、不飽和炭化水素基であってもよい。上記の炭化水素基は、好ましくは、飽和炭化水素基である。また、上記の炭化水素基は、芳香族の環を含む構造であってもよく、芳香環を含まない構造(脂肪族性炭化水素基)であってもよく、脂肪族性の環を含む構造の炭化水素基(脂環式炭化水素基)であってもよく、鎖状(直鎖状および分岐鎖状を包含する)の炭化水素基であってもよい。
X and Y in formula (W) are each independently preferably a hydrocarbon group having 10 to 40 carbon atoms, and the number of carbon atoms is more preferably 10 to 35, and further preferably 14 To 35, particularly preferably 20 to 32. If the number of carbon atoms is too small, the effect of imparting slipperiness to the top coat layer may be insufficient. The above hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. The above-mentioned hydrocarbon group is preferably a saturated hydrocarbon group. The above hydrocarbon group may have a structure containing an aromatic ring, or may have a structure containing no aromatic ring (aliphatic hydrocarbon group), or a structure containing an aliphatic ring. May be a hydrocarbon group (alicyclic hydrocarbon group) or a chain (including straight chain and branched chain) hydrocarbon group.
ワックスエステルとしては、式(W)におけるXおよびYが、それぞれ独立に、好ましくは、炭素原子数10~40の鎖状アルキル基である化合物であり、より好ましくは、炭素原子数10~40の直鎖状アルキル基である化合物である。このような化合物の具体例としては、例えば、セロチン酸ミリシル(CH3(CH2)24COO(CH2)29CH3)、パルミチン酸ミリシル(CH3(CH2)14COO(CH2)29CH3)、パルミチン酸セチル(CH3(CH2)14COO(CH2)15CH3)、ステアリル酸ステアリル(CH3(CH2)16COO(CH2)17CH3)などが挙げられる。
The wax ester is a compound in which X and Y in the formula (W) are each independently a chain alkyl group having 10 to 40 carbon atoms, more preferably 10 to 40 carbon atoms. It is a compound that is a linear alkyl group. Specific examples of such compounds, for example, cerotic myricyl (CH 3 (CH 2) 24 COO (CH 2) 29 CH 3), myricyl palmitate (CH 3 (CH 2) 14 COO (CH 2) 29 CH 3), cetyl palmitate (CH 3 (CH 2) 14 COO (CH 2) 15 CH 3), stearyl stearyl (CH 3 (CH 2) 16 COO (CH 2) 17 CH 3) , and the like.
ワックスエステルは、融点が、好ましくは50℃以上であり、より好ましくは60℃以上であり、さらに好ましくは70℃以上であり、特に好ましくは75℃以上である。このようなワックスエステルによれば、より高い耐白化性が実現され得る。ワックスエステルは、融点が100℃以下であることが好ましい。このようなワックスエステルは、滑り性を付与する効果が高いので、より耐スクラッチ性の高いトップコート層を形成し得る。ワックスエステルの融点が100℃以下であることは、ワックスエステルの水分散液を調製しやすいという点からも好ましい。このようなワックスエステルとしては、例えば、セロチン酸ミリシルを好ましく採用し得る。
The wax ester has a melting point of preferably 50° C. or higher, more preferably 60° C. or higher, further preferably 70° C. or higher, particularly preferably 75° C. or higher. With such a wax ester, higher whitening resistance can be realized. The wax ester preferably has a melting point of 100° C. or lower. Since such a wax ester has a high effect of imparting slipperiness, it can form a top coat layer having higher scratch resistance. It is also preferable that the melting point of the wax ester is 100° C. or lower from the viewpoint of easily preparing an aqueous dispersion of the wax ester. As such a wax ester, for example, myricyl cerotate can be preferably adopted.
トップコート層の原料として、このようなワックスエステルを含有する天然ワックスを利用することができる。このような天然ワックスとしては、不揮発分(NV)基準で、上記ワックスエステルの含有割合(2種以上のワックスエステルを含む場合にはそれらの含有割合の合計)が、好ましくは50重量%よりも多く、より好ましくは65重量%以上であり、さらに好ましくは75重量%以上である。このような天然ワックスとしては、例えば、カルナバワックス(一般に、セロチン酸ミリシルを、好ましくは60重量%以上、より好ましくは70重量%以上、さらに好ましくは80重量%以上の割合で含む。)、パームワックス等の植物性ワックス;蜜ロウ、鯨ロウ等の動物性ワックス;などが挙げられる。このような天然ワックスの融点は、好ましくは50℃以上であり、より好ましくは60℃以上であり、さらに好ましくは70℃以上であり、特に好ましくは75℃以上である。トップコート層の原料としては、化学的に合成されたワックスエステルを用いてもよいし、天然ワックスを精製してワックスエステルの純度を高めたものを用いてもよい。これらの原料は、1種のみであってもよいし、2種以上であってもよい。
A natural wax containing such a wax ester can be used as a raw material for the top coat layer. As such a natural wax, the content ratio of the above-mentioned wax ester (the total content ratio of the wax esters when two or more kinds of wax esters are contained) is preferably more than 50% by weight based on the nonvolatile content (NV). Most, more preferably 65% by weight or more, and further preferably 75% by weight or more. Examples of such a natural wax include carnauba wax (generally, containing myricyl cerotate in an amount of preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more). And vegetable waxes such as wax; animal waxes such as beeswax and whale wax; and the like. The melting point of such natural wax is preferably 50° C. or higher, more preferably 60° C. or higher, further preferably 70° C. or higher, particularly preferably 75° C. or higher. As a raw material for the top coat layer, a chemically synthesized wax ester may be used, or a natural wax purified to improve the purity of the wax ester may be used. These raw materials may be only one kind or two or more kinds.
トップコート層全体に占める滑り剤の割合は、好ましくは5重量%~50重量%であり、より好ましくは10重量%~40重量%である。滑り剤の含有割合が少なすぎると、耐スクラッチ性が低下しやすくなるおそれがある。滑り剤の含有割合が多すぎると、耐白化性の向上効果が不足しやすくなるおそれがある。
The proportion of the slip agent in the entire top coat layer is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight. If the content of the slipping agent is too low, the scratch resistance may be lowered. If the content of the slip agent is too high, the effect of improving the whitening resistance may be insufficient.
トップコート層は、ワックスエステルに加えて、他の滑り剤を含んでいてもよい。他の滑り剤としては、例えば、石油系ワックス(パラフィンワックス等)、鉱物系ワックス(モンタンワックス等)、高級脂肪酸(セロチン酸等)、中性脂肪(パルミチン酸トリグリセリド等)のような、ワックスエステル以外の各種ワックスが挙げられる。また、ワックスエステルに加えて、シリコーン系滑剤、フッ素系滑剤などを含有させてもよい。トップコート層の好ましい実施形態としては、シリコーン系滑剤、フッ素系滑剤を実質的に含有しない形態であり、例えば、シリコーン系滑剤とフッ素系滑剤の合計含有量がトップコート層全体の、好ましくは0.01重量%以下であり、より好ましくは検出限界以下である。
The top coat layer may contain other slip agent in addition to the wax ester. Examples of other lubricants include wax esters such as petroleum wax (paraffin wax), mineral wax (montane wax etc.), higher fatty acid (cerotic acid etc.) and neutral fat (palmitic acid triglyceride etc.). Other various waxes are listed. Further, in addition to the wax ester, a silicone lubricant, a fluorine lubricant, etc. may be contained. A preferred embodiment of the top coat layer is a form in which a silicone-based lubricant and a fluorine-based lubricant are not substantially contained. For example, the total content of the silicone-based lubricant and the fluorine-based lubricant is preferably 0 or less. It is 0.01% by weight or less, more preferably the detection limit or less.
トップコート層は、必要に応じて、帯電防止成分、架橋剤、酸化防止剤、着色剤(顔料、染料等)、流動性調整剤(チクソトロピー剤、増粘剤等)、造膜助剤、界面活性剤(消泡剤、分散剤等)、防腐剤等の添加剤を含有し得る。
The topcoat layer is an antistatic component, a cross-linking agent, an antioxidant, a colorant (pigment, dye, etc.), a fluidity adjusting agent (thixotropic agent, thickener, etc.), a film-forming aid, an interface, if necessary. Additives such as activators (defoaming agents, dispersants, etc.), preservatives and the like may be contained.
<トップコート層の帯電防止成分>
トップコート層の好ましい実施形態は、帯電防止成分を含有する。帯電防止成分としては、粘着フィルムの帯電を防止または抑制する作用を発揮し得る成分である。トップコート層に帯電防止成分を含有させる場合、その帯電防止成分としては、例えば、有機または無機の導電性物質、各種の帯電防止剤等を用いることができる。また、前述の帯電防止層で使用され得る帯電防止剤を使用することも可能である。 <Antistatic component of top coat layer>
A preferred embodiment of the topcoat layer contains an antistatic component. The antistatic component is a component capable of exhibiting the action of preventing or suppressing the charge of the adhesive film. When the top coat layer contains an antistatic component, as the antistatic component, for example, an organic or inorganic conductive substance, various antistatic agents, etc. can be used. It is also possible to use antistatic agents which can be used in the antistatic layers mentioned above.
トップコート層の好ましい実施形態は、帯電防止成分を含有する。帯電防止成分としては、粘着フィルムの帯電を防止または抑制する作用を発揮し得る成分である。トップコート層に帯電防止成分を含有させる場合、その帯電防止成分としては、例えば、有機または無機の導電性物質、各種の帯電防止剤等を用いることができる。また、前述の帯電防止層で使用され得る帯電防止剤を使用することも可能である。 <Antistatic component of top coat layer>
A preferred embodiment of the topcoat layer contains an antistatic component. The antistatic component is a component capable of exhibiting the action of preventing or suppressing the charge of the adhesive film. When the top coat layer contains an antistatic component, as the antistatic component, for example, an organic or inorganic conductive substance, various antistatic agents, etc. can be used. It is also possible to use antistatic agents which can be used in the antistatic layers mentioned above.
有機導電性物質としては、4級アンモニウム塩、ピリジニウム塩、第1アミノ基、第2アミノ基、第3アミノ基等のカチオン性官能基を有するカチオン型帯電防止剤;スルホン酸塩や硫酸エステル塩、ホスホン酸塩、リン酸エステル塩等のアニオン性官能基を有するアニオン型帯電防止剤;アルキルベタインおよびその誘導体、イミダゾリンおよびその誘導体、アラニンおよびその誘導体等の両性イオン型帯電防止剤;アミノアルコールおよびその誘導体、グリセリンおよびその誘導体、ポリエチレングリコールおよびその誘導体等のノニオン型帯電防止剤;上記カチオン型、アニオン型、両性イオン型のイオン導電性基(例えば、4級アンモニウム塩基)を有するモノマーを重合もしくは共重合して得られたイオン導電性重合体;ポリチオフェン、ポリアニリン、ポリピロール、ポリエチレンイミン、アリルアミン系重合体等の導電性ポリマー;などが挙げられる。このような帯電防止剤は、1種のみであってもよいし、2種以上であってもよい。
As the organic conductive substance, a quaternary ammonium salt, a pyridinium salt, a cationic antistatic agent having a cationic functional group such as a primary amino group, a secondary amino group, and a tertiary amino group; a sulfonate or a sulfate ester salt. , Phosphonate, phosphate ester and other anionic antistatic agents having anionic functional groups; alkylbetaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives, etc. zwitterionic antistatic agents; amino alcohols and Nonionic antistatic agents such as derivatives thereof, glycerin and derivatives thereof, polyethylene glycol and derivatives thereof; polymerization of monomers having the above-mentioned cation-type, anion-type, and zwitterion-type ion conductive groups (for example, quaternary ammonium salt groups) or Ion conductive polymers obtained by copolymerization; conductive polymers such as polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine polymers; and the like. Only one kind of such antistatic agent may be used, or two or more kinds thereof may be used.
無機導電性物質としては、例えば、酸化錫、酸化アンチモン、酸化インジウム、酸化カドミウム、酸化チタン、酸化亜鉛、インジウム、錫、アンチモン、金、銀、銅、アルミニウム、ニッケル、クロム、チタン、鉄、コバルト、ヨウ化銅、ITO(酸化インジウム/酸化錫)、ATO(酸化アンチモン/酸化錫)などが挙げられる。このような無機導電性物質は、1種のみであってもよいし、2種以上であってもよい。
Examples of the inorganic conductive substance include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron and cobalt. , Copper iodide, ITO (indium oxide/tin oxide), ATO (antimony oxide/tin oxide), and the like. Only one kind of such inorganic conductive material may be used, or two or more kinds thereof may be used.
帯電防止剤の例としては、カチオン型帯電防止剤、アニオン型帯電防止剤、両性イオン型帯電防止剤、ノニオン型帯電防止剤、上記カチオン型、アニオン型、両性イオン型のイオン導電性基を有する単量体を重合もしくは共重合して得られたイオン導電性重合体、などが挙げられる。
Examples of the antistatic agent include a cationic antistatic agent, an anionic antistatic agent, a zwitterionic antistatic agent, a nonionic antistatic agent, and the above-mentioned cationic, anionic, and zwitterionic ionically conductive groups. Examples thereof include ion conductive polymers obtained by polymerizing or copolymerizing monomers.
トップコート層が帯電防止成分を含有する場合、好ましくは、帯電防止成分が有機導電性物質を含む。有機導電性物質としては、各種の導電性ポリマーを好ましく用いることができる。このような構成によると、良好な帯電防止性と高い耐スクラッチ性とを両立させ得る。
When the top coat layer contains an antistatic component, the antistatic component preferably contains an organic conductive substance. As the organic conductive substance, various conductive polymers can be preferably used. With such a configuration, both good antistatic properties and high scratch resistance can be achieved.
導電性ポリマーとしては、例えば、ポリチオフェン、ポリアニリン、ポリピロール、ポリエチレンイミン、アリルアミン系重合体などが挙げられる。このような導電性ポリマーは、1種のみであってもよいし、2種以上であってもよい。また、他の帯電防止成分(無機導電性物質、帯電防止剤等)と組み合わせて用いてもよい。
Examples of conductive polymers include polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine-based polymers. Only one kind of such conductive polymer may be used, or two or more kinds thereof may be used. It may also be used in combination with other antistatic components (inorganic conductive substances, antistatic agents, etc.).
導電性ポリマーの使用量は、トップコート層に含まれるバインダ100重量部に対して、好ましくは1重量部~100重量部であり、より好ましくは2重量部~70重量部であり、さらに好ましくは3重量部~50重量部である。導電性ポリマーの使用量が少なすぎると、帯電防止効果が小さくなるおそれある。導電性ポリマーの使用量が多すぎると、トップコート層における導電性ポリマーの相溶性が不足気味となって、トップコート層の外観品位が低下したり、耐溶剤性が低下したりするおそれがある。
The amount of the conductive polymer used is preferably 1 part by weight to 100 parts by weight, more preferably 2 parts by weight to 70 parts by weight, and further preferably 100 parts by weight of the binder contained in the top coat layer. It is 3 to 50 parts by weight. If the amount of the conductive polymer used is too small, the antistatic effect may be reduced. If the amount of the conductive polymer used is too large, the compatibility of the conductive polymer in the topcoat layer tends to be insufficient, and the appearance quality of the topcoat layer may deteriorate or the solvent resistance may decrease. ..
導電性ポリマーとしては、好ましくは、ポリチオフェン、ポリアニリンが挙げられる。ポリチオフェンとしては、ポリスチレン換算の重量平均分子量Mwが、好ましくは40×104以下であり、より好ましくは30×104以下である。ポリアニリンとしては、ポリスチレン換算の重量平均分子量Mwが、好ましくは50×104以下であり、より好ましくは30×104以下である。導電性ポリマーのポリスチレン換算の重量平均分子量Mwは、好ましくは0.1×104以上であり、より好ましくは0.5×104以上である。なお、本明細書中においてポリチオフェンとは、無置換または置換チオフェンの重合体をいう。置換チオフェン重合体としては、例えば、ポリ(3,4-エチレンジオキシチオフェン)などが挙げられる。
The conductive polymer is preferably polythiophene or polyaniline. The polythiophene has a polystyrene-equivalent weight average molecular weight Mw of preferably 40×10 4 or less, more preferably 30×10 4 or less. The polyaniline has a polystyrene-equivalent weight average molecular weight Mw of preferably 50×10 4 or less, more preferably 30×10 4 or less. The polystyrene-equivalent weight average molecular weight Mw of the conductive polymer is preferably 0.1×10 4 or more, more preferably 0.5×10 4 or more. In this specification, polythiophene refers to a polymer of unsubstituted or substituted thiophene. Examples of the substituted thiophene polymer include poly(3,4-ethylenedioxythiophene).
トップコート層を形成する方法としては、トップコート層形成用のコーティング材を基材に塗付して乾燥または硬化させる方法を採用する場合、該コーティング材の調製に用いる導電性ポリマーとしては、該導電性ポリマーが水に溶解または分散した形態のもの(導電性ポリマー水溶液)を好ましく使用し得る。このような導電性ポリマー水溶液は、例えば、親水性官能基を有する導電性ポリマー(分子内に親水性官能基を有するモノマーを共重合させる等の手法により合成され得る導電性ポリマー)を水に溶解または分散させることにより調製することができる。上記親水性官能基としては、スルホ基、アミノ基、アミド基、イミノ基、ヒドロキシル基、メルカプト基、ヒドラジノ基、カルボキシル基、四級アンモニウム基、硫酸エステル基(-O-SO3H)、リン酸エステル基(例えば-O-PO(OH)2)などが挙げられる。このような親水性官能基は、塩を形成していてもよい。ポリチオフェン水溶液の市販品としては、例えば、ナガセケムテック社製の商品名「デナトロン」シリーズなどが挙げられる。ポリアニリンスルホン酸水溶液の市販品としては、例えば、三菱レイヨン社製の商品名「aqua-PASS」などが挙げられる。
As a method for forming the topcoat layer, when a method of applying a coating material for forming a topcoat layer to a substrate and drying or curing is adopted, as the conductive polymer used for preparing the coating material, A conductive polymer dissolved or dispersed in water (conductive polymer aqueous solution) can be preferably used. Such a conductive polymer aqueous solution is prepared by, for example, dissolving a conductive polymer having a hydrophilic functional group (a conductive polymer that can be synthesized by a method such as copolymerizing a monomer having a hydrophilic functional group in the molecule) in water. Alternatively, it can be prepared by dispersing. Examples of the hydrophilic functional group include sulfo group, amino group, amide group, imino group, hydroxyl group, mercapto group, hydrazino group, carboxyl group, quaternary ammonium group, sulfuric acid ester group (—O—SO 3 H), phosphorus Examples thereof include acid ester groups (eg, —O—PO(OH) 2 ). Such a hydrophilic functional group may form a salt. Examples of commercially available polythiophene aqueous solution include "Denatron" series manufactured by Nagase Chemtec Co., Ltd. Examples of commercial products of the polyaniline sulfonic acid aqueous solution include trade name “aqua-PASS” manufactured by Mitsubishi Rayon Co., Ltd.
コーティング材の調製においては、好ましくは、ポリチオフェン水溶液を使用する。ポリチオフェン水溶液としては、ポリスチレンスルホネート(PSS)を含むポリチオフェン水溶液(例えば、ポリチオフェンにPSSがドーパントとして添加された形態)が好ましい。このようなポリチオフェン水溶液は、ポリチオフェン:PSSを、好ましくは1:1~1:10の質量比で含有するものであり得る。このようなポリチオフェン水溶液におけるポリチオフェンとPSSとの合計含有量は、好ましくは1質量%~5重量%である。このようなポリチオフェン水溶液の市販品としては、例えば、H.C.Stark社の商品名「ベイトロン(Baytron)」などが挙げられる。なお、上記のようにPSSを含むポリチオフェン水溶液を用いる場合には、ポリチオフェンとPSSとの合計量が、バインダ100重量部に対して、好ましくは5重量部~200重量部であり、より好ましくは10重量部~100重量部であり、さらに好ましくは25重量部~70重量部である。
In the preparation of the coating material, it is preferable to use an aqueous polythiophene solution. As the polythiophene aqueous solution, a polythiophene aqueous solution containing polystyrene sulfonate (PSS) (for example, a form in which PSS is added as a dopant to polythiophene) is preferable. Such an aqueous polythiophene solution may contain polythiophene:PSS, preferably in a mass ratio of 1:1 to 1:10. The total content of polythiophene and PSS in such an aqueous polythiophene solution is preferably 1% by mass to 5% by mass. Examples of commercial products of such polythiophene aqueous solution include H.I. C. The trade name “Baytron” of Stark and the like can be mentioned. When the polythiophene aqueous solution containing PSS is used as described above, the total amount of polythiophene and PSS is preferably 5 parts by weight to 200 parts by weight, and more preferably 10 parts by weight with respect to 100 parts by weight of the binder. It is from 100 to 100 parts by weight, and more preferably from 25 to 70 parts by weight.
トップコート層は、必要に応じて、導電性ポリマーと、他の1種以上の帯電防止成分(導電性ポリマー以外の有機導電性物質、無機導電性物質、帯電防止剤など)とを共に含んでいてもよい。好ましくは、トップコート層が、導電性ポリマー以外の帯電防止成分を実質的に含有しない。すなわち、トップコート層に含まれる帯電防止成分が実質的に導電性ポリマーのみからなることが好ましい。
The topcoat layer optionally contains a conductive polymer and one or more other antistatic components (organic conductive substances other than conductive polymers, inorganic conductive substances, antistatic agents, etc.) together. You may stay. Preferably, the top coat layer contains substantially no antistatic component other than the conductive polymer. That is, it is preferable that the antistatic component contained in the topcoat layer consists essentially of a conductive polymer.
<架橋剤>
トップコート層は、好ましくは、架橋剤を含有する。架橋剤としては、一般的な樹脂の架橋に用いられるメラミン系架橋剤、イソシアネート系架橋剤、エポキシ系架橋剤等の架橋剤を適宜選択して用いることができる。このような架橋剤を用いることにより、耐スクラッチ性の向上、耐溶剤性の向上、印字密着性の向上、摩擦係数の低下(すなわち、滑り性の向上)、のうち少なくとも1つの効果が実現され得る。好ましくは、架橋剤がメラミン系架橋剤を含む。架橋剤が実質的にメラミン系架橋剤(メラミン系樹脂)のみからなる(すなわち、メラミン系架橋剤以外の架橋剤を実質的に含有しない)トップコート層であってもよい。 <Crosslinking agent>
The top coat layer preferably contains a crosslinking agent. As the cross-linking agent, a cross-linking agent such as a melamine-based cross-linking agent, an isocyanate-based cross-linking agent, or an epoxy-based cross-linking agent that is used for cross-linking general resins can be appropriately selected and used. By using such a cross-linking agent, at least one of the effects of improved scratch resistance, improved solvent resistance, improved print adhesion, and reduced friction coefficient (that is, improved slippage) is realized. obtain. Preferably, the cross-linking agent comprises a melamine-based cross-linking agent. It may be a top coat layer in which the cross-linking agent substantially consists of a melamine-based cross-linking agent (melamine-based resin) (that is, does not substantially contain a cross-linking agent other than the melamine-based cross-linking agent).
トップコート層は、好ましくは、架橋剤を含有する。架橋剤としては、一般的な樹脂の架橋に用いられるメラミン系架橋剤、イソシアネート系架橋剤、エポキシ系架橋剤等の架橋剤を適宜選択して用いることができる。このような架橋剤を用いることにより、耐スクラッチ性の向上、耐溶剤性の向上、印字密着性の向上、摩擦係数の低下(すなわち、滑り性の向上)、のうち少なくとも1つの効果が実現され得る。好ましくは、架橋剤がメラミン系架橋剤を含む。架橋剤が実質的にメラミン系架橋剤(メラミン系樹脂)のみからなる(すなわち、メラミン系架橋剤以外の架橋剤を実質的に含有しない)トップコート層であってもよい。 <Crosslinking agent>
The top coat layer preferably contains a crosslinking agent. As the cross-linking agent, a cross-linking agent such as a melamine-based cross-linking agent, an isocyanate-based cross-linking agent, or an epoxy-based cross-linking agent that is used for cross-linking general resins can be appropriately selected and used. By using such a cross-linking agent, at least one of the effects of improved scratch resistance, improved solvent resistance, improved print adhesion, and reduced friction coefficient (that is, improved slippage) is realized. obtain. Preferably, the cross-linking agent comprises a melamine-based cross-linking agent. It may be a top coat layer in which the cross-linking agent substantially consists of a melamine-based cross-linking agent (melamine-based resin) (that is, does not substantially contain a cross-linking agent other than the melamine-based cross-linking agent).
<トップコート層の一つの好ましい態様>
トップコート層の一つの好ましい態様は、基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種である場合、該トップコート層がウレタン系樹脂を含むバインダおよび帯電防止成分を含有する態様である。このように、トップコート層の帯電防止成分のバインダとしてウレタン系樹脂を含むバインダを採用することにより、ポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種を材料とする基材層の表面へのトップコート層の塗布形成性が優れるようになり、外観が良好なものとなり得るとともに、優れた帯電防止性を発現し得る。 <One preferable embodiment of the top coat layer>
In one preferred embodiment of the top coat layer, when the material of the base material layer is at least one selected from polyimide and polyether ether ketone, the top coat layer contains a binder containing a urethane resin and an antistatic component. It is a mode. In this way, by using a binder containing a urethane resin as the binder of the antistatic component of the top coat layer, the top surface of the base material layer made of at least one selected from polyimide and polyether ether ketone is used. The coatability of the coat layer becomes excellent, the appearance may be good, and the excellent antistatic property may be exhibited.
トップコート層の一つの好ましい態様は、基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種である場合、該トップコート層がウレタン系樹脂を含むバインダおよび帯電防止成分を含有する態様である。このように、トップコート層の帯電防止成分のバインダとしてウレタン系樹脂を含むバインダを採用することにより、ポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種を材料とする基材層の表面へのトップコート層の塗布形成性が優れるようになり、外観が良好なものとなり得るとともに、優れた帯電防止性を発現し得る。 <One preferable embodiment of the top coat layer>
In one preferred embodiment of the top coat layer, when the material of the base material layer is at least one selected from polyimide and polyether ether ketone, the top coat layer contains a binder containing a urethane resin and an antistatic component. It is a mode. In this way, by using a binder containing a urethane resin as the binder of the antistatic component of the top coat layer, the top surface of the base material layer made of at least one selected from polyimide and polyether ether ketone is used. The coatability of the coat layer becomes excellent, the appearance may be good, and the excellent antistatic property may be exhibited.
トップコート層の帯電防止成分のバインダとしては、ポリエステル樹脂を含むバインダが好ましい場合が多いが、基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種という特定の基材層に対しては、ポリエステル樹脂を含むバインダの親和性が低いことがあり、トップコート層の塗布形成後の外観が悪くなるおそれや、優れた帯電防止性を発現できないおそれがある。上記のように、基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種である場合、該トップコート層がウレタン系樹脂を含むバインダおよび帯電防止成分を含有する態様とすれば、基材層の表面へのトップコート層の塗布形成性が優れるようになり、外観が良好なものとなり得るとともに、優れた帯電防止性を発現し得る。
As the binder of the antistatic component of the topcoat layer, a binder containing a polyester resin is often preferable, but the material for the base material layer is at least one selected from polyimide and polyetheretherketone for a specific base material layer. In some cases, the binder containing the polyester resin may have a low affinity, and the appearance of the topcoat layer after coating and forming may be deteriorated, or the excellent antistatic property may not be exhibited. As described above, when the material of the base material layer is at least one selected from polyimide and polyetheretherketone, if the top coat layer contains a binder containing a urethane resin and an antistatic component, The coatability of the topcoat layer on the surface of the base material layer becomes excellent, the appearance may be good, and the excellent antistatic property may be exhibited.
<トップコート層の形成>
トップコート層は、上記樹脂成分および必要に応じて使用される添加剤が適当な溶媒に分散または溶解した液状組成物(トップコート層形成用コーティング材)を基材に付与することを含む手法によって好適に形成され得る。例えば、上記コーティング材を基材の第一面に塗付して乾燥させ、必要に応じて硬化処理(熱処理、紫外線処理など)を行う手法を好ましく採用し得る。上記コーティング材のNV(不揮発分)は、好ましくは5重量%以下であり、より好ましくは0.05重量%~5重量%であり、さらに好ましくは0.05重量%~1重量%であり、特に好ましくは0.10重量%~1重量%である。厚みの小さいトップコート層を形成する場合には、上記コーティング材のNVを、好ましくは0.05重量%~0.50重量%とし、より好ましくは0.10重量%~0.30重量%とする。このように低NVのコーティング材を用いることにより、より均一なトップコート層が形成され得る。 <Formation of top coat layer>
The topcoat layer is formed by a method including applying a liquid composition (a coating material for forming a topcoat layer) in which the above resin components and additives used as necessary are dispersed or dissolved in a suitable solvent to a substrate. It can be suitably formed. For example, a method in which the above-mentioned coating material is applied to the first surface of a base material, dried, and if necessary, a curing treatment (heat treatment, ultraviolet treatment, etc.) can be preferably adopted. The NV (nonvolatile content) of the coating material is preferably 5% by weight or less, more preferably 0.05% by weight to 5% by weight, further preferably 0.05% by weight to 1% by weight, Particularly preferably, it is 0.10% by weight to 1% by weight. When forming a thin topcoat layer, the NV of the coating material is preferably 0.05% by weight to 0.50% by weight, and more preferably 0.10% by weight to 0.30% by weight. To do. By using the low NV coating material as described above, a more uniform top coat layer can be formed.
トップコート層は、上記樹脂成分および必要に応じて使用される添加剤が適当な溶媒に分散または溶解した液状組成物(トップコート層形成用コーティング材)を基材に付与することを含む手法によって好適に形成され得る。例えば、上記コーティング材を基材の第一面に塗付して乾燥させ、必要に応じて硬化処理(熱処理、紫外線処理など)を行う手法を好ましく採用し得る。上記コーティング材のNV(不揮発分)は、好ましくは5重量%以下であり、より好ましくは0.05重量%~5重量%であり、さらに好ましくは0.05重量%~1重量%であり、特に好ましくは0.10重量%~1重量%である。厚みの小さいトップコート層を形成する場合には、上記コーティング材のNVを、好ましくは0.05重量%~0.50重量%とし、より好ましくは0.10重量%~0.30重量%とする。このように低NVのコーティング材を用いることにより、より均一なトップコート層が形成され得る。 <Formation of top coat layer>
The topcoat layer is formed by a method including applying a liquid composition (a coating material for forming a topcoat layer) in which the above resin components and additives used as necessary are dispersed or dissolved in a suitable solvent to a substrate. It can be suitably formed. For example, a method in which the above-mentioned coating material is applied to the first surface of a base material, dried, and if necessary, a curing treatment (heat treatment, ultraviolet treatment, etc.) can be preferably adopted. The NV (nonvolatile content) of the coating material is preferably 5% by weight or less, more preferably 0.05% by weight to 5% by weight, further preferably 0.05% by weight to 1% by weight, Particularly preferably, it is 0.10% by weight to 1% by weight. When forming a thin topcoat layer, the NV of the coating material is preferably 0.05% by weight to 0.50% by weight, and more preferably 0.10% by weight to 0.30% by weight. To do. By using the low NV coating material as described above, a more uniform top coat layer can be formed.
トップコート層形成用コーティング材を構成する溶媒としては、トップコート層形成成分を安定して溶解または分散し得るものが好ましい。このような溶媒は、有機溶剤、水、またはこれらの混合溶媒であり得る。有機溶剤としては、例えば、酢酸エチル等のエステル類;メチルエチルケトン、アセトン、シクロヘキサノン等のケトン類;テトラヒドロフラン(THF)、ジオキサン等の環状エーテル類;n-ヘキサン、シクロヘキサン等の脂肪族または脂環族炭化水素類;トルエン、キシレン等の芳香族炭化水素類;メタノール、エタノール、n-プロパノール、イソプロパノール、シクロヘキサノール等の脂肪族または脂環族アルコール類;アルキレングリコールモノアルキルエーテル(例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル)、ジアルキレングリコールモノアルキルエーテル等のグリコールエーテル類;などから選択される少なくとも1種が挙げられる。好ましくは、トップコート層形成用コーティング材を構成する溶媒が、水または水を主成分とする混合溶媒(例えば、水とエタノールとの混合溶媒)である。
As the solvent that constitutes the coating material for forming the top coat layer, one that can stably dissolve or disperse the components forming the top coat layer is preferable. Such a solvent may be an organic solvent, water, or a mixed solvent thereof. Examples of the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic carbonization such as n-hexane and cyclohexane. Hydrogens; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol; alkylene glycol monoalkyl ethers (eg ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether), glycol ethers such as dialkylene glycol monoalkyl ether; and the like. Preferably, the solvent constituting the coating material for forming the topcoat layer is water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
<トップコート層の性状>
トップコート層の厚さは、好ましくは3nm~500nmであり、より好ましくは3nm~100nmであり、さらに好ましくは3nm~60nmである。トップコート層の厚みが大きすぎると、粘着フィルムの透明性(光線透過性)が低下しやすくなるおそれがある。トップコート層の厚みが小さすぎると、トップコート層を均一に形成することが困難となるおそれがあり、例えば、トップコート層の厚みにおいて、場所による厚みのバラツキが大きくなるおそれがあり、このため、粘着フィルムの外観にムラが生じやすくなるおそれがある。 <Properties of top coat layer>
The thickness of the top coat layer is preferably 3 nm to 500 nm, more preferably 3 nm to 100 nm, and further preferably 3 nm to 60 nm. If the thickness of the top coat layer is too large, the transparency (light transmittance) of the pressure-sensitive adhesive film may be likely to decrease. If the thickness of the top coat layer is too small, it may be difficult to uniformly form the top coat layer, and for example, in the thickness of the top coat layer, there may be a large variation in thickness depending on the location. However, the appearance of the pressure-sensitive adhesive film may be likely to be uneven.
トップコート層の厚さは、好ましくは3nm~500nmであり、より好ましくは3nm~100nmであり、さらに好ましくは3nm~60nmである。トップコート層の厚みが大きすぎると、粘着フィルムの透明性(光線透過性)が低下しやすくなるおそれがある。トップコート層の厚みが小さすぎると、トップコート層を均一に形成することが困難となるおそれがあり、例えば、トップコート層の厚みにおいて、場所による厚みのバラツキが大きくなるおそれがあり、このため、粘着フィルムの外観にムラが生じやすくなるおそれがある。 <Properties of top coat layer>
The thickness of the top coat layer is preferably 3 nm to 500 nm, more preferably 3 nm to 100 nm, and further preferably 3 nm to 60 nm. If the thickness of the top coat layer is too large, the transparency (light transmittance) of the pressure-sensitive adhesive film may be likely to decrease. If the thickness of the top coat layer is too small, it may be difficult to uniformly form the top coat layer, and for example, in the thickness of the top coat layer, there may be a large variation in thickness depending on the location. However, the appearance of the pressure-sensitive adhesive film may be likely to be uneven.
トップコート層の厚みは、トップコート層の断面を透過型電子顕微鏡(TEM)にて観察することにより把握することができる。例えば、目的の試料(トップコート層が形成された基材や、基材を備える粘着フィルムなど)について、トップコート層を明瞭にする目的で重金属染色処理を行った後、樹脂包埋を行い、超薄切片法により試料断面のTEM観察を行って得られる結果を、トップコート層の厚さとして好ましく採用することができる。TEMとしては、例えば、日立社製のTEM(型式「H-7650」)などを用いることができる。後述する実施例では、加速電圧:100kV、倍率:60,000倍の条件で得られた断面画像について、二値化処理を行った後、視野内のサンプル長さでトップコートの断面積を除算することでトップコート層の厚み(視野内の平均厚み)を実測している。なお、重金属染色を行わなくてもトップコート層を十分明瞭に観察し得る場合には、重金属染色処理を省略してもよい。あるいは、TEMにより把握される厚みと、各種の厚み検出装置(例えば、表面粗さ計、干渉厚み計、赤外分光測定機、各種X線回折装置等)による検出結果との相関につき、検量線を作成して計算を行うことにより、トップコート層の厚みを求めてもよい。
The thickness of the top coat layer can be understood by observing the cross section of the top coat layer with a transmission electron microscope (TEM). For example, for a target sample (a base material having a top coat layer formed thereon, an adhesive film including a base material, etc.), a heavy metal dyeing treatment is performed for the purpose of clarifying the top coat layer, followed by resin embedding, The result obtained by TEM observation of the cross section of the sample by the ultrathin section method can be preferably adopted as the thickness of the topcoat layer. As the TEM, for example, a TEM (model “H-7650”) manufactured by Hitachi, Ltd. can be used. In Examples described later, a cross-sectional image obtained under the conditions of accelerating voltage: 100 kV and magnification: 60,000 times was binarized, and then the cross-sectional area of the top coat was divided by the sample length in the visual field. By doing so, the thickness of the top coat layer (average thickness in the visual field) is measured. The heavy metal dyeing process may be omitted if the topcoat layer can be observed sufficiently clearly without heavy metal dyeing. Alternatively, there is a calibration curve for the correlation between the thickness grasped by the TEM and the detection result by various thickness detection devices (for example, surface roughness meter, interference thickness meter, infrared spectrophotometer, various X-ray diffractometers, etc.). The thickness of the top coat layer may be determined by preparing the above and calculating.
トップコート層の表面において測定される表面抵抗率は、好ましくは1012Ω以下であり、より好ましくは104Ω~1012Ωであり、さらに好ましくは104Ω~1011Ωであり、特に好ましくは5×104Ω~1010Ωであり、最も好ましくは104Ω~109Ωである。このような表面抵抗率を示す粘着フィルムは、例えば、液晶セルや半導体装置等のように静電気を嫌う物品の加工または搬送過程等において使用される粘着フィルムとして好適に利用され得る。表面抵抗率の値は、市販の絶縁抵抗測定装置を用いて、23℃、50%RHの雰囲気下で測定される表面抵抗の値から算出することができる。
The surface resistivity measured on the surface of the top coat layer is preferably 10 12 Ω or less, more preferably 10 4 Ω to 10 12 Ω, further preferably 10 4 Ω to 10 11 Ω, and particularly preferably It is preferably 5×10 4 Ω to 10 10 Ω, and most preferably 10 4 Ω to 10 9 Ω. The pressure-sensitive adhesive film having such a surface resistivity can be suitably used as a pressure-sensitive adhesive film used, for example, in the processing or transportation process of articles such as liquid crystal cells and semiconductor devices that are sensitive to static electricity. The surface resistivity value can be calculated from the surface resistance value measured in an atmosphere of 23° C. and 50% RH using a commercially available insulation resistance measuring device.
トップコート層の摩擦係数は、好ましくは0.4以下である。このように摩擦係数の低いトップコート層とすると、トップコート層に荷重(スクラッチ傷を生じさせるような荷重)が加わった場合に、その荷重をトップコート層の表面に沿って受け流し、荷重による摩擦力を軽減することができる。このことによって、トップコート層の凝集破壊(トップコート層がその内部で破壊する損傷態様)や界面破壊(トップコート層が基材背面から剥がれる損傷態様)が起こりにくくなる。したがって、粘着フィルムにスクラッチ傷を生じる事象をより防止することができる。摩擦係数の下限としては、他の特性(例えば、外観品位や印字性など)とのバランスを考慮して、好ましくは0.1以上であり、より好ましくは0.15以上である。摩擦係数としては、例えば、23℃、50%RHの測定環境下において、トップコート層の表面を垂直荷重40mNで擦過して求められる値を採用することができる。滑り剤の使用量は、好ましい摩擦係数が実現されるように設定するとよい。摩擦係数の調整には、例えば、架橋剤の添加や成膜条件の調整によりトップコート層の架橋密度を高めることも有効である。
The friction coefficient of the top coat layer is preferably 0.4 or less. When a top coat layer with a low coefficient of friction is used in this way, when a load (a load that causes scratches) is applied to the top coat layer, the load is received along the surface of the top coat layer and the friction caused by the load The power can be reduced. As a result, cohesive failure of the topcoat layer (damage mode in which the topcoat layer breaks inside) and interface failure (damage mode in which the topcoat layer peels from the back surface of the substrate) are less likely to occur. Therefore, it is possible to further prevent the occurrence of scratches on the adhesive film. The lower limit of the coefficient of friction is preferably 0.1 or more, more preferably 0.15 or more, in consideration of the balance with other characteristics (for example, appearance quality and printability). As the friction coefficient, for example, a value obtained by rubbing the surface of the top coat layer with a vertical load of 40 mN under a measurement environment of 23° C. and 50% RH can be adopted. The amount of the slip agent used may be set so that a preferable coefficient of friction is realized. For adjusting the friction coefficient, it is also effective to increase the crosslink density of the topcoat layer by adding a crosslinker or adjusting film forming conditions.
粘着フィルムは、その背面(トップコート層の表面)が、油性インキにより(例えば、油性マーキングペンを用いて)容易に印字できる性質を有することが好ましい。このような粘着フィルムは、該粘着フィルムを貼り付けた状態で行われる被着体(例えば、光学部品)の加工や搬送等の過程において、保護対象たる被着体の識別番号等を上記粘着フィルムに記載して表示することに適している。したがって、外観品位に加えて印字性にも優れた表面保護フィルムが好ましい。例えば、溶剤がアルコール系であって顔料を含むタイプの油性インキに対して高い印字性を有することが好ましい。また、印字されたインキが擦れや転着により取れにくい(すなわち、印字密着性に優れる)ことが好ましい。粘着フィルムは、印字を修正または消去する際に該印字をアルコール(例えば、エチルアルコール)で拭き取っても外観に目立った変化を生じない程度の耐溶剤性を有することが好ましい。
It is preferable that the back surface (surface of the top coat layer) of the adhesive film has a property that it can be easily printed with an oil-based ink (for example, using an oil-based marking pen). In such a pressure-sensitive adhesive film, the identification number or the like of the adherend to be protected in the process of processing or transporting the adherend (for example, an optical component) that is performed with the pressure-sensitive adhesive film attached, It is suitable for displaying and displaying. Therefore, a surface protective film having excellent printability in addition to appearance quality is preferable. For example, it is preferable that the solvent is alcoholic and has high printability with respect to an oil-based ink of a type including a pigment. Further, it is preferable that the printed ink is difficult to be removed due to rubbing or transfer (that is, the printing adhesion is excellent). The pressure-sensitive adhesive film preferably has solvent resistance to the extent that when the print is corrected or erased, the print is wiped off with alcohol (for example, ethyl alcohol) so that the appearance is not significantly changed.
トップコート層は、好ましくは、滑り剤としてのワックスエステルを含有するため、トップコート層の表面にさらなる剥離処理(例えば、シリコーン系剥離剤や長鎖アルキル系剥離剤などの任意の適切な剥離処理剤を塗付して乾燥させる処理)を施さない態様においても、十分な滑り性(例えば、上述した好ましい摩擦係数)を実現し得る。このようにトップコート層の表面にさらなる剥離処理が施されていない態様は、剥離処理剤に起因する白化(例えば、加熱加湿条件下に保存されることによる白化)を未然に防止し得るなどの点で好ましい。また、耐溶剤性の点からも有利である。
The topcoat layer preferably contains a wax ester as a slip agent, so that the surface of the topcoat layer is subjected to further release treatment (for example, any suitable release treatment such as a silicone-based release agent or a long-chain alkyl-based release agent). Sufficient slipperiness (for example, the above-mentioned preferable friction coefficient) can be realized even in a mode in which the treatment of applying the agent and drying is not performed. In this manner, the embodiment in which the surface of the top coat layer is not further subjected to the peeling treatment can prevent the whitening (for example, the whitening due to the storage under the heating and humidifying conditions) caused by the peeling treatment agent. It is preferable in terms. It is also advantageous in terms of solvent resistance.
粘着フィルムは、基材、粘着剤層、及び、トップコート層に加えて、さらに他の層を含む態様でも実施され得る。かかる「他の層」の配置としては、基材の第一面(背面)とトップコート層との間、基材の第二面(前面)と粘着剤層との間等が例示される。基材背面とトップコート層との間に配置される層は、例えば、帯電防止成分を含む層(帯電防止層)であり得る。基材前面と粘着剤層との間に配置される層は、例えば、上記第二面に対する粘着剤層の投錨性を高める下塗り層(アンカー層)、帯電防止層等であり得る。基材前面に帯電防止層が配置され、該帯電防止層の上にアンカー層が配置され、その上に粘着剤層が配置された構成の粘着フィルムであってもよい。
The pressure-sensitive adhesive film may be embodied in a mode including other layers in addition to the base material, the pressure-sensitive adhesive layer, and the top coat layer. Examples of the arrangement of the "other layer" include between the first surface (back surface) of the base material and the top coat layer, between the second surface (front surface) of the base material and the adhesive layer, and the like. The layer arranged between the back surface of the substrate and the topcoat layer can be, for example, a layer containing an antistatic component (antistatic layer). The layer arranged between the front surface of the substrate and the pressure-sensitive adhesive layer may be, for example, an undercoat layer (anchor layer) that enhances the anchoring property of the pressure-sensitive adhesive layer to the second surface, an antistatic layer, or the like. The pressure-sensitive adhesive film may have a structure in which an antistatic layer is disposed on the front surface of a substrate, an anchor layer is disposed on the antistatic layer, and a pressure-sensitive adhesive layer is disposed thereon.
≪≪フォルダブルデバイスおよびローラブルデバイス≫≫
本発明の粘着フィルムは、屈曲性および透明性に優れるので、例えば、可動屈曲部を有するベンダブルデバイス(曲げることが可能なデバイス)やフォルダブルデバイス(折りたたむことが可能なデバイス)やローラブルデバイス(丸めることが可能なデバイス)に好適に備えられ得る。本発明の粘着フィルムは、特に、屈曲性および透明性に優れるので、これまで適用がより難しかったフォルダブルデバイス(折りたたむことが可能なデバイス)やローラブルデバイス(丸めることが可能なデバイス)に好適に備えられ得る。 ≪<<Foldable devices and Rollable devices>>»
Since the pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, for example, a bendable device (a bendable device), a foldable device (a foldable device), or a rollable device (having a movable bending portion) (a bendable device). It is suitable for a rollable device). The pressure-sensitive adhesive film of the present invention is particularly excellent in flexibility and transparency, and thus is suitable for a foldable device (foldable device) and a rollable device (rollable device) that have been difficult to apply until now. Can be prepared for.
本発明の粘着フィルムは、屈曲性および透明性に優れるので、例えば、可動屈曲部を有するベンダブルデバイス(曲げることが可能なデバイス)やフォルダブルデバイス(折りたたむことが可能なデバイス)やローラブルデバイス(丸めることが可能なデバイス)に好適に備えられ得る。本発明の粘着フィルムは、特に、屈曲性および透明性に優れるので、これまで適用がより難しかったフォルダブルデバイス(折りたたむことが可能なデバイス)やローラブルデバイス(丸めることが可能なデバイス)に好適に備えられ得る。 ≪<<Foldable devices and Rollable devices>>»
Since the pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, for example, a bendable device (a bendable device), a foldable device (a foldable device), or a rollable device (having a movable bending portion) (a bendable device). It is suitable for a rollable device). The pressure-sensitive adhesive film of the present invention is particularly excellent in flexibility and transparency, and thus is suitable for a foldable device (foldable device) and a rollable device (rollable device) that have been difficult to apply until now. Can be prepared for.
本発明のフォルダブルデバイスは、本発明の粘着フィルムを備える。本発明のフォルダブルデバイスは、本発明の粘着フィルムを備えていれば、任意の適切な他の部材を含んでいてもよい。
The foldable device of the present invention includes the adhesive film of the present invention. The foldable device of the present invention may include any appropriate other member as long as it has the adhesive film of the present invention.
本発明のローラブルデバイスは、本発明の粘着フィルムを備える。本発明のローラブルデバイスは、本発明の粘着フィルムを備えていれば、任意の適切な他の部材を含んでいてもよい。
The rollable device of the present invention includes the adhesive film of the present invention. The rollable device of the present invention may include any appropriate other member as long as it has the adhesive film of the present invention.
図1は、本発明の粘着フィルムの一つの使用形態の代表例として、本発明のフォルダブルデバイスの一つの実施形態を示す概略断面図である。図1において、本発明のフォルダブルデバイス1000は、カバーフィルム10、粘着剤層20、偏光板30、粘着剤層40、タッチセンサー50、粘着剤層60、OLED70、本発明の粘着フィルム100を備える。本発明の粘着フィルム100は、図1においては、粘着剤層80と基材層90から構成されている。粘着剤層20、粘着剤層40、粘着剤層60は。本発明の粘着フィルム100を構成する粘着剤層80と同じ組成の粘着剤を含む粘着剤層であってもよいし異なる組成の粘着剤を含む粘着剤層であってもよい。
FIG. 1 is a schematic cross-sectional view showing one embodiment of the foldable device of the present invention as a representative example of one usage form of the adhesive film of the present invention. 1, a foldable device 1000 of the present invention includes a cover film 10, an adhesive layer 20, a polarizing plate 30, an adhesive layer 40, a touch sensor 50, an adhesive layer 60, an OLED 70, and an adhesive film 100 of the present invention. .. The adhesive film 100 of the present invention is composed of an adhesive layer 80 and a base material layer 90 in FIG. The pressure-sensitive adhesive layer 20, the pressure-sensitive adhesive layer 40, and the pressure-sensitive adhesive layer 60. It may be a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive having the same composition as the pressure-sensitive adhesive layer 80 constituting the pressure-sensitive adhesive film 100 of the present invention, or may be a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive having a different composition.
本発明の粘着フィルムは、屈曲性および透明性に優れるので、例えば、可動屈曲部を有するベンダブルデバイス(曲げることが可能なデバイス)やフォルダブルデバイス(折りたたむことが可能なデバイス)やローラブルデバイス(丸めることが可能なデバイス)の背面(ディスプレイ面の反対の面)に好適に備えられ得る。図1は、フォルダブルデバイス(折りたたむことが可能なデバイス)の背面(ディスプレイ面の反対の面)に備えられている図である。
Since the pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, for example, a bendable device (a bendable device), a foldable device (a foldable device), or a rollable device (having a movable bending portion) (a bendable device). It can suitably be provided on the back side of the rollable device) (opposite the display side). FIG. 1 is a diagram provided on a back surface (a surface opposite to a display surface) of a foldable device (a foldable device).
以下に、実施例および比較例を挙げて、本発明をより具体的に説明する。ただし、本発明は、それらに何ら制限されるものではない。なお、以下の説明において、「部」および「%」は、特に明記のない限り、重量基準である。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited thereto. In the following description, “part” and “%” are based on weight unless otherwise specified.
<tanδ>
粘弾性測定装置「RSA-G2」(ティー・エイ・インスツルメント・ジャパン株式会社製)にて、引張りモードで、サンプルサイズ幅5mm×距離15mm、Axial force 100gにて測定を行った。歪み掃引(Oscilation amplitude)モードにて、周波数は1Hz、測定温度は90℃、浸漬時間60秒、歪みの測定域を0.01%から1.0%までに設定し、その間の歪みでの測定を行った。各歪みでのtanδの値をグラフ化し、0.1%の歪みと0.7%の歪みのtanδをグラフから求めた。厚みについては、粘着フィルムに対して貯蔵弾性率・損失弾性率とも基材の剛性が大きく、粘着剤に関しては影響が無視できるものとして、粘着剤の厚みを除いた基材の厚みのみを入力して測定を行った。
tanδは下記の式にて求めた。
tanδ=損失弾性率/貯蔵弾性率 <tanδ>
The viscoelasticity measuring device "RSA-G2" (manufactured by TA Instruments Japan Co., Ltd.) was used in the tensile mode to measure thesample size width 5 mm x distance 15 mm and axial force 100 g. In the strain sweep mode, the frequency is 1 Hz, the measurement temperature is 90° C., the immersion time is 60 seconds, the strain measurement range is set from 0.01% to 1.0%, and the strain is measured during that period. I went. The value of tan δ at each strain was graphed, and the tan δ of 0.1% strain and 0.7% strain was obtained from the graph. As for the thickness, it is assumed that both the storage modulus and loss modulus of the base material have a large rigidity with respect to the adhesive film, and the influence of the adhesive can be ignored, so only the thickness of the base material excluding the thickness of the adhesive is entered. Was measured.
Tan δ was calculated by the following formula.
tan δ=loss elastic modulus/storage elastic modulus
粘弾性測定装置「RSA-G2」(ティー・エイ・インスツルメント・ジャパン株式会社製)にて、引張りモードで、サンプルサイズ幅5mm×距離15mm、Axial force 100gにて測定を行った。歪み掃引(Oscilation amplitude)モードにて、周波数は1Hz、測定温度は90℃、浸漬時間60秒、歪みの測定域を0.01%から1.0%までに設定し、その間の歪みでの測定を行った。各歪みでのtanδの値をグラフ化し、0.1%の歪みと0.7%の歪みのtanδをグラフから求めた。厚みについては、粘着フィルムに対して貯蔵弾性率・損失弾性率とも基材の剛性が大きく、粘着剤に関しては影響が無視できるものとして、粘着剤の厚みを除いた基材の厚みのみを入力して測定を行った。
tanδは下記の式にて求めた。
tanδ=損失弾性率/貯蔵弾性率 <tanδ>
The viscoelasticity measuring device "RSA-G2" (manufactured by TA Instruments Japan Co., Ltd.) was used in the tensile mode to measure the
Tan δ was calculated by the following formula.
tan δ=loss elastic modulus/storage elastic modulus
<屈曲試験>
フラットな状態の粘着フィルムを、図2に示すように、粘着剤層面を外側にして粘着フィルムが6Φで屈曲した状態で、シリコーン処理セパレータのシリコーン処理面で挟む態様で固定して、90℃にて48時間保持した。その後、屈曲を解放し、23℃、50%RHにて24時間放置させた後に、折曲がったフィルムの角度を測定した。完全に元通りの状態に戻った場合を180度、最初の固定における折曲がった状態がそのまま維持した場合を0度とした。 <Bending test>
As shown in FIG. 2, the flat pressure-sensitive adhesive film is fixed in a state of being sandwiched between the silicone-treated surfaces of the silicone-treated separator with the pressure-sensitive adhesive film bent at 6Φ so that the temperature is 90° C. For 48 hours. After that, the bending was released, and the film was allowed to stand at 23° C. and 50% RH for 24 hours, and then the angle of the bent film was measured. The case where it completely returned to the original state was set to 180 degrees, and the case where the bent state in the first fixing was maintained as it was was set to 0 degree.
フラットな状態の粘着フィルムを、図2に示すように、粘着剤層面を外側にして粘着フィルムが6Φで屈曲した状態で、シリコーン処理セパレータのシリコーン処理面で挟む態様で固定して、90℃にて48時間保持した。その後、屈曲を解放し、23℃、50%RHにて24時間放置させた後に、折曲がったフィルムの角度を測定した。完全に元通りの状態に戻った場合を180度、最初の固定における折曲がった状態がそのまま維持した場合を0度とした。 <Bending test>
As shown in FIG. 2, the flat pressure-sensitive adhesive film is fixed in a state of being sandwiched between the silicone-treated surfaces of the silicone-treated separator with the pressure-sensitive adhesive film bent at 6Φ so that the temperature is 90° C. For 48 hours. After that, the bending was released, and the film was allowed to stand at 23° C. and 50% RH for 24 hours, and then the angle of the bent film was measured. The case where it completely returned to the original state was set to 180 degrees, and the case where the bent state in the first fixing was maintained as it was was set to 0 degree.
<剥がれ評価>
厚みが50μmのPETフィルム(東レ製、S10)に、粘着フィルムを貼り合せ、図3に示すように粘着フィルムが内側になるように折り曲げて、90℃で48時間保持した後、固定された状態を解放させ、該PETフィルムからの粘着フィルムの剥がれを目視で観察した。評価は下記の基準にしたがって行った。
○:PETフィルムからの剥がれが見られないもの。
×:PETフィルムからの剥がれが見られるもの。 <Peeling evaluation>
Adhesive film was attached to a PET film (Toray, S10) with a thickness of 50 μm, and the adhesive film was bent so that the adhesive film was on the inside as shown in FIG. 3 and kept at 90° C. for 48 hours, and then fixed. Was released, and peeling of the adhesive film from the PET film was visually observed. The evaluation was performed according to the following criteria.
Good: Peeling from the PET film is not seen.
X: Peeling from the PET film is seen.
厚みが50μmのPETフィルム(東レ製、S10)に、粘着フィルムを貼り合せ、図3に示すように粘着フィルムが内側になるように折り曲げて、90℃で48時間保持した後、固定された状態を解放させ、該PETフィルムからの粘着フィルムの剥がれを目視で観察した。評価は下記の基準にしたがって行った。
○:PETフィルムからの剥がれが見られないもの。
×:PETフィルムからの剥がれが見られるもの。 <Peeling evaluation>
Adhesive film was attached to a PET film (Toray, S10) with a thickness of 50 μm, and the adhesive film was bent so that the adhesive film was on the inside as shown in FIG. 3 and kept at 90° C. for 48 hours, and then fixed. Was released, and peeling of the adhesive film from the PET film was visually observed. The evaluation was performed according to the following criteria.
Good: Peeling from the PET film is not seen.
X: Peeling from the PET film is seen.
<ヘイズ、全光線透過率の測定>
ヘイズメーターHM-150((株)村上色彩技術研究所製)を使用し、JIS-K-7136に準拠し、ヘイズ(%)=(Td/Tt)×100(Td:拡散透過率、Tt:全光線透過率)により算出した。なお、全光線透過率は、JIS-K-7316に準拠して測定した。 <Measurement of haze and total light transmittance>
Haze meter HM-150 (manufactured by Murakami Color Research Laboratory Co., Ltd.) is used, and in accordance with JIS-K-7136, haze (%)=(Td/Tt)×100 (Td: diffuse transmittance, Tt: Total light transmittance) was calculated. The total light transmittance was measured according to JIS-K-7316.
ヘイズメーターHM-150((株)村上色彩技術研究所製)を使用し、JIS-K-7136に準拠し、ヘイズ(%)=(Td/Tt)×100(Td:拡散透過率、Tt:全光線透過率)により算出した。なお、全光線透過率は、JIS-K-7316に準拠して測定した。 <Measurement of haze and total light transmittance>
Haze meter HM-150 (manufactured by Murakami Color Research Laboratory Co., Ltd.) is used, and in accordance with JIS-K-7136, haze (%)=(Td/Tt)×100 (Td: diffuse transmittance, Tt: Total light transmittance) was calculated. The total light transmittance was measured according to JIS-K-7316.
<ヤング率>
サンプル片を幅10mmに短冊状に切り出し、25℃の温度環境下で万能引張圧縮試験機(テンシロン)にて、上記短冊状のサンプル片をチャック間距離100mmにて長手方向に引っ張って測定し、得られたS-S(Strain-Strength)カーブよりヤング率を求めた。測定条件としては、引張速度が200mm/min、チャック間が50mmであった。S-Sカーブからヤング率を求める方法は、S-Sカーブのグラフを作成し、変位1mm~2mmの範囲においてグラフに接線(一次式)を引き、接線の傾斜から求めた。 <Young's modulus>
The sample piece was cut into a strip shape with a width of 10 mm, and the strip-shaped sample piece was pulled in a longitudinal direction at a chuck distance of 100 mm with a universal tensile compression tester (Tensilon) under a temperature environment of 25° C. to measure, Young's modulus was determined from the obtained SS (Strain-Strength) curve. The measurement conditions were a pulling speed of 200 mm/min and a chuck gap of 50 mm. The Young's modulus was calculated from the SS curve by drawing a graph of the SS curve, drawing a tangent line (linear equation) on the graph in the displacement range of 1 mm to 2 mm, and calculating from the slope of the tangent line.
サンプル片を幅10mmに短冊状に切り出し、25℃の温度環境下で万能引張圧縮試験機(テンシロン)にて、上記短冊状のサンプル片をチャック間距離100mmにて長手方向に引っ張って測定し、得られたS-S(Strain-Strength)カーブよりヤング率を求めた。測定条件としては、引張速度が200mm/min、チャック間が50mmであった。S-Sカーブからヤング率を求める方法は、S-Sカーブのグラフを作成し、変位1mm~2mmの範囲においてグラフに接線(一次式)を引き、接線の傾斜から求めた。 <Young's modulus>
The sample piece was cut into a strip shape with a width of 10 mm, and the strip-shaped sample piece was pulled in a longitudinal direction at a chuck distance of 100 mm with a universal tensile compression tester (Tensilon) under a temperature environment of 25° C. to measure, Young's modulus was determined from the obtained SS (Strain-Strength) curve. The measurement conditions were a pulling speed of 200 mm/min and a chuck gap of 50 mm. The Young's modulus was calculated from the SS curve by drawing a graph of the SS curve, drawing a tangent line (linear equation) on the graph in the displacement range of 1 mm to 2 mm, and calculating from the slope of the tangent line.
<粘着力>
粘着フィルムを幅25mm、長さ150mmに切断し、評価用サンプルとした。温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面をガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)に、2.0kgローラー1往復により貼り付けた。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、引っ張り速度300mm/分で剥離し、粘着力を測定した。 <Adhesive strength>
The adhesive film was cut into a width of 25 mm and a length of 150 mm to obtain a sample for evaluation. In an atmosphere of a temperature of 23° C. and a humidity of 50% RH, the surface of the pressure-sensitive adhesive layer of the sample for evaluation was attached to a glass plate (Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) by reciprocating a 2.0 kg roller once. I attached it. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, using a universal tensile tester (Minebea Co., product name: TCM-1kNB), peeling was performed at a peeling angle of 180 degrees and a pulling speed of 300 mm/min. Then, the adhesive strength was measured.
粘着フィルムを幅25mm、長さ150mmに切断し、評価用サンプルとした。温度23℃、湿度50%RHの雰囲気下で、評価用サンプルの粘着剤層表面をガラス板(松浪硝子工業株式会社製、商品名:マイクロスライドガラスS)に、2.0kgローラー1往復により貼り付けた。温度23℃、湿度50%RHの雰囲気下で30分間養生した後、万能引張試験機(ミネベア株式会社製、製品名:TCM-1kNB)を用い、剥離角度180度、引っ張り速度300mm/分で剥離し、粘着力を測定した。 <Adhesive strength>
The adhesive film was cut into a width of 25 mm and a length of 150 mm to obtain a sample for evaluation. In an atmosphere of a temperature of 23° C. and a humidity of 50% RH, the surface of the pressure-sensitive adhesive layer of the sample for evaluation was attached to a glass plate (Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) by reciprocating a 2.0 kg roller once. I attached it. After curing for 30 minutes in an atmosphere of a temperature of 23° C. and a humidity of 50% RH, using a universal tensile tester (Minebea Co., product name: TCM-1kNB), peeling was performed at a peeling angle of 180 degrees and a pulling speed of 300 mm/min. Then, the adhesive strength was measured.
<塗布性>
塗布したトップコート層(帯電防止層含有)に円形状にムラが発生した個数をカウントする。A4サイズで2枚作成し平均個数を算出した。
2以下は良好、3個以上は不良と判断した。円形状のムラ部分は、トップコート層の厚みが薄くなっており、見た目の外観として欠点となっている部分であり、帯電防止剤をはじいてしまい、全く塗布できなかったものは、「ハジキ」とした。 <Applicability>
The number of circular irregularities in the applied top coat layer (including the antistatic layer) is counted. Two sheets of A4 size were prepared and the average number was calculated.
2 or less were judged to be good, and 3 or more were judged to be defective. The circular uneven part is a part where the thickness of the top coat layer is thin and it is a defect in appearance, and the one that could not be applied at all because it repelled the antistatic agent was “Hajiki” And
塗布したトップコート層(帯電防止層含有)に円形状にムラが発生した個数をカウントする。A4サイズで2枚作成し平均個数を算出した。
2以下は良好、3個以上は不良と判断した。円形状のムラ部分は、トップコート層の厚みが薄くなっており、見た目の外観として欠点となっている部分であり、帯電防止剤をはじいてしまい、全く塗布できなかったものは、「ハジキ」とした。 <Applicability>
The number of circular irregularities in the applied top coat layer (including the antistatic layer) is counted. Two sheets of A4 size were prepared and the average number was calculated.
2 or less were judged to be good, and 3 or more were judged to be defective. The circular uneven part is a part where the thickness of the top coat layer is thin and it is a defect in appearance, and the one that could not be applied at all because it repelled the antistatic agent was “Hajiki” And
<表面抵抗値(実施例8用)>
実施例8において、帯電防止処理層を形成した層を、体積抵抗計 Model 152-1 152P-2P プローブ(トレック・ジャパン株式会社製)にて、電圧10Vにて測定を行った。 <Surface resistance value (for Example 8)>
The layer on which the antistatic treatment layer was formed in Example 8 was measured with a volume resistance meter Model 152-1 152P-2P probe (manufactured by Trek Japan KK) at a voltage of 10V.
実施例8において、帯電防止処理層を形成した層を、体積抵抗計 Model 152-1 152P-2P プローブ(トレック・ジャパン株式会社製)にて、電圧10Vにて測定を行った。 <Surface resistance value (for Example 8)>
The layer on which the antistatic treatment layer was formed in Example 8 was measured with a volume resistance meter Model 152-1 152P-2P probe (manufactured by Trek Japan KK) at a voltage of 10V.
<表面抵抗率(実施例9~17、比較例6~9用>
実施例9~17、比較例6~9において、抵抗率計(三菱ケミカルアナリティック製、「ハイレスタUP MCP-HT450型」)を用い、粘着フィルムの粘着剤層非付設面にURSプローブを接触させ、印加電圧100V、電圧印加時間10秒の条件で表面抵抗率を測定した。 <Surface resistivity (for Examples 9 to 17 and Comparative Examples 6 to 9)>
In Examples 9 to 17 and Comparative Examples 6 to 9, a resistivity meter (manufactured by Mitsubishi Chemical Analytic, “HIRESTA UP MCP-HT450 type”) was used to bring the URS probe into contact with the surface without the adhesive layer of the adhesive film. The surface resistivity was measured under conditions of an applied voltage of 100 V and a voltage application time of 10 seconds.
実施例9~17、比較例6~9において、抵抗率計(三菱ケミカルアナリティック製、「ハイレスタUP MCP-HT450型」)を用い、粘着フィルムの粘着剤層非付設面にURSプローブを接触させ、印加電圧100V、電圧印加時間10秒の条件で表面抵抗率を測定した。 <Surface resistivity (for Examples 9 to 17 and Comparative Examples 6 to 9)>
In Examples 9 to 17 and Comparative Examples 6 to 9, a resistivity meter (manufactured by Mitsubishi Chemical Analytic, “HIRESTA UP MCP-HT450 type”) was used to bring the URS probe into contact with the surface without the adhesive layer of the adhesive film. The surface resistivity was measured under conditions of an applied voltage of 100 V and a voltage application time of 10 seconds.
[製造例1]:粘着剤組成物Aの調製
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル:133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマー(a)の溶液を得た。
次に、アクリル系ポリマー(a1)の溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(a)(固形分)100重量部に対して固形分換算で1重量部となるように添加し、粘着剤組成物Aを調製した。 [Production Example 1]: Preparation of adhesive composition A 2-Ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA) ): 9 parts by weight, 2-hydroxyethyl acrylate (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 parts by weight, and acetic acid as a polymerization solvent. Ethyl: 133 parts by weight was put into a separable flask and stirred for 1 hour while introducing nitrogen gas. After removing the oxygen in the polymerization system in this way, the temperature was raised to 65° C. and the reaction was carried out for 10 hours, and then ethyl acetate was added to obtain a solution of the acrylic polymer (a) having a solid content concentration of 30% by weight. It was
Next, in the solution of the acrylic polymer (a1), an isocyanate-based crosslinking agent (trade name "Takenate D110N", manufactured by Mitsui Chemicals, Inc.) was added to 100 parts by weight of the acrylic polymer (a) (solid content) as a solid content. The pressure-sensitive adhesive composition A was prepared by adding 1 part by weight in terms of conversion.
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル:133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマー(a)の溶液を得た。
次に、アクリル系ポリマー(a1)の溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(a)(固形分)100重量部に対して固形分換算で1重量部となるように添加し、粘着剤組成物Aを調製した。 [Production Example 1]: Preparation of adhesive composition A 2-Ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA) ): 9 parts by weight, 2-hydroxyethyl acrylate (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 parts by weight, and acetic acid as a polymerization solvent. Ethyl: 133 parts by weight was put into a separable flask and stirred for 1 hour while introducing nitrogen gas. After removing the oxygen in the polymerization system in this way, the temperature was raised to 65° C. and the reaction was carried out for 10 hours, and then ethyl acetate was added to obtain a solution of the acrylic polymer (a) having a solid content concentration of 30% by weight. It was
Next, in the solution of the acrylic polymer (a1), an isocyanate-based crosslinking agent (trade name "Takenate D110N", manufactured by Mitsui Chemicals, Inc.) was added to 100 parts by weight of the acrylic polymer (a) (solid content) as a solid content. The pressure-sensitive adhesive composition A was prepared by adding 1 part by weight in terms of conversion.
[製造例2]:粘着剤組成物Bの調製
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、2-エチルヘキシルアクリレート(2EHA)96.2重量部、ヒドロキシエチルアクリレート(HEA)3.8重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.2重量部、酢酸エチル150重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を60℃付近に保って6時間重合反応を行い、アクリル系ポリマー(b)の溶液(40重量%)を調製した。アクリル系ポリマー(b)の重量平均分子量は54万であった。
次に、アクリル系ポリマー(b)の溶液(40重量%)を酢酸エチルで25重量%に希釈し、この溶液400重量部(固形分100重量部)に、架橋剤として、3官能イソシアネート化合物であるヘキサメチレンジイソシアネートのイソシアヌル体(東ソー社製、コロネートHX)4重量部(固形分4重量部)、架橋触媒としてジラウリン酸ジオクチルスズ(東京ファインケミカル社製、エンビライザーOL-1、1重量%酢酸エチル溶液)2重量部(固形分0.02重量部)、アセチルアセトン3重量部を加えて、混合攪拌を行い、粘着剤組成物Bを調製した。 [Production Example 2]: Preparation of adhesive composition B In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser, 96.2 parts by weight of 2-ethylhexyl acrylate (2EHA) and hydroxyethyl were added. 3.8 parts by weight of acrylate (HEA), 0.2 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator, and 150 parts by weight of ethyl acetate were charged, and nitrogen gas was introduced with gentle stirring. Polymerization reaction was carried out for 6 hours while maintaining the liquid temperature in the flask at around 60°C to prepare a solution (40% by weight) of the acrylic polymer (b). The weight average molecular weight of the acrylic polymer (b) was 540,000.
Next, the acrylic polymer (b) solution (40% by weight) was diluted to 25% by weight with ethyl acetate, and 400 parts by weight of this solution (solid content 100 parts by weight) was added with a trifunctional isocyanate compound as a crosslinking agent. 4 parts by weight of isocyanuric hexamethylene diisocyanate (manufactured by Tosoh Corporation, Coronate HX) (4 parts by weight of solid content), dioctyltin dilaurate as a crosslinking catalyst (manufactured by Tokyo Fine Chemical Co., Enbilizer OL-1, 1% by weight ethyl acetate) Solution) 2 parts by weight (solid content 0.02 part by weight) and acetylacetone 3 parts by weight were added and mixed and stirred to prepare an adhesive composition B.
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、2-エチルヘキシルアクリレート(2EHA)96.2重量部、ヒドロキシエチルアクリレート(HEA)3.8重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.2重量部、酢酸エチル150重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を60℃付近に保って6時間重合反応を行い、アクリル系ポリマー(b)の溶液(40重量%)を調製した。アクリル系ポリマー(b)の重量平均分子量は54万であった。
次に、アクリル系ポリマー(b)の溶液(40重量%)を酢酸エチルで25重量%に希釈し、この溶液400重量部(固形分100重量部)に、架橋剤として、3官能イソシアネート化合物であるヘキサメチレンジイソシアネートのイソシアヌル体(東ソー社製、コロネートHX)4重量部(固形分4重量部)、架橋触媒としてジラウリン酸ジオクチルスズ(東京ファインケミカル社製、エンビライザーOL-1、1重量%酢酸エチル溶液)2重量部(固形分0.02重量部)、アセチルアセトン3重量部を加えて、混合攪拌を行い、粘着剤組成物Bを調製した。 [Production Example 2]: Preparation of adhesive composition B In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser, 96.2 parts by weight of 2-ethylhexyl acrylate (2EHA) and hydroxyethyl were added. 3.8 parts by weight of acrylate (HEA), 0.2 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator, and 150 parts by weight of ethyl acetate were charged, and nitrogen gas was introduced with gentle stirring. Polymerization reaction was carried out for 6 hours while maintaining the liquid temperature in the flask at around 60°C to prepare a solution (40% by weight) of the acrylic polymer (b). The weight average molecular weight of the acrylic polymer (b) was 540,000.
Next, the acrylic polymer (b) solution (40% by weight) was diluted to 25% by weight with ethyl acetate, and 400 parts by weight of this solution (
[実施例1]
市販の剥離ライナー(ダイアホイルMRF-38」、三菱樹脂株式会社製)を用意した。剥離ライナーの一方の面(剥離面)に粘着剤組成物Aを、乾燥後の厚みが25μmとなるように塗布し、130℃で3分間乾燥させた。このようにして、粘着剤組成物Aに対応するアクリル系粘着剤Aにより構成された厚み25μmの粘着剤層を、剥離ライナーの剥離面上に形成した。
基材層として、厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)を用意した。この基材層の一方の面に、上記剥離ライナー上に形成された粘着剤層を貼り合わせた。上記剥離ライナーは、そのまま粘着剤層上に残し、該粘着剤層の表面(粘着剤層面)の保護に使用した。得られた構造体を80℃のラミネータ(0.3MPa、速度0.5m/分)に1回通過させた後、50℃のオーブン中で1日間エージングした。このようにして、粘着フィルム(1)を得た。
結果を表1に示した。 [Example 1]
A commercially available release liner (DIAFOIL MRF-38", manufactured by Mitsubishi Plastics, Inc.) was prepared. The pressure-sensitive adhesive composition A was applied to one surface (release surface) of the release liner so that the thickness after drying was 25 μm, and dried at 130° C. for 3 minutes. In this way, a pressure-sensitive adhesive layer having a thickness of 25 μm and composed of the acrylic pressure-sensitive adhesive A corresponding to the pressure-sensitive adhesive composition A was formed on the release surface of the release liner.
As the base material layer, a polyimide base material (trade name “Kapton”, manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 μm was prepared. The pressure-sensitive adhesive layer formed on the release liner was attached to one surface of the base material layer. The release liner was left as it was on the pressure-sensitive adhesive layer and used to protect the surface of the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer surface). The obtained structure was passed once through a laminator at 80° C. (0.3 MPa, speed 0.5 m/min), and then aged in an oven at 50° C. for 1 day. Thus, the adhesive film (1) was obtained.
The results are shown in Table 1.
市販の剥離ライナー(ダイアホイルMRF-38」、三菱樹脂株式会社製)を用意した。剥離ライナーの一方の面(剥離面)に粘着剤組成物Aを、乾燥後の厚みが25μmとなるように塗布し、130℃で3分間乾燥させた。このようにして、粘着剤組成物Aに対応するアクリル系粘着剤Aにより構成された厚み25μmの粘着剤層を、剥離ライナーの剥離面上に形成した。
基材層として、厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)を用意した。この基材層の一方の面に、上記剥離ライナー上に形成された粘着剤層を貼り合わせた。上記剥離ライナーは、そのまま粘着剤層上に残し、該粘着剤層の表面(粘着剤層面)の保護に使用した。得られた構造体を80℃のラミネータ(0.3MPa、速度0.5m/分)に1回通過させた後、50℃のオーブン中で1日間エージングした。このようにして、粘着フィルム(1)を得た。
結果を表1に示した。 [Example 1]
A commercially available release liner (DIAFOIL MRF-38", manufactured by Mitsubishi Plastics, Inc.) was prepared. The pressure-sensitive adhesive composition A was applied to one surface (release surface) of the release liner so that the thickness after drying was 25 μm, and dried at 130° C. for 3 minutes. In this way, a pressure-sensitive adhesive layer having a thickness of 25 μm and composed of the acrylic pressure-sensitive adhesive A corresponding to the pressure-sensitive adhesive composition A was formed on the release surface of the release liner.
As the base material layer, a polyimide base material (trade name “Kapton”, manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 μm was prepared. The pressure-sensitive adhesive layer formed on the release liner was attached to one surface of the base material layer. The release liner was left as it was on the pressure-sensitive adhesive layer and used to protect the surface of the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer surface). The obtained structure was passed once through a laminator at 80° C. (0.3 MPa, speed 0.5 m/min), and then aged in an oven at 50° C. for 1 day. Thus, the adhesive film (1) was obtained.
The results are shown in Table 1.
[実施例2]
基材層として、厚み50μmのポリイミド系基材(商品名「ユーピレックス-50S」、宇部興産株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(2)を得た。
結果を表1に示した。 [Example 2]
An adhesive film (2) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 μm (trade name “UPILEX-50S”, manufactured by Ube Industries, Ltd.) was used as the substrate layer.
The results are shown in Table 1.
基材層として、厚み50μmのポリイミド系基材(商品名「ユーピレックス-50S」、宇部興産株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(2)を得た。
結果を表1に示した。 [Example 2]
An adhesive film (2) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 μm (trade name “UPILEX-50S”, manufactured by Ube Industries, Ltd.) was used as the substrate layer.
The results are shown in Table 1.
[実施例3]
基材層として、厚み50μmのポリイミド系基材(商品名「ピクシオBP」、株式会社カネカ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(3)を得た。
結果を表1に示した。 [Example 3]
An adhesive film (3) was obtained in the same manner as in Example 1 except that a polyimide base material having a thickness of 50 μm (trade name “Pixio BP”, manufactured by Kaneka Corporation) was used as the base material layer.
The results are shown in Table 1.
基材層として、厚み50μmのポリイミド系基材(商品名「ピクシオBP」、株式会社カネカ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(3)を得た。
結果を表1に示した。 [Example 3]
An adhesive film (3) was obtained in the same manner as in Example 1 except that a polyimide base material having a thickness of 50 μm (trade name “Pixio BP”, manufactured by Kaneka Corporation) was used as the base material layer.
The results are shown in Table 1.
[実施例4]
基材層として、厚み50μmのポリイミド系基材(商品名「ユーピレックス-50RN」、宇部興産株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(4)を得た。
結果を表1に示した。 [Example 4]
An adhesive film (4) was obtained in the same manner as in Example 1 except that a polyimide base material having a thickness of 50 μm (trade name “UPILEX-50RN”, manufactured by Ube Industries, Ltd.) was used as the base material layer.
The results are shown in Table 1.
基材層として、厚み50μmのポリイミド系基材(商品名「ユーピレックス-50RN」、宇部興産株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(4)を得た。
結果を表1に示した。 [Example 4]
An adhesive film (4) was obtained in the same manner as in Example 1 except that a polyimide base material having a thickness of 50 μm (trade name “UPILEX-50RN”, manufactured by Ube Industries, Ltd.) was used as the base material layer.
The results are shown in Table 1.
[実施例5]
基材層として、厚み50μmのポリエーテルエーテルケトン(PEEK)系基材(商品名「Shin-Etsu Sepla Film」、無延伸製膜高結晶、信越ポリマー株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(5)を得た。
結果を表1に示した。 [Example 5]
Examples except that a 50 μm thick polyetheretherketone (PEEK)-based substrate (trade name “Shin-Etsu Sepla Film”, non-stretched film-forming high crystal, manufactured by Shin-Etsu Polymer Co., Ltd.) was used as the substrate layer The same procedure as in 1 was carried out to obtain an adhesive film (5).
The results are shown in Table 1.
基材層として、厚み50μmのポリエーテルエーテルケトン(PEEK)系基材(商品名「Shin-Etsu Sepla Film」、無延伸製膜高結晶、信越ポリマー株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(5)を得た。
結果を表1に示した。 [Example 5]
Examples except that a 50 μm thick polyetheretherketone (PEEK)-based substrate (trade name “Shin-Etsu Sepla Film”, non-stretched film-forming high crystal, manufactured by Shin-Etsu Polymer Co., Ltd.) was used as the substrate layer The same procedure as in 1 was carried out to obtain an adhesive film (5).
The results are shown in Table 1.
[実施例6]
基材層として、厚み50μmのポリイミド系基材(商品名「ネオプリムS100」、三菱ガス化学株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(6)を得た。
結果を表1に示した。 [Example 6]
An adhesive film (6) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 μm (trade name “Neoprim S100”, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used as the substrate layer.
The results are shown in Table 1.
基材層として、厚み50μmのポリイミド系基材(商品名「ネオプリムS100」、三菱ガス化学株式会社製)を用いた以外は、実施例1と同様に行い、粘着フィルム(6)を得た。
結果を表1に示した。 [Example 6]
An adhesive film (6) was obtained in the same manner as in Example 1 except that a polyimide-based substrate having a thickness of 50 μm (trade name “Neoprim S100”, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used as the substrate layer.
The results are shown in Table 1.
[実施例7]
基材層として、厚み25μmのポリエーテルエーテルケトン(PEEK)系基材(商品名「エクスピーク」、クラボウ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(7)を得た。
結果を表1に示した。 [Example 7]
An adhesive film (7) was obtained in the same manner as in Example 1 except that a 25 μm-thick polyetheretherketone (PEEK) base material (trade name “Expeak”, manufactured by Kurabo Industries) was used as the base material layer. It was
The results are shown in Table 1.
基材層として、厚み25μmのポリエーテルエーテルケトン(PEEK)系基材(商品名「エクスピーク」、クラボウ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(7)を得た。
結果を表1に示した。 [Example 7]
An adhesive film (7) was obtained in the same manner as in Example 1 except that a 25 μm-thick polyetheretherketone (PEEK) base material (trade name “Expeak”, manufactured by Kurabo Industries) was used as the base material layer. It was
The results are shown in Table 1.
[比較例1]
基材層として、厚み25μmのポリエステル系基材(商品名「ルミラーS10」、東レ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(C1)を得た。
結果を表1に示した。 [Comparative Example 1]
An adhesive film (C1) was obtained in the same manner as in Example 1 except that a 25 μm-thick polyester base material (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer.
The results are shown in Table 1.
基材層として、厚み25μmのポリエステル系基材(商品名「ルミラーS10」、東レ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(C1)を得た。
結果を表1に示した。 [Comparative Example 1]
An adhesive film (C1) was obtained in the same manner as in Example 1 except that a 25 μm-thick polyester base material (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer.
The results are shown in Table 1.
[比較例2]
基材層として、厚み50μmのポリエステル系基材(商品名「ルミラーS10」、東レ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(C2)を得た。
結果を表1に示した。 [Comparative example 2]
An adhesive film (C2) was obtained in the same manner as in Example 1 except that a 50 μm-thick polyester base material (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer.
The results are shown in Table 1.
基材層として、厚み50μmのポリエステル系基材(商品名「ルミラーS10」、東レ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(C2)を得た。
結果を表1に示した。 [Comparative example 2]
An adhesive film (C2) was obtained in the same manner as in Example 1 except that a 50 μm-thick polyester base material (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer.
The results are shown in Table 1.
[比較例3]
粘着剤組成物Aに代えて粘着剤組成物Bを用い、基材層として、厚み50μmのポリエステル系基材(商品名「ルミラーS10」、東レ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(C3)を得た。
結果を表1に示した。 [Comparative Example 3]
Same as Example 1 except that the pressure-sensitive adhesive composition B was used in place of the pressure-sensitive adhesive composition A, and a polyester base material having a thickness of 50 μm (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer. Then, an adhesive film (C3) was obtained.
The results are shown in Table 1.
粘着剤組成物Aに代えて粘着剤組成物Bを用い、基材層として、厚み50μmのポリエステル系基材(商品名「ルミラーS10」、東レ製)を用いた以外は、実施例1と同様に行い、粘着フィルム(C3)を得た。
結果を表1に示した。 [Comparative Example 3]
Same as Example 1 except that the pressure-sensitive adhesive composition B was used in place of the pressure-sensitive adhesive composition A, and a polyester base material having a thickness of 50 μm (trade name “Lumirror S10”, manufactured by Toray) was used as the base material layer. Then, an adhesive film (C3) was obtained.
The results are shown in Table 1.
[比較例4]
粘着剤組成物Aに代えて粘着剤組成物Bを用いた以外は、実施例6と同様に行い、粘着フィルム(C4)を得た。
結果を表1に示した。 [Comparative Example 4]
An adhesive film (C4) was obtained in the same manner as in Example 6 except that the adhesive composition B was used instead of the adhesive composition A.
The results are shown in Table 1.
粘着剤組成物Aに代えて粘着剤組成物Bを用いた以外は、実施例6と同様に行い、粘着フィルム(C4)を得た。
結果を表1に示した。 [Comparative Example 4]
An adhesive film (C4) was obtained in the same manner as in Example 6 except that the adhesive composition B was used instead of the adhesive composition A.
The results are shown in Table 1.
[比較例5]
粘着剤組成物Aに代えて粘着剤組成物Bを用いた以外は、実施例7と同様に行い、粘着フィルム(C5)を得た。
結果を表1に示した。 [Comparative Example 5]
An adhesive film (C5) was obtained in the same manner as in Example 7, except that the adhesive composition B was used instead of the adhesive composition A.
The results are shown in Table 1.
粘着剤組成物Aに代えて粘着剤組成物Bを用いた以外は、実施例7と同様に行い、粘着フィルム(C5)を得た。
結果を表1に示した。 [Comparative Example 5]
An adhesive film (C5) was obtained in the same manner as in Example 7, except that the adhesive composition B was used instead of the adhesive composition A.
The results are shown in Table 1.
[製造例3]:帯電防止処理ポリイミドフィルムAの作製
帯電防止剤(ソルベックス社製、マイクロソルバーRMd-142、酸化スズとポリエステル樹脂を主成分とする)10重量部を、水30重量部とメタノール70重量部からなる混合溶媒で希釈することにより帯電防止剤溶液を調製した。得られた帯電防止剤溶液を、基材である厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)の上にマイヤーバーを用いて塗布し、130℃で1分間乾燥することにより溶剤を除去して、帯電防止層(厚さ:0.2μm)を形成し、帯電防止処理ポリイミドフィルムAを作製した。 [Production Example 3]: Preparation of antistatic-treatedpolyimide film A 10 parts by weight of antistatic agent (Microsolver RMd-142, manufactured by Solvex Co., containing tin oxide and polyester resin as main components), 30 parts by weight of water and methanol An antistatic agent solution was prepared by diluting with 70 parts by weight of a mixed solvent. The obtained antistatic agent solution was applied onto a 50 μm-thick polyimide base material (trade name “Kapton”, manufactured by Toray DuPont Co., Ltd.), which is a base material, using a Meyer bar, and at 130° C. for 1 minute. The solvent was removed by drying to form an antistatic layer (thickness: 0.2 μm), and an antistatic-treated polyimide film A was produced.
帯電防止剤(ソルベックス社製、マイクロソルバーRMd-142、酸化スズとポリエステル樹脂を主成分とする)10重量部を、水30重量部とメタノール70重量部からなる混合溶媒で希釈することにより帯電防止剤溶液を調製した。得られた帯電防止剤溶液を、基材である厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)の上にマイヤーバーを用いて塗布し、130℃で1分間乾燥することにより溶剤を除去して、帯電防止層(厚さ:0.2μm)を形成し、帯電防止処理ポリイミドフィルムAを作製した。 [Production Example 3]: Preparation of antistatic-treated
[実施例8]
基材として帯電防止処理ポリイミドフィルムAを使用した以外は実施例1と同様に行い、粘着フィルム(8)を得た。表面抵抗値は、5×106Ωであった。 [Example 8]
An adhesive film (8) was obtained in the same manner as in Example 1 except that the antistatic-treated polyimide film A was used as the substrate. The surface resistance value was 5×10 6 Ω.
基材として帯電防止処理ポリイミドフィルムAを使用した以外は実施例1と同様に行い、粘着フィルム(8)を得た。表面抵抗値は、5×106Ωであった。 [Example 8]
An adhesive film (8) was obtained in the same manner as in Example 1 except that the antistatic-treated polyimide film A was used as the substrate. The surface resistance value was 5×10 6 Ω.
[製造例4]:トップコート層形成ポリイミドフィルムBの作成
<コーティング材Bの調製>
バインダとしてのポリエステル樹脂(バインダ)を25重量%含む分散液(東洋紡株式会社製品、商品名「バイナロールMD-1480」(飽和共重合ポリエステル樹脂の水分散液);以下「バインダ分散液」ともいう。)を用意した。
また、滑り剤として、カルナウバワックス(日本ワックス社製、商品名「精製カルナウバワックッス2号粉末」)の水分散液(以下「滑り剤分散液」ともいう。)を用意した。
さらに、導電性ポリマーとして、ポリ(3,4-ジオキシチオフェン)(PEDOT)0.5重量%、及び、ポリスチレンスルホネート(数平均分子量15万)(PSS)0.8重量%を含む水溶液(H.C.Stark社製品、商品名「Baytron P」;以下「導電性ポリマー水溶液」ともいう。)を用意した。
水とエタノールとの混合溶媒(重量比が50:50)に、上記バインダ分散液を固形分量で100重量部と、上記滑り剤分散液を固形分量で30重量部と、上記導電性ポリマー水溶液を固形分量で50重量部と、メラミン系架橋剤7重量部とを加え、約20分間攪拌して、十分に混合した。このようにして、NVが約0.15重量%のコーティング材Bを調製した。
<トップコート層形成ポリイミドフィルムBの作成>
基材である厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)の上に、上記コーティング材Bをバーコーターで塗付し、130℃に2分間加熱して乾燥させた。このようにして、ポリイミド系基材の片面に厚さ10nmの透明なトップコート層を有する基材(トップコート層形成ポリイミドフィルムB)を作製した。 [Manufacturing Example 4]: Preparation of polyimide film B for forming top coat layer <Preparation of coating material B>
Dispersion containing 25% by weight of a polyester resin (binder) as a binder (manufactured by Toyobo Co., Ltd., trade name "Binaroll MD-1480" (aqueous dispersion of saturated copolyester resin); hereinafter also referred to as "binder dispersion". ) Was prepared.
In addition, as a slip agent, an aqueous dispersion of carnauba wax (manufactured by Nippon Wax Co., Ltd., trade name “Purified Carnauba Waxus No. 2 powder”) (hereinafter also referred to as “slipper dispersion”) was prepared.
Further, an aqueous solution containing 0.5% by weight of poly(3,4-dioxythiophene) (PEDOT) and 0.8% by weight of polystyrene sulfonate (number average molecular weight 150,000) (PSS) as a conductive polymer (H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution”) was prepared.
In a mixed solvent of water and ethanol (weight ratio of 50:50), 100 parts by weight of the binder dispersion liquid in solid content, 30 parts by weight of the slip agent dispersion liquid in solid content, and the conductive polymer aqueous solution were added. 50 parts by weight of solid content and 7 parts by weight of melamine-based cross-linking agent were added, and the mixture was stirred for about 20 minutes and mixed sufficiently. Thus, coating material B having an NV of about 0.15% by weight was prepared.
<Preparation of top coat layer forming polyimide film B>
The coating material B is applied by a bar coater on a polyimide base material (trade name "Kapton", manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 μm, which is a base material, and dried by heating at 130° C. for 2 minutes. Let Thus, a base material (topcoat layer forming polyimide film B) having a transparent topcoat layer having a thickness of 10 nm on one surface of the polyimide base material was produced.
<コーティング材Bの調製>
バインダとしてのポリエステル樹脂(バインダ)を25重量%含む分散液(東洋紡株式会社製品、商品名「バイナロールMD-1480」(飽和共重合ポリエステル樹脂の水分散液);以下「バインダ分散液」ともいう。)を用意した。
また、滑り剤として、カルナウバワックス(日本ワックス社製、商品名「精製カルナウバワックッス2号粉末」)の水分散液(以下「滑り剤分散液」ともいう。)を用意した。
さらに、導電性ポリマーとして、ポリ(3,4-ジオキシチオフェン)(PEDOT)0.5重量%、及び、ポリスチレンスルホネート(数平均分子量15万)(PSS)0.8重量%を含む水溶液(H.C.Stark社製品、商品名「Baytron P」;以下「導電性ポリマー水溶液」ともいう。)を用意した。
水とエタノールとの混合溶媒(重量比が50:50)に、上記バインダ分散液を固形分量で100重量部と、上記滑り剤分散液を固形分量で30重量部と、上記導電性ポリマー水溶液を固形分量で50重量部と、メラミン系架橋剤7重量部とを加え、約20分間攪拌して、十分に混合した。このようにして、NVが約0.15重量%のコーティング材Bを調製した。
<トップコート層形成ポリイミドフィルムBの作成>
基材である厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)の上に、上記コーティング材Bをバーコーターで塗付し、130℃に2分間加熱して乾燥させた。このようにして、ポリイミド系基材の片面に厚さ10nmの透明なトップコート層を有する基材(トップコート層形成ポリイミドフィルムB)を作製した。 [Manufacturing Example 4]: Preparation of polyimide film B for forming top coat layer <Preparation of coating material B>
Dispersion containing 25% by weight of a polyester resin (binder) as a binder (manufactured by Toyobo Co., Ltd., trade name "Binaroll MD-1480" (aqueous dispersion of saturated copolyester resin); hereinafter also referred to as "binder dispersion". ) Was prepared.
In addition, as a slip agent, an aqueous dispersion of carnauba wax (manufactured by Nippon Wax Co., Ltd., trade name “Purified Carnauba Waxus No. 2 powder”) (hereinafter also referred to as “slipper dispersion”) was prepared.
Further, an aqueous solution containing 0.5% by weight of poly(3,4-dioxythiophene) (PEDOT) and 0.8% by weight of polystyrene sulfonate (number average molecular weight 150,000) (PSS) as a conductive polymer (H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution”) was prepared.
In a mixed solvent of water and ethanol (weight ratio of 50:50), 100 parts by weight of the binder dispersion liquid in solid content, 30 parts by weight of the slip agent dispersion liquid in solid content, and the conductive polymer aqueous solution were added. 50 parts by weight of solid content and 7 parts by weight of melamine-based cross-linking agent were added, and the mixture was stirred for about 20 minutes and mixed sufficiently. Thus, coating material B having an NV of about 0.15% by weight was prepared.
<Preparation of top coat layer forming polyimide film B>
The coating material B is applied by a bar coater on a polyimide base material (trade name "Kapton", manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 μm, which is a base material, and dried by heating at 130° C. for 2 minutes. Let Thus, a base material (topcoat layer forming polyimide film B) having a transparent topcoat layer having a thickness of 10 nm on one surface of the polyimide base material was produced.
[製造例5]:トップコート層形成ポリイミドフィルムCの作成
<コーティング材Cの調製>
バインダとしてエチレングリコール25mol%とネオペチングリコール25mol%とテレフタル酸30mol%とアジピン酸10mol%とトリレンジイソシアネート10mol%からなるポリエステルウレタン樹脂を25重量%含む水溶液;以下「バインダ分散液」ともいう。)を用意した。
また、滑り剤として、カルナウバワックス(日本ワックス社製、商品名「精製カルナウバワックッス2号粉末」)の水分散液(以下「滑り剤分散液」ともいう。)を用意した。
さらに、導電性ポリマーとして、ポリ(3,4-ジオキシチオフェン)(PEDOT)0.5重量%、及び、ポリスチレンスルホネート(数平均分子量15万)(PSS)0.8重量%を含む水溶液(H.C.Stark社製品、商品名「Baytron P」;以下「導電性ポリマー水溶液」ともいう。)を用意した。
さらに分散剤としてポリエチレングリコール(PEG)アルキルエーテル 10重量%、ポリビニルアルコール10重量%を含む水溶液を用意した。
水とエタノールとの混合溶媒(重量比が50:50)に、上記バインダ分散液を固形分比で40重量部と、上記滑り剤分散液を固形分量で5重量部と、上記導電性ポリマー水溶液を固形分量で8重量部と、上記分散剤40重量部と、メラミン系架橋剤7重量部とを加え、約20分間攪拌して、十分に混合した。このようにして、NVが約0.30重量%のコーティング材Cを調製した。
<トップコート層形成ポリイミドフィルムCの作成>
基材である厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)の上に、上記コーティング材Cをバーコーターで塗付し、130℃に2分間加熱して乾燥させた。このようにして、ポリイミド系基材の片面に厚さ50nmの透明なトップコート層を有する基材(トップコート層形成ポリイミドフィルムC)を作製した。 [Manufacturing Example 5]: Preparation of top coat layer forming polyimide film C <Preparation of coating material C>
An aqueous solution containing 25% by weight of a polyester urethane resin composed of 25 mol% of ethylene glycol, 25 mol% of neopetin glycol, 30 mol% of terephthalic acid, 10 mol% of adipic acid and 10 mol% of tolylene diisocyanate as a binder; hereinafter also referred to as "binder dispersion liquid". ) Was prepared.
In addition, as a slip agent, an aqueous dispersion of carnauba wax (manufactured by Nippon Wax Co., Ltd., trade name “Purified Carnauba Waxus No. 2 powder”) (hereinafter also referred to as “slipper dispersion”) was prepared.
Further, an aqueous solution containing 0.5% by weight of poly(3,4-dioxythiophene) (PEDOT) and 0.8% by weight of polystyrene sulfonate (number average molecular weight 150,000) (PSS) as a conductive polymer (H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution”) was prepared.
Further, an aqueous solution containing 10% by weight of polyethylene glycol (PEG) alkyl ether and 10% by weight of polyvinyl alcohol was prepared as a dispersant.
In a mixed solvent of water and ethanol (weight ratio 50:50), 40 parts by weight of the binder dispersion liquid in solid content, 5 parts by weight of the slip agent dispersion liquid in solid content, and the conductive polymer aqueous solution. 8 parts by weight of solid content, 40 parts by weight of the above dispersant, and 7 parts by weight of melamine-based cross-linking agent were added, and the mixture was stirred for about 20 minutes and mixed sufficiently. Thus, coating material C having an NV of about 0.30% by weight was prepared.
<Preparation of top coat layer forming polyimide film C>
The coating material C is applied with a bar coater onto a polyimide base material (trade name "Kapton", manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 μm, which is a base material, and heated at 130° C. for 2 minutes to dry. Let In this way, a base material (topcoat layer forming polyimide film C) having a transparent topcoat layer having a thickness of 50 nm on one surface of the polyimide base material was produced.
<コーティング材Cの調製>
バインダとしてエチレングリコール25mol%とネオペチングリコール25mol%とテレフタル酸30mol%とアジピン酸10mol%とトリレンジイソシアネート10mol%からなるポリエステルウレタン樹脂を25重量%含む水溶液;以下「バインダ分散液」ともいう。)を用意した。
また、滑り剤として、カルナウバワックス(日本ワックス社製、商品名「精製カルナウバワックッス2号粉末」)の水分散液(以下「滑り剤分散液」ともいう。)を用意した。
さらに、導電性ポリマーとして、ポリ(3,4-ジオキシチオフェン)(PEDOT)0.5重量%、及び、ポリスチレンスルホネート(数平均分子量15万)(PSS)0.8重量%を含む水溶液(H.C.Stark社製品、商品名「Baytron P」;以下「導電性ポリマー水溶液」ともいう。)を用意した。
さらに分散剤としてポリエチレングリコール(PEG)アルキルエーテル 10重量%、ポリビニルアルコール10重量%を含む水溶液を用意した。
水とエタノールとの混合溶媒(重量比が50:50)に、上記バインダ分散液を固形分比で40重量部と、上記滑り剤分散液を固形分量で5重量部と、上記導電性ポリマー水溶液を固形分量で8重量部と、上記分散剤40重量部と、メラミン系架橋剤7重量部とを加え、約20分間攪拌して、十分に混合した。このようにして、NVが約0.30重量%のコーティング材Cを調製した。
<トップコート層形成ポリイミドフィルムCの作成>
基材である厚み50μmのポリイミド系基材(商品名「カプトン」、東レ・デュポン株式会社製)の上に、上記コーティング材Cをバーコーターで塗付し、130℃に2分間加熱して乾燥させた。このようにして、ポリイミド系基材の片面に厚さ50nmの透明なトップコート層を有する基材(トップコート層形成ポリイミドフィルムC)を作製した。 [Manufacturing Example 5]: Preparation of top coat layer forming polyimide film C <Preparation of coating material C>
An aqueous solution containing 25% by weight of a polyester urethane resin composed of 25 mol% of ethylene glycol, 25 mol% of neopetin glycol, 30 mol% of terephthalic acid, 10 mol% of adipic acid and 10 mol% of tolylene diisocyanate as a binder; hereinafter also referred to as "binder dispersion liquid". ) Was prepared.
In addition, as a slip agent, an aqueous dispersion of carnauba wax (manufactured by Nippon Wax Co., Ltd., trade name “Purified Carnauba Waxus No. 2 powder”) (hereinafter also referred to as “slipper dispersion”) was prepared.
Further, an aqueous solution containing 0.5% by weight of poly(3,4-dioxythiophene) (PEDOT) and 0.8% by weight of polystyrene sulfonate (number average molecular weight 150,000) (PSS) as a conductive polymer (H C. Stark product, trade name “Baytron P”; hereinafter also referred to as “conductive polymer aqueous solution”) was prepared.
Further, an aqueous solution containing 10% by weight of polyethylene glycol (PEG) alkyl ether and 10% by weight of polyvinyl alcohol was prepared as a dispersant.
In a mixed solvent of water and ethanol (weight ratio 50:50), 40 parts by weight of the binder dispersion liquid in solid content, 5 parts by weight of the slip agent dispersion liquid in solid content, and the conductive polymer aqueous solution. 8 parts by weight of solid content, 40 parts by weight of the above dispersant, and 7 parts by weight of melamine-based cross-linking agent were added, and the mixture was stirred for about 20 minutes and mixed sufficiently. Thus, coating material C having an NV of about 0.30% by weight was prepared.
<Preparation of top coat layer forming polyimide film C>
The coating material C is applied with a bar coater onto a polyimide base material (trade name "Kapton", manufactured by Toray DuPont Co., Ltd.) having a thickness of 50 μm, which is a base material, and heated at 130° C. for 2 minutes to dry. Let In this way, a base material (topcoat layer forming polyimide film C) having a transparent topcoat layer having a thickness of 50 nm on one surface of the polyimide base material was produced.
[実施例9]
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例1と同様に行い、粘着フィルム(9)を得た。
結果を表2に示した。 [Example 9]
An adhesive film (9) was obtained in the same manner as in Example 1 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例1と同様に行い、粘着フィルム(9)を得た。
結果を表2に示した。 [Example 9]
An adhesive film (9) was obtained in the same manner as in Example 1 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
[実施例10]
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例2と同様に行い、粘着フィルム(10)を得た。
結果を表2に示した。 [Example 10]
An adhesive film (10) was obtained in the same manner as in Example 2 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例2と同様に行い、粘着フィルム(10)を得た。
結果を表2に示した。 [Example 10]
An adhesive film (10) was obtained in the same manner as in Example 2 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
[実施例11]
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例4と同様に行い、粘着フィルム(11)を得た。
結果を表2に示した。 [Example 11]
An adhesive film (11) was obtained in the same manner as in Example 4, except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例4と同様に行い、粘着フィルム(11)を得た。
結果を表2に示した。 [Example 11]
An adhesive film (11) was obtained in the same manner as in Example 4, except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
[実施例12]
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例7と同様に行い、粘着フィルム(12)を得た。
結果を表2に示した。 [Example 12]
An adhesive film (12) was obtained in the same manner as in Example 7 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は実施例7と同様に行い、粘着フィルム(12)を得た。
結果を表2に示した。 [Example 12]
An adhesive film (12) was obtained in the same manner as in Example 7 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
[実施例13]
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例1と同様に行い、粘着フィルム(13)を得た。
結果を表2に示した。 [Example 13]
An adhesive film (13) was obtained in the same manner as in Example 1 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例1と同様に行い、粘着フィルム(13)を得た。
結果を表2に示した。 [Example 13]
An adhesive film (13) was obtained in the same manner as in Example 1 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
[実施例14]
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例2と同様に行い、粘着フィルム(14)を得た。
結果を表2に示した。 [Example 14]
An adhesive film (14) was obtained in the same manner as in Example 2 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例2と同様に行い、粘着フィルム(14)を得た。
結果を表2に示した。 [Example 14]
An adhesive film (14) was obtained in the same manner as in Example 2 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
[実施例15]
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例3と同様に行い、粘着フィルム(15)を得た。
結果を表2に示した。 [Example 15]
An adhesive film (15) was obtained in the same manner as in Example 3 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例3と同様に行い、粘着フィルム(15)を得た。
結果を表2に示した。 [Example 15]
An adhesive film (15) was obtained in the same manner as in Example 3 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
[実施例16]
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例4と同様に行い、粘着フィルム(16)を得た。
結果を表2に示した。 [Example 16]
An adhesive film (16) was obtained in the same manner as in Example 4, except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例4と同様に行い、粘着フィルム(16)を得た。
結果を表2に示した。 [Example 16]
An adhesive film (16) was obtained in the same manner as in Example 4, except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
[実施例17]
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例7と同様に行い、粘着フィルム(17)を得た。
結果を表2に示した。 [Example 17]
An adhesive film (17) was obtained in the same manner as in Example 7, except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は実施例7と同様に行い、粘着フィルム(17)を得た。
結果を表2に示した。 [Example 17]
An adhesive film (17) was obtained in the same manner as in Example 7, except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
[比較例6]
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は比較例1と同様に行い、粘着フィルム(C6)を得た。
結果を表2に示した。 [Comparative Example 6]
An adhesive film (C6) was obtained in the same manner as in Comparative Example 1 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は比較例1と同様に行い、粘着フィルム(C6)を得た。
結果を表2に示した。 [Comparative Example 6]
An adhesive film (C6) was obtained in the same manner as in Comparative Example 1 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
[比較例7]
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は比較例2と同様に行い、粘着フィルム(C7)を得た。
結果を表2に示した。 [Comparative Example 7]
An adhesive film (C7) was obtained in the same manner as in Comparative Example 2 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムBを使用した以外は比較例2と同様に行い、粘着フィルム(C7)を得た。
結果を表2に示した。 [Comparative Example 7]
An adhesive film (C7) was obtained in the same manner as in Comparative Example 2 except that the top coat layer-forming polyimide film B was used as the substrate.
The results are shown in Table 2.
[比較例8]
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は比較例1と同様に行い、粘着フィルム(C8)を得た。
結果を表2に示した。 [Comparative Example 8]
An adhesive film (C8) was obtained in the same manner as in Comparative Example 1 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は比較例1と同様に行い、粘着フィルム(C8)を得た。
結果を表2に示した。 [Comparative Example 8]
An adhesive film (C8) was obtained in the same manner as in Comparative Example 1 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
[比較例9]
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は比較例2と同様に行い、粘着フィルム(C9)を得た。
結果を表2に示した。 [Comparative Example 9]
An adhesive film (C9) was obtained in the same manner as in Comparative Example 2 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
基材としてトップコート層形成ポリイミドフィルムCを使用した以外は比較例2と同様に行い、粘着フィルム(C9)を得た。
結果を表2に示した。 [Comparative Example 9]
An adhesive film (C9) was obtained in the same manner as in Comparative Example 2 except that the top coat layer-forming polyimide film C was used as the substrate.
The results are shown in Table 2.
本発明の粘着フィルムは、屈曲性および透明性に優れるので、例えば、可動屈曲部を有するベンダブルデバイス(曲げることが可能なデバイス)やフォルダブルデバイス(折りたたむことが可能なデバイス)やローラブルデバイス(丸めることが可能なデバイス)に好適に備えられ得る。
Since the pressure-sensitive adhesive film of the present invention is excellent in flexibility and transparency, for example, a bendable device (a bendable device), a foldable device (a foldable device), or a rollable device (having a movable bending portion) (a bendable device). It is suitable for a rollable device).
1000 フォルダブルデバイス
100 粘着フィルム
10 カバーフィルム
20 粘着剤層
30 偏光板
40 粘着剤層
50 タッチセンサー
60 粘着剤層
70 OLED
80 粘着剤層
90 基材層
1 6Φガラス棒
2 シリコーン処理セパレータ
3 接着剤層
4 固定ガラス
5 PETフィルム
1000Foldable device 100 Adhesive film 10 Cover film 20 Adhesive layer 30 Polarizing plate 40 Adhesive layer 50 Touch sensor 60 Adhesive layer 70 OLED
80Adhesive Layer 90 Base Material Layer 1 6Φ Glass Rod 2 Silicone Treated Separator 3 Adhesive Layer 4 Fixed Glass 5 PET Film
100 粘着フィルム
10 カバーフィルム
20 粘着剤層
30 偏光板
40 粘着剤層
50 タッチセンサー
60 粘着剤層
70 OLED
80 粘着剤層
90 基材層
1 6Φガラス棒
2 シリコーン処理セパレータ
3 接着剤層
4 固定ガラス
5 PETフィルム
1000
80
Claims (20)
- 基材層と粘着剤層を有する粘着フィルムであって、
粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)が0.1以下である、
粘着フィルム。 An adhesive film having a base material layer and an adhesive layer,
Tan δ (0.7%) at a strain of 0.7% measured in the tensile mode of the viscoelasticity measuring device is 0.1 or less,
Adhesive film. - 基材層と粘着剤層を有する粘着フィルムであって、
粘弾性測定装置の引張モードにおいて測定した歪み0.7%におけるtanδ(0.7%)と歪み0.1%におけるtanδ(0.1%)との差(tanδ(0.7%)-tanδ(0.1%))が0.05以下である、
粘着フィルム。 An adhesive film having a base material layer and an adhesive layer,
The difference between tan δ (0.7%) at a strain of 0.7% and tan δ (0.1%) at a strain of 0.1% measured in the tensile mode of the viscoelasticity measuring device (tan δ (0.7%)-tan δ (0.1%)) is 0.05 or less,
Adhesive film. - 6Φで屈曲させて90℃にて48時間保持させた後に、該屈曲を解放し、23℃、50%RHにて24時間放置させた後の屈曲角度が60度~180度である、請求項1または2に記載の粘着フィルム。 The bending angle is 60° to 180° after being bent at 6Φ and held at 90° C. for 48 hours, then released, and allowed to stand at 23° C. and 50% RH for 24 hours. The pressure-sensitive adhesive film according to 1 or 2.
- 前記基材層の前記粘着剤層を有する面と反対側の面にトップコート層を有する、請求項1から3までのいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 1 to 3, which has a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer.
- 前記トップコート層が、ポリエステル樹脂およびウレタン系樹脂から選ばれる少なくとも1種を含むバインダを含有する、請求項4に記載の粘着フィルム。 The pressure-sensitive adhesive film according to claim 4, wherein the top coat layer contains a binder containing at least one selected from polyester resins and urethane resins.
- 前記バインダがウレタン系樹脂を含む、請求項5に記載の粘着フィルム。 The adhesive film according to claim 5, wherein the binder contains a urethane resin.
- 前記トップコート層が帯電防止成分を含有する、請求項4から6までのいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 4 to 6, wherein the top coat layer contains an antistatic component.
- 前記基材層の23℃におけるヤング率が6.0×107Pa以上である、請求項1から7までのいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to claim 1, wherein the base layer has a Young's modulus at 23° C. of 6.0×10 7 Pa or more.
- 前記基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種である、請求項8に記載の粘着フィルム。 The pressure-sensitive adhesive film according to claim 8, wherein the material of the base material layer is at least one selected from polyimide and polyether ether ketone.
- 前記基材層の前記粘着剤層を有する面と反対側の面にトップコート層を有し、該トップコート層がウレタン系樹脂を含むバインダおよび帯電防止成分を含有し、前記基材層の材料がポリイミドおよびポリエーテルエーテルケトンから選ばれる少なくとも1種である、請求項1から3までのいずれかに記載の粘着フィルム。 A material of the base material layer having a topcoat layer on the surface of the base material layer opposite to the surface having the pressure-sensitive adhesive layer, the topcoat layer containing a binder containing an urethane resin and an antistatic component. The pressure-sensitive adhesive film according to any one of claims 1 to 3, wherein is at least one selected from polyimide and polyether ether ketone.
- 全光線透過率が20%以上である、請求項1から10までのいずれかに記載の粘着フィルム。 The adhesive film according to any one of claims 1 to 10, which has a total light transmittance of 20% or more.
- ヘイズが15%以下である、請求項1から11までのいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 1 to 11, which has a haze of 15% or less.
- 前記粘着剤層の、23℃における、引張速度300mm/分、180度ピールでの、SUS板に対する粘着力が1N/25mm以上である、請求項1から12までのいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 1 to 12, wherein the pressure-sensitive adhesive layer has a pressure-sensitive adhesive force of 1 N/25 mm or more to a SUS plate at a pulling speed of 300 mm/min and a peel of 180 degrees at 23°C.
- 前記粘着剤層がアクリル系粘着剤を含む、請求項1から13までのいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 1 to 13, wherein the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive.
- フォルダブル部材に貼り付けられる、請求項1から14までのいずれかに記載の粘着フィルム。 The adhesive film according to any one of claims 1 to 14, which is attached to a foldable member.
- 前記フォルダブル部材がOLEDである、請求項15に記載の粘着フィルム。 The adhesive film according to claim 15, wherein the foldable member is an OLED.
- ローラブル部材に貼り付けられる、請求項1から16までのいずれかに記載の粘着フィルム。 The adhesive film according to any one of claims 1 to 16, which is attached to a rollable member.
- 前記ローラブル部材がOLEDである、請求項17に記載の粘着フィルム。 The adhesive film according to claim 17, wherein the rollable member is an OLED.
- 請求項1から14までのいずれかに記載の粘着フィルムを備えるフォルダブルデバイス。 Foldable device comprising the adhesive film according to any one of claims 1 to 14.
- 請求項1から14までのいずれかに記載の粘着フィルムを備えるローラブルデバイス。
A rollable device comprising the adhesive film according to any one of claims 1 to 14.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201980078499.9A CN113165362B (en) | 2018-11-28 | 2019-11-15 | Adhesive film, foldable device, and rollable device |
KR1020217015741A KR102579623B1 (en) | 2018-11-28 | 2019-11-15 | Adhesive films, foldable devices and rollable devices |
SG11202103223SA SG11202103223SA (en) | 2018-11-28 | 2019-11-15 | Adhesive film, foldable device, and rollable device |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-221906 | 2018-11-28 | ||
JP2018221906 | 2018-11-28 | ||
JP2019-110014 | 2019-06-13 | ||
JP2019110014 | 2019-06-13 | ||
JP2019206027A JP2020204010A (en) | 2018-11-28 | 2019-11-14 | Adhesive film, foldable device and rollable device |
JP2019-206027 | 2019-11-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020110772A1 true WO2020110772A1 (en) | 2020-06-04 |
Family
ID=70851986
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/044831 WO2020110772A1 (en) | 2018-11-28 | 2019-11-15 | Adhesive film, foldable device, and rollable device |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2024052821A (en) |
WO (1) | WO2020110772A1 (en) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007169458A (en) * | 2005-12-22 | 2007-07-05 | Fujimori Kogyo Co Ltd | Protecting film |
JP2011168049A (en) * | 2010-01-21 | 2011-09-01 | Nitto Denko Corp | Transparent film and use thereof |
JP2012057037A (en) * | 2010-09-08 | 2012-03-22 | Nitto Denko Corp | Double-sided adhesive tape for fixing flexible printed circuit board and flexible printed circuit board with the tape |
JP2013075978A (en) * | 2011-09-30 | 2013-04-25 | Nitto Denko Corp | Adhesive sheet |
JP2015044970A (en) * | 2013-07-30 | 2015-03-12 | 日東電工株式会社 | Surface protective film and optical member |
JP2015229759A (en) * | 2014-06-06 | 2015-12-21 | 日東電工株式会社 | Adhesive sheet for optics |
JP2016138234A (en) * | 2015-01-22 | 2016-08-04 | 日東電工株式会社 | Optical adhesive sheet |
JP2017024262A (en) * | 2015-07-22 | 2017-02-02 | 日東電工株式会社 | Electrically conductive film laminate having transparent adhesive layer |
JP2017025205A (en) * | 2015-07-22 | 2017-02-02 | 日東電工株式会社 | Cover member with transparent conductive layer having transparent adhesive layer |
JP2017119749A (en) * | 2015-12-28 | 2017-07-06 | 日東電工株式会社 | Protective film for transparent conductive film and laminate |
JP2018027996A (en) * | 2016-08-15 | 2018-02-22 | 日東電工株式会社 | Adhesive layer for flexible image display device, laminate for flexible image display device, and flexible image display device |
JP2018168305A (en) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | Adhesive sheet, laminate, and device |
-
2019
- 2019-11-15 WO PCT/JP2019/044831 patent/WO2020110772A1/en active Application Filing
-
2024
- 2024-02-21 JP JP2024024876A patent/JP2024052821A/en active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007169458A (en) * | 2005-12-22 | 2007-07-05 | Fujimori Kogyo Co Ltd | Protecting film |
JP2011168049A (en) * | 2010-01-21 | 2011-09-01 | Nitto Denko Corp | Transparent film and use thereof |
JP2012057037A (en) * | 2010-09-08 | 2012-03-22 | Nitto Denko Corp | Double-sided adhesive tape for fixing flexible printed circuit board and flexible printed circuit board with the tape |
JP2013075978A (en) * | 2011-09-30 | 2013-04-25 | Nitto Denko Corp | Adhesive sheet |
JP2015044970A (en) * | 2013-07-30 | 2015-03-12 | 日東電工株式会社 | Surface protective film and optical member |
JP2015229759A (en) * | 2014-06-06 | 2015-12-21 | 日東電工株式会社 | Adhesive sheet for optics |
JP2016138234A (en) * | 2015-01-22 | 2016-08-04 | 日東電工株式会社 | Optical adhesive sheet |
JP2017024262A (en) * | 2015-07-22 | 2017-02-02 | 日東電工株式会社 | Electrically conductive film laminate having transparent adhesive layer |
JP2017025205A (en) * | 2015-07-22 | 2017-02-02 | 日東電工株式会社 | Cover member with transparent conductive layer having transparent adhesive layer |
JP2017119749A (en) * | 2015-12-28 | 2017-07-06 | 日東電工株式会社 | Protective film for transparent conductive film and laminate |
JP2018027996A (en) * | 2016-08-15 | 2018-02-22 | 日東電工株式会社 | Adhesive layer for flexible image display device, laminate for flexible image display device, and flexible image display device |
JP2018168305A (en) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | Adhesive sheet, laminate, and device |
Also Published As
Publication number | Publication date |
---|---|
JP2024052821A (en) | 2024-04-12 |
TW202031857A (en) | 2020-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102579623B1 (en) | Adhesive films, foldable devices and rollable devices | |
JP6249617B2 (en) | Surface protection film | |
JP6258681B2 (en) | Surface protective film and optical member | |
JP6704671B2 (en) | Adhesive sheet and optical member | |
TWI660988B (en) | Surface protective film and optical component | |
JP6419548B2 (en) | Surface protective film, method for manufacturing surface protective film, and optical member | |
JP6092034B2 (en) | Surface protective film and optical member | |
US20130130024A1 (en) | Release agent composition, release sheet, and pressure-sensitive adhesive body | |
JP6594637B2 (en) | Adhesive sheet and optical member | |
US20180029329A1 (en) | Release agent composition, release sheet, single-sided pressure-sensitive adhesive sheet and double-sided (faced) pressure-sensitive adhesive sheet | |
JP2015163690A (en) | double-sided adhesive sheet | |
JP2015027766A (en) | Surface protective film and optical member | |
JP6546806B2 (en) | Optical surface protection film with separator | |
JP6599618B2 (en) | Adhesive sheet and optical member | |
JP6993543B1 (en) | Protective film, foldable device, and rollable device | |
JP6599619B2 (en) | Adhesive sheet and optical member | |
KR102476947B1 (en) | Pressure-sensitive adhesive sheet, and optical member | |
JP6594636B2 (en) | Adhesive sheet and optical member | |
WO2020110772A1 (en) | Adhesive film, foldable device, and rollable device | |
JP7036488B2 (en) | Substrate-less double-sided adhesive sheet | |
TW202204446A (en) | Film with top coat layer, reinforcing film and image display device in which a change in contact angle before and after a surface activation treatment is limited | |
TWI846764B (en) | Adhesive film, foldable device, and roll-up device | |
JP2019061682A (en) | Surface protective film, production method of surface protective film, and optical member |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19891320 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20217015741 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19891320 Country of ref document: EP Kind code of ref document: A1 |