KR20210116482A - laminated film for reinforcement - Google Patents

Abstract

It is a laminated film for reinforcement which has a surface protection film and a separator, Comprising: The laminated film for reinforcement which can peel smoothly a separator from the surface of an adhesive layer is provided. The reinforcing laminated film of the present invention is a reinforcing laminated film having a separator, a pressure-sensitive adhesive layer (1), a reinforcing substrate, and a surface protection film in this order, and the separator and the pressure-sensitive adhesive layer (1) are directly laminated, , the reinforcing substrate and the surface protection film are directly laminated, and the separator includes a substrate layer (1), and the surface protection film includes a substrate layer (2) and an adhesive layer (2), The pressure-sensitive adhesive layer 2 is directly laminated on the reinforcing substrate, and the instrument peeling force P of the reinforcing substrate in the reinforcing laminated film is the instrumental peeling force Q of the separator in the reinforcing laminated film. bigger than

Description

laminated film for reinforcement

The present invention relates to a laminated film for reinforcement.

In order to impart rigidity or impact resistance to an optical member or electronic member, etc., in some cases, a reinforcing film (reinforcing base material provided with an adhesive layer) is bonded in advance to the exposed surface side of the optical member or electronic member, etc. Patent Document 1). Usually, such a film for reinforcing has an adhesive layer for bonding, and for the protection of the surface of this adhesive layer, a separator is normally provided in the surface of an adhesive layer during the time of use.

In addition, in order to prevent damage to the surface of the reinforcing film during processing, assembly, inspection, transportation, etc., processing, assembly, inspection, transportation, etc. sometimes it is done. Such a surface protection film peels from the film for reinforcement when the need of surface protection is no longer (patent document 2).

In such a reinforcing laminated film having such a surface protection film and a separator, when the separator is peeled from the surface of the pressure-sensitive adhesive layer, the separator is smoothly peeled from the surface of the pressure-sensitive adhesive layer so as not to be peeled off at the interface between the surface protection film and the reinforcing film, etc. What you can do is important.

Japanese Patent No. 6366199 Publication Japanese Patent Laid-Open No. 2016-17109

The subject of this invention is a laminated film for reinforcement which has a surface protection film and a separator, Comprising: It is providing the laminated film for reinforcement which can peel smoothly a separator from the surface of an adhesive layer.

The laminated film for reinforcement of the present invention comprises:

It is a laminated film for reinforcement having a separator, an adhesive layer (1), a substrate for reinforcement, and a surface protection film in this order,

The separator and the pressure-sensitive adhesive layer 1 are directly laminated,

The reinforcing substrate and the surface protection film are directly laminated,

The separator includes a base layer (1),

The surface protection film includes a base material layer (2) and an adhesive layer (2), and the pressure-sensitive adhesive layer (2) is directly laminated on the reinforcing substrate,

The instrument peeling force P of the said base material for reinforcement in this laminated film for reinforcement is larger than the instrument peeling force Q of the said separator in this laminated film for reinforcement.

In one embodiment, the said base material for reinforcement is a plastic film.

In one embodiment, the thickness of the said base material for reinforcement is 25 micrometers - 500 micrometers.

In one embodiment, the thickness of the said separator is 1 micrometer - 100 micrometers.

In one embodiment, the thickness of the said surface protection film is 5 micrometers - 500 micrometers.

In one embodiment, the said adhesive layer 1 is comprised from at least 1 sort(s) selected from the group which consists of an acrylic adhesive, a urethane adhesive, a rubber-type adhesive, and a silicone adhesive.

In one embodiment, the acrylic pressure-sensitive adhesive is formed of an acrylic pressure-sensitive adhesive composition, and the acrylic pressure-sensitive adhesive composition is (a component) an alkyl ester having 4 to 12 carbon atoms in the alkyl ester moiety (meth)acrylic acid alkylester, (component b) An acrylic polymer formed by polymerization from a composition (A) comprising at least one selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid, (component c) polyfunctional isocyanate crosslinking agent and epoxy At least one selected from the group consisting of a system crosslinking agent is included.

In one embodiment, the said adhesive layer 2 is comprised from at least 1 sort(s) selected from the group which consists of an acrylic adhesive, a urethane adhesive, a rubber-type adhesive, and a silicone adhesive.

In one embodiment, the said adhesive layer 2 is comprised from at least 1 sort(s) chosen from the group which consists of an acrylic adhesive and a urethane type adhesive.

In one embodiment, the acrylic pressure-sensitive adhesive is formed of an acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer (2), and the acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer (2) has 4 to 12 carbon atoms in the alkyl group of the alkyl ester (component p) An acrylic polymer formed by polymerization from a composition (B) comprising at least one selected from the group consisting of phosphorus (meth)acrylic acid alkyl ester, (q component) (meth)acrylic acid ester having an OH group, and (meth)acrylic acid; and (r component) at least one selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent.

In one embodiment, said (p component) is 2-ethylhexyl acrylate, said (q component) is 2-hydroxyethyl acrylate, and said (r component) is a polyfunctional isocyanate type crosslinking agent.

In one embodiment, the said (r component) is a trimethylol propane/tolylene diisocyanate adduct.

In one embodiment, the temperature of the pressure-sensitive adhesive layer 1 of the pressure-sensitive adhesive layer 1 exposed by peeling the separator at a temperature of 23°C, a humidity of 50%RH, a peeling angle of 150°C, and a peeling rate of 10m/min, a temperature of 23°C, a humidity of 50%RH, The initial adhesive force with respect to the glass plate in 180 degreeC of peeling angles and 300 mm/min of peeling rates is 1.0 N/25 mm or more.

ADVANTAGE OF THE INVENTION According to this invention, it is a laminated film for reinforcement which has a surface protection film and a separator, Comprising: The laminated film for reinforcement which can peel smoothly a separator from the surface of an adhesive layer can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of one Embodiment of the laminated|multilayer film for reinforcement of this invention.

In the present specification, where the expression "weight" exists, it may be replaced with "mass" commonly used as an SI-based unit for indicating weight.

In this specification, when there is an expression "(meth)acryl", it means "acryl and/or methacryl", and when there is an expression "(meth)acrylate", "acrylate and/or methacryl" rate", and when the expression "(meth)allyl" is used, "allyl and/or methallyl" is meant, and when the expression "(meth)acrolein" is present, "acrolein and/or meta means "crolein".

≪≪Laminated film for reinforcement≫≫

The laminated film for reinforcement of this invention has a separator, the adhesive layer 1, the base material for reinforcement, and a surface protection film in this order. As long as the laminated film for reinforcement of this invention has a separator, the adhesive layer 1, the base material for reinforcement, and a surface protection film in this order, even if it has any appropriate other layer within the range which does not impair the effect of this invention, do.

The laminated film for reinforcement of this invention WHEREIN: A separator and the adhesive layer 1 are laminated|stacked directly.

In the laminated film for reinforcement of the present invention, the substrate for reinforcement and the surface protection film are directly laminated.

The laminated film for reinforcement of this invention WHEREIN: The separator contains the base material layer (1).

The laminated film for reinforcement of this invention WHEREIN: The surface protection film contains the base material layer 2 and the adhesive layer 2, The said adhesive layer 2 is laminated|stacked directly on the base material for reinforcement.

The overall thickness of the laminated film for reinforcement of the present invention is preferably 80 µm to 600 µm, more preferably 90 µm to 500 µm, still more preferably from the viewpoint of further expressing the effect of the present invention. is 95 μm to 400 μm, particularly preferably 100 μm to 300 μm.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of one Embodiment of the laminated|multilayer film for reinforcement of this invention. 1, the reinforcing laminated film 1000 of the present invention has a separator 100, an adhesive layer (1) 200, a reinforcing base material 300, and a surface protection film 400 in this order, The surface protection film 400 includes a base layer (2) (410) and an adhesive layer (2) (420).

Taking Fig. 1 as an example, in one embodiment of the method of using the laminated film 1000 for reinforcement of the present invention, first, the separator 100 is peeled to expose the pressure-sensitive adhesive layer 1, 200, and the optical member or electronic It bonds to the exposed surface side, such as a member, and reinforces this optical member and this electronic member. The surface protection film 400 is adhered to the product in this state to prevent damage to the surface of the reinforcing base material 300 when processing, assembling, inspecting, transporting, etc. When it disappears, it peels from the base material 300 for reinforcement.

In the reinforcing laminated film of the present invention, two members that can be peeled during use, that is, a separator and a surface protection film, by appropriately designing the difference in the magnitude of the instrument peeling force when each is to be peeled. , the separator can be smoothly peeled from the surface of the pressure-sensitive adhesive layer. If such a design is not carried out, when the separator is peeled from the surface of the pressure-sensitive adhesive layer, there is a fear that peeling at an unintended location, such as peeling off at the interface between the surface protection film and the reinforcing substrate, may occur single or concurrently. have.

As said design, in the laminated film for reinforcement of this invention, the gauge peeling force P of the said base material for reinforcement in the laminated film for reinforcement is larger than the gauge peeling force Q of the said separator in the said laminated film for reinforcement. The detail of the measuring method of the instrument peel force P and the instrument peel force Q is mentioned later.

The instrument peeling force P is preferably 0.1N/25mm to 20N/25mm, more preferably 0.5N/25mm to 15N/25mm, from the point where the effect of the present invention can be further expressed, More preferably, they are 1.0N/25mm - 10N/25mm, Especially preferably, they are 1.0N/25mm - 8N/25mm.

The instrument peeling force Q is, from the viewpoint that the effect of the present invention can be further expressed, preferably 0.1N/25mm to 10N/25mm, more preferably 0.3N/25mm to 7N/25mm, More preferably, they are 0.5N/25mm - 5N/25mm, Especially preferably, they are 0.7N/25mm - 3N/25mm.

The difference (PQ) between the instrument peel force P and the instrument peel force Q is preferably 0.001 N/25 mm to 10 N/25 mm, more preferably 0.005 N, from the viewpoint that the effect of the present invention can be further expressed. /25 mm to 8 N/25 mm, more preferably 0.01 N/25 mm to 6 N/25 mm, and particularly preferably 0.05 N/25 mm to 5 N/25 mm.

The laminated film for reinforcement of this invention can be manufactured by arbitrary appropriate methods within the range which does not impair the effect of this invention. For example, a pressure-sensitive adhesive layer 1 is formed on a reinforcing base material, a separator is bonded on the formed pressure-sensitive adhesive layer 1, and, on the other hand, the surface of the reinforcing base material on the opposite side of the pressure-sensitive adhesive layer 1 is protected. It can manufacture by bonding a film.

≪Separator≫

The separator is laminated directly on the pressure-sensitive adhesive layer 1 . When the laminated film for reinforcement of the present invention is used, preferably first, the separator is peeled to expose the pressure-sensitive adhesive layer 1, and the adhesive layer 1 is bonded to the exposed surface side of the optical member or the electronic member, and the optical member or the electronic member. reinforce the member.

The thickness of the separator is preferably 1 µm to 100 µm, more preferably 5 µm to 90 µm, further preferably 10 µm to 80 µm from the viewpoint of further expressing the effect of the present invention, Especially preferably, it is 20 micrometers - 75 micrometers.

The separator, Preferably, the base material layer 1 is included. A separator can contain other arbitrary appropriate layers according to the objective in the range which does not impair the effect of this invention other than the base material layer 1.

<Base layer (1)>

As the base material layer 1, the base material layer formed from arbitrary suitable materials is employable in the range which does not impair the effect of this invention. Examples of such a material include a plastic film, a nonwoven fabric, paper, metal foil, a woven fabric, a rubber sheet, a foam sheet, and a laminate of these (especially a laminate including a plastic film).

As a plastic film, For example, the plastic film comprised from polyester-type resin, such as a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), and a polybutylene terephthalate (PBT); Plastics composed of olefinic resins containing α-olefins such as polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA) as a monomer component film; a plastic film composed of polyvinyl chloride (PVC); a plastic film composed of a vinyl acetate-based resin; plastic film composed of polycarbonate (PC); a plastic film composed of polyphenylene sulfide (PPS); plastic films composed of amide-based resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); a plastic film composed of a polyimide-based resin; plastic film composed of polyetheretherketone (PEEK); plastic films composed of olefin-based resins such as polyethylene (PE) and polypropylene (PP); Fluorine resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. made up of plastic film; and the like.

Examples of the nonwoven fabric include nonwoven fabrics made of natural fibers having heat resistance such as nonwoven fabrics made of manila hemp; synthetic resin nonwoven fabrics such as polypropylene resin nonwoven fabric, polyethylene resin nonwoven fabric, and ester resin nonwoven fabric; and the like.

One layer may be sufficient as the base material layer 1, and two or more layers may be sufficient as it.

The thickness of the base layer 1 is preferably 4 µm to 500 µm, more preferably 10 µm to 400 µm, further preferably 15 µm to the point that the effect of the present invention can be further expressed. It is 350 micrometers, Especially preferably, it is 20 micrometers - 300 micrometers.

The base material layer 1 may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-pressure electric shock exposure, ionizing radiation treatment, and coating treatment with a primer.

The base material layer 1 may contain arbitrary appropriate other additives in the range which does not impair the effect of this invention.

<Release layer>

The separator may have a mold release layer in order to improve the peelability from the adhesive layer 1 . When the separator has a release layer, the side of the release layer of the separator is directly laminated on the pressure-sensitive adhesive layer 1 .

As the material for forming the mold release layer, any appropriate material for forming the mold release layer can be adopted as long as the effects of the present invention are not impaired. As such a forming material, a silicone type mold release agent, a fluorine type mold release agent, a long-chain alkyl type mold release agent, a fatty acid amide type mold release agent, etc. are mentioned, for example. Among these, a silicone type mold release agent is preferable. The release layer can be formed as an application layer.

As the thickness of the mold release layer, any appropriate thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention. As such thickness, Preferably they are 10 nm - 2000 nm, More preferably, they are 10 nm - 1500 nm, More preferably, they are 10 nm - 1000 nm, Especially preferably, they are 10 nm - 500 nm.

The number of mold release layers may be one, and two or more layers may be sufficient as them.

As a silicone type mold release layer, an addition reaction type silicone resin is mentioned, for example. As an addition reaction type silicone resin, Specifically, For example, Shin-Etsu Chemical Co., Ltd. KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-847T; TPR-6700, TPR-6710, TPR-6721 made by Toshiba Silicone; SD7220 and SD7226 manufactured by Toray Dow Corning; and the like. The application amount (after drying) of the silicone-based release layer is preferably 0.01 g/m 2 to 2 g/m 2, more preferably 0.01 g/m 2 to 1 g/m 2, further preferably 0.01 g/m 2 to 0.5 g/m 2 is m2.

Formation of the release layer is, for example, after applying the forming material on any appropriate layer by a conventionally known application method such as reverse gravure coat, bar coat, die coat, etc., it is usually about 120 to 200°C. It can be carried out by hardening by performing heat treatment in Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed.

≪Adhesive layer (1)≫

The adhesive layer 1 can employ|adopt arbitrary appropriate adhesive layers in the range which does not impair the effect of this invention. One layer may be sufficient as the adhesive layer 1, and two or more layers may be sufficient as it.

The thickness of the pressure-sensitive adhesive layer 1 is preferably from 0.5 µm to 150 µm, more preferably from 1 µm to 100 µm, still more preferably from 3 µm to the point which can further express the effect of the present invention. 80 µm, particularly preferably 5 µm to 50 µm, and most preferably 10 µm to 30 µm.

When the adhesive layer 1 is used for the reinforcement laminated|multilayer film of this invention, Preferably, a separator is peeled, the adhesive layer 1 is exposed, and it bonds to the exposed surface side of an optical member, an electronic member, etc., and this optical member I reinforce the corresponding electronic member. That is, after bonding the adhesive layer 1 to the exposed surface side, such as an optical member and an electronic member, peeling like a surface protection film is not premised. For this reason, the pressure-sensitive adhesive layer 1 is preferably designed to have an adhesive force of a certain level or higher. Specifically, the temperature 23°C, humidity 50%RH, peel angle 180°C of the pressure-sensitive adhesive layer 1 exposed by peeling the separator at a temperature of 23°C, a humidity of 50%RH, a peeling angle of 150°C, and a peeling rate of 10m/min. , The initial adhesive force to the glass plate at a peeling rate of 300 mm/min is preferably 1.0 N/25 mm or more, more preferably 2.0 N/25 mm or more, and still more preferably 3.0 N/25 mm or more. , particularly preferably at least 4.0 N/25 mm, and most preferably at least 4.5 N/25 mm. Realistically, the upper limit of the said initial stage adhesive force becomes like this. Preferably it is 5.0 N/25 mm or less.

The pressure-sensitive adhesive layer 1 is preferably composed of at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive.

The adhesive layer 1 can be formed by arbitrary appropriate methods. As such a method, for example, a pressure-sensitive adhesive composition (at least one selected from the group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, and a silicone pressure-sensitive adhesive composition) is applied on any appropriate substrate, and, if necessary, The method of heating and drying, making it harden|cure as needed, and forming an adhesive layer on the said base material is mentioned. As such a coating method, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater, a roll brush coater, etc. method can be mentioned.

<Acrylic adhesive>

The acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.

The acrylic pressure-sensitive adhesive composition preferably contains an acrylic polymer and a crosslinking agent from the viewpoint of further expressing the effect of the present invention.

The acrylic polymer may be referred to as a so-called base polymer in the field of acrylic pressure-sensitive adhesives. The number of acrylic polymers may be one, and 2 or more types may be sufficient as them.

The content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, and still more preferably 70% by weight to 100% by weight in terms of solid content. %, particularly preferably 80% to 100% by weight, and most preferably 90% to 100% by weight.

As the acrylic polymer, any appropriate acrylic polymer can be employed as long as the effects of the present invention are not impaired.

The weight average molecular weight of the acrylic polymer is preferably 100,000 to 3,000,000, more preferably 150,000 to 2,000,000, still more preferably 200,000 to 1,500,000, particularly preferably from the viewpoint of further expressing the effect of the present invention. is 250,000 to 1,000,000.

As an acrylic polymer, from the point which can further express the effect of this invention, Preferably (a component) C4-C12 (meth)acrylic acid alkylester of the alkyl group of the alkylester part, (b component) OH group It is an acrylic polymer formed by superposition|polymerization from the composition (A) containing at least 1 sort(s) selected from the group which consists of (meth)acrylic acid ester and (meth)acrylic acid which has. (a component) and (b component) may be each independently, and only 1 type may be sufficient as them, and 2 or more types may be sufficient as them.

As the (meth)acrylic acid alkylester (component a) having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, for example, (meth)acrylic acid n-butyl, (meth)acrylate isobutyl, (meth)acrylic acid s-butyl, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate octyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate isooctyl, (meth) acrylate ) Nonyl acrylate, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate isodecyl, (meth) acrylate undecyl, (meth) acrylate dodecyl, etc. are mentioned. Among these, from the viewpoint that the effect of the present invention can be further expressed, (meth)acrylic acid n-butyl and (meth)acrylic acid 2-ethylhexyl are preferable, More preferably, acrylic acid n-butyl, acrylic acid 2- ethylhexyl.

At least one (component b) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid, for example, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid hydroxypropyl, ( (meth)acrylic acid ester, (meth)acrylic acid, etc. which have OH groups, such as meth)acrylic-acid hydroxybutyl, are mentioned. Among these, since the effect of this invention can be further expressed, (meth)acrylic-acid 2-hydroxyethyl and (meth)acrylic acid are preferable, More preferably, they are 2-hydroxyethyl acrylate and acrylic acid.

The composition (A) may contain copolymerizable monomers other than the component (a) and the component (b). The number of copolymerizable monomers may be one, and 2 or more types may be sufficient as them. Examples of such a copolymerizable monomer include itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (eg, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride). of carboxyl group-containing monomers (with the exception of (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N -amide group containing monomers, such as hydroxyethyl (meth)acrylamide; amino group-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate; Epoxy group-containing monomers, such as (meth)acrylic-acid glycidyl and (meth)acrylic-acid methylglycidyl; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, Heterocyclic containing vinyl-type monomers, such as vinyloxazole; Sulfonic acid group-containing monomers, such as sodium vinylsulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; imide group-containing monomers such as cyclohexyl maleimide and isopropyl maleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth)acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; (meth)acrylic acid ester which has aromatic hydrocarbon groups, such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; olefins and dienes such as ethylene, butadiene, isoprene, and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and the like.

As a copolymerizable monomer, a polyfunctional monomer can also be employ|adopted. A polyfunctional monomer means the monomer which has two or more ethylenically unsaturated groups in 1 molecule. As an ethylenically unsaturated group, any suitable ethylenically unsaturated group can be employ|adopted in the range which does not impair the effect of this invention. As such an ethylenically unsaturated group, radically polymerizable functional groups, such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group), are mentioned, for example. Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neo Pentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol propane tri (meth) acrylate, Tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, etc. are mentioned. The number of such polyfunctional monomers may be one, and 2 or more types may be sufficient as them.

As a copolymerizable monomer, (meth)acrylic-acid alkoxyalkyl ester is also employable. As the (meth)acrylic acid alkoxyalkyl ester, for example, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid methoxytriethylene glycol, (meth)acrylic acid 3-methoxy propyl, (meth)acrylic acid 3-ethoxypropyl, (meth)acrylic acid 4-methoxybutyl, (meth)acrylic acid 4-ethoxybutyl, etc. are mentioned. The number of (meth)acrylic acid alkoxyalkyl esters may be one, and 2 or more types may be sufficient as them.

The content of the (meth)acrylic acid alkyl ester (component a) having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety is the total amount (100 weight) of the monomer components constituting the acrylic polymer from the viewpoint that the effect of the present invention can be further expressed. %), preferably 50 wt% or more, more preferably 60 wt% to 100 wt%, still more preferably 70 wt% to 100 wt%, particularly preferably 80 wt% to 100 wt% %am.

The content of at least one (component b) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid is a monomer component constituting the acrylic polymer from the viewpoint that the effect of the present invention can be further expressed. With respect to the whole amount (100 weight%), Preferably it is 0.1 weight% or more, More preferably, it is 1.0 weight% - 50 weight%, More preferably, it is 1.5 weight% - 40 weight%, Especially preferably, it is 2.0 weight%. % to 30% by weight.

The composition (A) may contain any appropriate other component within the range which does not impair the effect of this invention. As such other components, a polymerization initiator, a chain transfer agent, a solvent, etc. are mentioned, for example. Any suitable content can be employ|adopted for content of these other components in the range which does not impair the effect of this invention.

As a polymerization initiator, a thermal polymerization initiator, a photoinitiator (photoinitiator), etc. can be employ|adopted according to the kind of polymerization reaction. The number of polymerization initiators may be one, and 2 or more types may be sufficient as them.

The thermal polymerization initiator can be preferably employed when obtaining the acrylic polymer by solution polymerization. Examples of such thermal polymerization initiators include azo polymerization initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox polymerization initiators, and the like. Among these thermal polymerization initiators, the azo-type initiator disclosed in Unexamined-Japanese-Patent No. 2002-69411 is especially preferable. Such an azo polymerization initiator is preferable because the decomposition product of the polymerization initiator does not easily remain in the acrylic polymer as a portion causing generation of a gas (outgas) generated by heating. Examples of the azo polymerization initiator include 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile (hereinafter sometimes referred to as AMBN). ), 2,2'-azobis(2-methylpropionic acid)dimethyl, and 4,4'-azobis-4-cyanovaleric acid. The amount of the azo polymerization initiator used is preferably 0.01 parts by weight to 5.0 parts by weight, more preferably 0.05 parts by weight to 4.0 parts by weight, with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer, and further Preferably it is 0.1 weight part - 3.0 weight part, Especially preferably, it is 0.15 weight part - 3.0 weight part, Most preferably, it is 0.20 weight part - 2.0 weight part.

A photoinitiator is preferably employable when obtaining an acrylic polymer by active energy ray polymerization. Examples of the photopolymerization initiator include a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, a benzoin-based photopolymerization initiator, and a benzyl-based photopolymerization initiator. an initiator, a benzophenone-based photopolymerization initiator, a ketal-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, and the like.

As a benzoin ether type photoinitiator, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-di phenylethan-1-one, anisolemethyl ether, and the like. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4 -(t-butyl)dichloroacetophenone etc. are mentioned. Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. have. As an aromatic sulfonyl chloride type|system|group photoinitiator, 2-naphthalene sulfonyl chloride etc. are mentioned, for example. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. As a benzoin type photoinitiator, benzoin etc. are mentioned, for example. As a benzyl type photoinitiator, benzyl etc. are mentioned, for example. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenylketone. As a ketal-type photoinitiator, benzyl dimethyl ketal etc. are mentioned, for example. As a thioxanthone type photoinitiator, For example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4- dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diiso A propyl thioxanthone, a dodecyl thioxanthone, etc. are mentioned.

The amount of the photopolymerization initiator used is preferably 0.01 parts by weight to 3.0 parts by weight, more preferably 0.015 parts by weight to 2.0 parts by weight, still more preferably with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer. is 0.02 parts by weight to 1.5 parts by weight, particularly preferably 0.025 parts by weight to 1.0 parts by weight, and most preferably 0.03 parts by weight to 0.50 parts by weight.

The acrylic pressure-sensitive adhesive composition may contain a crosslinking agent. By using a crosslinking agent, the cohesive force of an acrylic adhesive can be improved, and the effect of this invention can be expressed further. The number of crosslinking agents may be one, and 2 or more types may be sufficient as them.

Examples of the crosslinking agent include polyfunctional isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents. , an aziridine-based crosslinking agent, an amine-based crosslinking agent, and the like. Among these, it is at least 1 type (component c) selected from the group which preferably consists of a polyfunctional isocyanate type crosslinking agent and an epoxy type crosslinking agent from the point which can further express the effect of this invention.

Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; and aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Kogyo Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane) Urethane Kogyo Co., Ltd. make, trade name "Coronate HL"), trade name "Coronate HX" (Nippon Polyurethane Kogyo Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemical Co., Ltd. make, Commercial items, such as a brand name "Takenate 110N"), are also mentioned.

As the epoxy crosslinking agent (polyfunctional epoxy compound), for example, 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 di Glycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether Dil ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2-hydroxyethyl) isocyanurate, resorcindiglycidyl ester In addition to cidyl ether and bisphenol-S-diglycidyl ether, an epoxy-based resin having two or more epoxy groups in the molecule may be mentioned. As an epoxy-type crosslinking agent, commercial items, such as a brand name "Tetrad C" (made by Mitsubishi Gas Chemical Co., Ltd.), are also mentioned.

Any suitable content can be employ|adopted for content of the crosslinking agent in an acrylic adhesive composition in the range which does not impair the effect of this invention. As such content, for example, from the point which can further express the effect of this invention, with respect to solid content (100 weight part) of an acrylic polymer, Preferably it is 0.1 weight part - 5.0 weight part, More preferably, it is 0.2 It is a weight part - 4.5 weight part, More preferably, it is 0.3 weight part - 4.0 weight part, Especially preferably, it is 0.4 weight part - 3.5 weight part.

The acrylic pressure-sensitive adhesive composition may contain any appropriate other components within a range that does not impair the effects of the present invention. Examples of such other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antioxidants, and inorganic fillers. , organic fillers, metal powders, colorants (pigments or dyes, etc.), thin materials, ultraviolet absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents , a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

<Urethane adhesive>

The urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition.

The urethane-based pressure-sensitive adhesive composition contains at least one selected from the group consisting of urethane prepolymers and polyols, and a crosslinking agent, from the viewpoint that the effects of the present invention can be further expressed.

At least one selected from the group consisting of urethane prepolymers and polyols may be referred to as a so-called base polymer in the field of urethane pressure-sensitive adhesives. The number of urethane prepolymers may be one, and 2 or more types may be sufficient as them. The number of polyols may be one, and 2 or more types may be sufficient as them.

[Urethane prepolymer]

The urethane prepolymer is preferably a polyurethane polyol, and more preferably, a polyester polyol (a1) or a polyether polyol (a2), each alone or as a mixture of (a1) and (a2), in the presence of a catalyst It is made by making it react with an organic polyisocyanate compound (a3) under or under a catalyst.

As the polyester polyol (a1), any suitable polyester polyol can be used. As such a polyester polyol (a1), the polyester polyol obtained by making an acid component and a glycol component react, for example is mentioned. As an acid component, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, etc. are mentioned, for example. As the glycol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxy Ethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerol, trimethylol propane, pentaerythritol etc. are mentioned as a polyol component. Examples of the polyester polyol (a1) include a polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone.

As the molecular weight of the polyester polyol (a1), it is possible to use from a low molecular weight to a high molecular weight. As molecular weight of polyester polyol (a1), from the point which can further express the effect of this invention, a number average molecular weight becomes like this. Preferably it is 100-100000. When the number average molecular weight is less than 100, the reactivity becomes high and there exists a possibility that it may become easy to gelatinize. When the number average molecular weight exceeds 100000, the reactivity becomes low, and there is a possibility that the cohesive force of the polyurethane polyol itself becomes small. The amount of the polyester polyol (a1) used is preferably 0 mol% to 90 mol% among polyols constituting the polyurethane polyol from the viewpoint that the effect of the present invention can be further expressed.

As the polyether polyol (a2), any appropriate polyether polyol can be used. As such a polyether polyol (a2), for example, water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, etc. low molecular weight polyols are used as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetra Polyether polyol obtained by superposing|polymerizing oxirane compounds, such as hydrofuran, is mentioned. Specific examples of the polyether polyol (a2) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As molecular weight of polyether polyol (a2), it can use from low molecular weight to high molecular weight. As molecular weight of polyether polyol (a2), from the point which can further express the effect of this invention, a number average molecular weight becomes like this. Preferably it is 100-100000. When the number average molecular weight is less than 100, the reactivity becomes high and there exists a possibility that it may become easy to gelatinize. When the number average molecular weight exceeds 100000, the reactivity becomes low, and there is a possibility that the cohesive force of the polyurethane polyol itself becomes small. The amount of the polyether polyol (a2) used is preferably 0 mol% to 90 mol% among polyols constituting the polyurethane polyol from the viewpoint that the effect of the present invention can be further expressed.

The polyether polyol (a2) may contain a part thereof as needed, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, ethylenediamine, Polyvalent amines such as N-aminoethylethanolamine, isophoronediamine, and xylylenediamine can be used in combination.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, and a polyether polyol having a number average molecular weight of 100 to 100000 and having at least 3 or more hydroxyl groups in one molecule may be partially or entirely used. . As the polyether polyol (a2), when a polyether polyol having a number average molecular weight of 100 to 100000 and having at least 3 or more hydroxyl groups in one molecule is partially or entirely used, the effects of the present invention can be further expressed; Together, the balance between adhesive force and peelability can be improved. In such a polyether polyol, when the number average molecular weight is less than 100, the reactivity becomes high, and there exists a possibility that it may become easy to gelatinize. Moreover, in such a polyether polyol, when a number average molecular weight exceeds 100000, reactivity may become low and there exists a possibility that the cohesive force of polyurethane polyol itself may become small further. The number average molecular weight of such a polyether polyol is a point which can further express the effect of this invention, More preferably, it is 100-10000.

As the organic polyisocyanate compound (a3), any appropriate organic polyisocyanate compound can be used. As such an organic polyisocyanate compound (a3), aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned, for example.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4-tolyl. Rendiisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'- Diphenyl ether diisocyanate, 4,4',4"- triphenylmethane triisocyanate, etc. are mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. Isocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, etc. are mentioned.

As aromatic aliphatic polyisocyanate, for example, ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4 - Diethylbenzene, 1, 4- tetramethyl xylylene diisocyanate, 1, 3- tetramethyl xylylene diisocyanate, etc. are mentioned.

Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4- Cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanato) Methyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, etc. are mentioned.

As the organic polyisocyanate compound (a3), a trimethylolpropane adduct body, a biuret body reacted with water, a trimer having an isocyanurate ring, etc. can be used in combination.

Any suitable catalyst can be used as a catalyst which can be used when obtaining a polyurethane polyol. As such a catalyst, a tertiary amine-type compound, an organometallic compound, etc. are mentioned, for example.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU).

As an organometallic compound, a tin type compound, a non-tin type compound, etc. are mentioned, for example.

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, and dibutyl Tin sulfide, tributyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate , 2-ethyl tin hexanoate, and the like.

Examples of the non-tin-based compound include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate; and the like.

When a catalyst is used to obtain a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, exist, because of a difference in reactivity, in a system of a single catalyst, gelation or the reaction solution becomes cloudy It is easy to cause problems that you are doing. Then, by using two types of catalysts when obtaining a polyurethane polyol, it becomes easy to control the reaction rate, the selectivity of a catalyst, etc., and these problems can be solved. Examples of the combination of these two types of catalysts include tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably It is a combination of dibutyltin dilaurate and 2-ethyl tin hexanoate. The compounding ratio is, in terms of weight ratio, 2-ethylhexanoate tin/dibutyltin dilaurate, preferably less than 1, more preferably 0.2 to 0.6. When the compounding ratio is 1 or more, there is a possibility that gelation becomes easy due to the balance of catalytic activity.

When using a catalyst when obtaining a polyurethane polyol, the amount of the catalyst used is preferably 0.01% by weight to the total amount of the polyester polyol (a1), the polyether polyol (a2), and the organic polyisocyanate compound (a3). 1.0% by weight.

When a catalyst is used to obtain the polyurethane polyol, the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. When it becomes 100 degreeC or more, there exists a possibility that control of a reaction rate and a crosslinked structure may become difficult, and there exists a possibility that it may become difficult to obtain the polyurethane polyol which has a predetermined molecular weight.

When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol under no catalyst, it is preferable to make it react for 3 hours or more.

As a method for obtaining the polyurethane polyol, for example, 1) a method of adding polyester polyol, polyether polyol, catalyst, and organic polyisocyanate to the flask, 2) adding polyester polyol, polyether polyol, and catalyst to the flask and adding organic polyisocyanate. As a method of obtaining a polyurethane polyol, in controlling reaction, the method of 2) is preferable.

When obtaining a polyurethane polyol, arbitrary appropriate solvents can be used. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone etc. are mentioned, for example. Among these solvents, toluene is preferable.

[Polyol]

As a polyol, Preferably, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and a castor oil type polyol are mentioned, for example. As a polyol, More preferably, it is a polyether polyol.

As a polyester polyol, it can obtain by the esterification reaction of a polyol component and an acid component, for example.

Examples of the polyol component include ethylene glycol, diethylene 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-nonanediol, 2- Methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, etc. are mentioned. Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimeric acid, azelaic acid, sebacic acid, 1,12-dodecanoic 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, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid acid, these acid anhydrides, etc. are mentioned.

Examples of the polyether polyol include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, polyether polyol obtained by addition polymerization of alkylene oxides, such as ethylene oxide, propylene oxide, and a butylene oxide, using hydroquinone etc.) etc. as an initiator. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned, for example.

Examples of the polycaprolactone polyol include caprolactone-based polyesterdiol obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

As a polycarbonate polyol, For example, polycarbonate polyol obtained by making the said polyol component and phosgene polycondensate; The polyol component and dicarbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate polycarbonate polyols obtained by transesterifying esters; Copolymerization polycarbonate polyol obtained by using together 2 or more types of said polyol component; a polycarbonate polyol obtained by esterifying the various polycarbonate polyols with a carboxyl group-containing compound; polycarbonate polyols obtained by etherifying the various polycarbonate polyols with a hydroxyl group-containing compound; a polycarbonate polyol obtained by transesterifying the various polycarbonate polyols with an ester compound; a polycarbonate polyol obtained by transesterifying the various polycarbonate polyols with a hydroxyl group-containing compound; polyester-based polycarbonate polyols obtained by polycondensation reaction of the various polycarbonate polyols and dicarboxylic acid compounds; copolymerized polyether-based polycarbonate polyols obtained by copolymerizing the various polycarbonate polyols with alkylene oxides; and the like.

Examples of the castor oil-based polyol include a castor oil-based polyol obtained by reacting a castor oil fatty acid with the polyol component. Specific examples thereof include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.

The number average molecular weight Mn of the polyol is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, particularly preferably from the viewpoint of further expressing the effect of the present invention. is 500 to 30000.

As a polyol, from the point which can further express the effect of this invention, Preferably, the number average molecular weight Mn which has three OH groups contains the polyol (A1) whose number average molecular weight Mn is 300-100000. The number of polyols (A1) may be one, and 2 or more types may be sufficient as them.

The content of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, still more preferably from the viewpoint of further expressing the effect of the present invention. 50% by weight to 100% by weight.

The number average molecular weight Mn of the polyol (A1) is preferably 1000 to 100000, more preferably more than 1000 and 80000 or less, further preferably 1100 to 70000, more preferably 1200 to 60000, still more preferably 1300 to 50000, still more preferably 1400 to 40000, still more preferably 1500 to 35000, particularly preferably 1700 to 32000, most preferably usually from 2000 to 30000.

The polyol may contain the polyol (A2) whose number average molecular weight Mn which has 3 or more OH groups is 20000 or less. The number of polyols (A2) may be one, and 2 or more types may be sufficient as them. The number average molecular weight Mn of the polyol (A2) is preferably 100 to 20000, more preferably 150 to 10000, still more preferably 200 to 7500, from the viewpoint of further expressing the effects of the present invention, Especially preferably, it is 300-6000, Most preferably, it is 300-5000. The polyol (A2) is preferably a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), and a polyol having five OH groups, from the viewpoint of further expressing the effects of the present invention as the polyol (A2). (pentaol) and a polyol (hexanol) having 6 OH groups are mentioned.

As the polyol (A2), the total amount of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexanol) is to further express the effect of the present invention. From that point, the content ratio in the polyol is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight or less.

The content of the polyol (A2) in the polyol is preferably 95% by weight or less, and more preferably 0 to 75% by weight from the viewpoint that the effect of the present invention can be further expressed.

The content ratio of the polyol having 4 or more OH groups and having a number average molecular weight Mn of 20000 or less as the polyol (A2) is preferably less than 70% by weight relative to the entire polyol from the viewpoint that the effect of the present invention can be further expressed. More preferably, it is 60 weight% or less, More preferably, it is 50 weight% or less, Especially preferably, it is 40 weight% or less, Most preferably, it is 30 weight% or less.

[crosslinking agent]

The urethane-based pressure-sensitive adhesive composition preferably contains a crosslinking agent from the viewpoint of further expressing the effect of the present invention.

The urethane prepolymer and polyol as the base polymer can each be combined with a crosslinking agent to become a component of the urethane-based pressure-sensitive adhesive composition.

The crosslinking agent to be combined with the urethane prepolymer and polyol as the base polymer is preferably a polyfunctional isocyanate-based crosslinking agent from the viewpoint of further expressing the effects of the present invention.

As the polyfunctional isocyanate-based crosslinking agent, any suitable polyfunctional isocyanate-based crosslinking agent that can be used in the urethanization reaction can be employed. Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; and aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Kogyo Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane) Urethane Kogyo Co., Ltd. make, trade name "Coronate HL"), trade name "Coronate HX" (Nippon Polyurethane Kogyo Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemical Co., Ltd. make, Commercial items, such as a brand name "Takenate 110N"), are also mentioned.

[Urethane-based pressure-sensitive adhesive composition]

The urethane-type adhesive composition can contain arbitrary appropriate other components in the range which does not impair the effect of this invention. Examples of such other components include polymer components other than urethane prepolymers and polyols, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antioxidants, Inorganic fillers, organic fillers, metal powders, colorants (pigments and dyes, etc.), thin materials, deterioration inhibitors, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, A heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, etc. are mentioned.

The urethane pressure-sensitive adhesive composition preferably contains a deterioration inhibitor from the viewpoint of further expressing the effect of the present invention. The number of deterioration inhibitors may be one, and 2 or more types may be sufficient as them.

As a deterioration inhibitor, Preferably, antioxidant, a ultraviolet absorber, and a light stabilizer are mentioned at the point which can express the effect of this invention further.

As antioxidant, a radical chain inhibitor, a peroxide decomposing agent, etc. are mentioned, for example.

As a radical chain inhibitor, a phenol type antioxidant, an amine type antioxidant, etc. are mentioned, for example.

As a phenolic antioxidant, a monophenol-type antioxidant, a bisphenol-type antioxidant, a polymer type phenol-type antioxidant, etc. are mentioned, for example. Examples of the monophenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate etc. are mentioned. Examples of the bisphenol-based antioxidant include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4 ,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1 -Dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, etc. can be heard Examples of the high molecular weight phenolic antioxidant include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)prop Cypionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3',5'-di- t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocophenol, etc. are mentioned.

Examples of the peroxide decomposing agent include sulfur-based antioxidants and phosphorus-based antioxidants. As the sulfur-based antioxidant, for example, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, etc. can be heard As phosphorus antioxidant, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, etc. are mentioned, for example.

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, an oxalic acid anilide-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a triazine-based ultraviolet absorber.

As a benzophenone type|system|group ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4- octoxy benzophenone, 2-hydroxy-4 are, for example. -Dodecyloxy benzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-me oxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, and the like.

Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2 -(2'-hydroxyl-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxyl-3'-tert-butyl-5'-methylphenyl)-5-chloro Benzotriazole, 2-(2'-hydroxyl-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxyl-3',5'-di- tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3'',4'', 5'',6'',-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6- (2H-benzotriazol-2-yl)phenol], 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, etc. are mentioned.

Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, and the like. can be heard

As a light stabilizer, a hindered amine type light stabilizer, an ultraviolet stabilizer, etc. are mentioned, for example. Examples of the hindered amine light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4- piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, and the like. Examples of the ultraviolet stabilizer include nickelbis(octylphenyl)sulfide, [2,2'-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di- tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylate, benzoate-type quencher, nickel-dibutyldithiocarbamate, etc. are mentioned.

[A urethane-based polymer formed from a urethane-based pressure-sensitive adhesive composition containing a urethane prepolymer and a polyfunctional isocyanate-based crosslinking agent]

The number of urethane prepolymers may be one, and 2 or more types may be sufficient as them. The number of polyfunctional isocyanate type crosslinking agents may be one, and 2 or more types may be sufficient as them.

As a method of forming a urethane-based polymer from a urethane-based pressure-sensitive adhesive composition containing a urethane prepolymer and a polyfunctional isocyanate-based crosslinking agent, any suitable production method can be adopted as long as it is a method for producing a urethane-based polymer using a so-called “urethane prepolymer” as a raw material. have.

The number average molecular weight Mn of the urethane prepolymer is preferably 3000 to 1,000,000 from the viewpoint of further expressing the effect of the present invention.

In the urethane prepolymer and the polyfunctional isocyanate-based crosslinking agent, the equivalent ratio of the NCO group and the OH group is preferably 5.0 or less as the NCO group/OH group from the viewpoint of further expressing the effects of the present invention, and more preferably is 0.01 to 4.75, more preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, and most preferably 0.05 to 4.0.

The content of the polyfunctional isocyanate-based crosslinking agent is, from the viewpoint of further expressing the effects of the present invention, the polyfunctional isocyanate-based crosslinking agent is preferably 0.01 to 30 parts by weight, based on 100 parts by weight of the urethane prepolymer, More preferably, it is 0.05 part by weight - 25 weight part, More preferably, it is 0.1 weight part - 20 weight part, Especially preferably, it is 0.5 weight part - 17.5 weight part, Most preferably, it is 1 weight part - 15 weight part am.

[A urethane-based polymer formed from a urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based crosslinking agent]

The number of polyols may be one, and 2 or more types may be sufficient as them. The number of polyfunctional isocyanate type crosslinking agents may be one, and 2 or more types may be sufficient as them.

The equivalent ratio of the NCO group and the OH group in the polyol and the polyfunctional isocyanate-based crosslinking agent is NCO group/OH group from the viewpoint of further expressing the effect of the present invention, preferably 5.0 or less, more preferably 0.1 to 3.0, more preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0.

The content of the polyfunctional isocyanate-based crosslinking agent is, from the viewpoint of further expressing the effects of the present invention, the polyfunctional isocyanate-based crosslinking agent is preferably 1.0 to 30 parts by weight, based on 100 parts by weight of the polyol, more Preferably it is 1.5 parts by weight to 27 parts by weight, more preferably 2.0 parts by weight to 25 parts by weight, particularly preferably 2.3 parts by weight to 23 parts by weight, and most preferably 2.5 parts by weight to 20 parts by weight .

The urethane-based polymer formed from the urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based crosslinking agent is specifically, preferably formed by curing a urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based crosslinking agent. As a method of curing a urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based crosslinking agent to form a urethane-based polymer, any method, such as a urethanation reaction method using bulk polymerization or solution polymerization, etc. Appropriate methods may be employed.

In order to cure the urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based crosslinking agent, a catalyst is preferably used. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example.

Examples of the organometallic compound include an iron-based compound, a tin-based compound, a titanium-based compound, a zirconium-based compound, a lead-based compound, a cobalt-based compound, and a zinc-based compound. Among these, an iron-type compound and a tin-type compound are preferable from the point of a reaction rate and the pot life of an adhesive layer.

Examples of the iron-based compound include iron acetylacetonate, iron 2-ethylhexanoate, and ferric nases.

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, Tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, 2 -Ethyl tin hexanoate, etc. are mentioned.

Examples of the titanium-based compound include dibutyl titanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride.

As a zirconium type compound, zirconium naphthenate, zirconium acetylacetonate, etc. are mentioned, for example.

Examples of the lead-based compound include lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.

Examples of the cobalt-based compound include cobalt 2-ethylhexanoate and cobalt benzoate.

Examples of the zinc-based compound include zinc naphthenate and zinc 2-ethylhexanoate.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo-(5,4,0)-undecene-7.

The number of catalysts may be one, and 2 or more types may be sufficient as them. Moreover, you may use together a catalyst, a crosslinking retarder, etc. The amount of the catalyst is preferably 0.005 parts by weight to 1.00 parts by weight, more preferably 0.01 parts by weight to 0.75 parts by weight, and further Preferably it is 0.01 weight part - 0.50 weight part, Especially preferably, it is 0.01 weight part - 0.20 weight part.

<Rubber-based adhesive>

As a rubber-type adhesive, arbitrary appropriate rubber-type adhesives, such as a well-known rubber-type adhesive described in Unexamined-Japanese-Patent No. 2015-074771 etc., can be employ|adopted, for example, in the range which does not impair the effect of this invention. One type may be sufficient as these, and 2 or more types may be sufficient as them. A rubber-type adhesive can contain arbitrary appropriate components in the range which does not impair the effect of this invention.

<Silicone-based adhesive>

As a silicone adhesive, arbitrary appropriate silicone adhesives, such as a well-known silicone adhesive described in Unexamined-Japanese-Patent No. 2014-047280 etc., can be employ|adopted, for example, in the range which does not impair the effect of this invention. One type may be sufficient as these, and 2 or more types may be sufficient as them. The silicone pressure-sensitive adhesive may contain any appropriate component within a range that does not impair the effects of the present invention.

≪Materials for the reinforcement≫

As the reinforcing base material, a reinforcing base material formed of any suitable material can be employed as long as the effects of the present invention are not impaired. Examples of such a material include a plastic film, a nonwoven fabric, paper, metal foil, a woven fabric, a rubber sheet, a foam sheet, and a laminate of these (especially a laminate including a plastic film).

As a base material for reinforcement, a plastic film is preferable at the point which can further express the effect of this invention.

As a plastic film, For example, the plastic film comprised from polyester-type resin, such as a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), and a polybutylene terephthalate (PBT); Plastics composed of olefinic resins containing α-olefins such as polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA) as a monomer component film; a plastic film composed of polyvinyl chloride (PVC); a plastic film composed of a vinyl acetate-based resin; plastic film composed of polycarbonate (PC); a plastic film composed of polyphenylene sulfide (PPS); plastic films composed of amide-based resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); a plastic film composed of a polyimide-based resin; plastic film composed of polyetheretherketone (PEEK); plastic films composed of olefin-based resins such as polyethylene (PE) and polypropylene (PP); Fluorine resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. made up of plastic film; and the like.

As the thickness of the reinforcing base material, any appropriate thickness can be adopted according to the purpose within a range that does not impair the effects of the present invention. As such a thickness, it is preferably 25 µm to 500 µm, more preferably 25 µm to 400 µm, still more preferably 25 µm to 300 µm from the viewpoint of further expressing the effect of the present invention, More preferably, they are 25 micrometers - 200 micrometers, More preferably, they are 25 micrometers - 150 micrometers, More preferably, they are 25 micrometers - 100 micrometers, Especially preferably, they are 25 micrometers - 75 micrometers. In addition, as the thickness of the reinforcing base material is thinner, interfacial peeling occurs at an unintended location (typically, the interface between the surface protection film and the reinforcing film) when the separator is peeled from the reinforcing laminated film. there is a risk of throwing it away. Specifically, even when the instrument peeling force P of the reinforcing substrate is larger than the instrument peeling force Q of the separator, if the thickness of the reinforcing substrate is too thin, unintentional cases of peeling the separator from the reinforcing laminated film The risk of interfacial peeling in a location increases, especially when the instrument peeling force P is small, the risk becomes higher. In addition, when it is desired to design the laminated film for reinforcement of the present invention by employing a thin substrate for reinforcement, it is preferable to employ a surface protection film having a pressure-sensitive adhesive layer composed of a specific acrylic pressure-sensitive adhesive, as will be described later.

One layer may be sufficient as the base material for reinforcement, and two or more layers may be sufficient as it.

The base material for reinforcement may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, chromic acid treatment, ozone exposure, flame exposure, high-pressure electric shock exposure, ionizing radiation treatment, and coating treatment with a primer.

The reinforcing base material may contain arbitrary appropriate additives according to the purpose within the range which does not impair the effect of this invention.

≪Surface protection film≫

A surface protection film contains the base material layer 2 and the adhesive layer 2, The said adhesive layer 2 is laminated|stacked directly on the base material for reinforcement. As long as the surface protection film contains the base material layer 2 and the adhesive layer 2, it may be equipped with arbitrary appropriate other members in the range which does not impair the effect of this invention. Typically, the surface protection film consists of the base material layer 2 and the adhesive layer 2 .

The thickness of the surface protection film is preferably 5 µm to 500 µm, more preferably 10 µm to 400 µm, still more preferably 20 µm to 300 µm from the viewpoint of further expressing the effect of the present invention. and particularly preferably 30 μm to 200 μm, and most preferably 40 μm to 100 μm.

A surface protection film can be manufactured by arbitrary appropriate methods. As such a manufacturing method, for example,

(1) a method of applying a solution or a hot melt of a material for forming the pressure-sensitive adhesive layer 2 on the base layer 2;

(2) a method of transferring the pressure-sensitive adhesive layer 2 formed by applying a solution or hot melt of the material for forming the pressure-sensitive adhesive layer 2 on the separator onto the base material layer 2;

(3) a method of extruding the forming material of the pressure-sensitive adhesive layer 2 on the base layer 2 to form and apply;

(4) a method of extruding the base material layer 2 and the pressure-sensitive adhesive layer 2 in two or multiple layers;

(5) a method of single-layer laminating of the pressure-sensitive adhesive layer (2) on the base layer (2) or a method of laminating the pressure-sensitive adhesive layer (2) together with the laminate layer in two layers;

(6) Method of laminating the adhesive layer 2 and the forming material of the base material layer 2, such as a film and a lamination layer, in two layers or multilayer

etc., it can carry out according to arbitrary suitable manufacturing methods.

As a method of application|coating, the roll coater method, the comma coater method, the die coater method, the reverse coater method, the silkscreen method, the gravure coater method etc. can be used, for example.

<Base layer (2)>

One layer may be sufficient as the base material layer 2, and two or more layers may be sufficient as it. The base material layer 2 may be extended|stretched.

Since the thickness of the base material layer 2 can further express the effect of this invention, Preferably they are 4 micrometers - 450 micrometers, More preferably, they are 8 micrometers - 350 micrometers, More preferably, they are 12 micrometers - 250 μm, particularly preferably 16 μm to 150 μm, and most preferably 20 μm to 100 μm.

About the surface on which the adhesive layer 2 of the base material layer 2 is not laid, for the purpose of formation of an easy winding object, etc., to the base material layer 2, fatty acid amide, polyethyleneimine, a long chain, for example. It is possible to perform a release treatment by adding an alkyl-based additive or the like, or to provide a coating layer containing any appropriate release agent such as silicone-based, long-chain alkyl-based or fluorine-based release agent.

As the base material layer 2, the base material layer formed of arbitrary suitable materials is employable in the range which does not impair the effect of this invention. Examples of such a material include a plastic film, a nonwoven fabric, paper, metal foil, a woven fabric, a rubber sheet, a foam sheet, and a laminate of these (especially a laminate including a plastic film).

As the base material layer 2, it is a point which can further express the effect of this invention, Preferably it is a plastic film.

As a plastic film, For example, the plastic film comprised from polyester-type resin, such as a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), and a polybutylene terephthalate (PBT); Plastics composed of olefinic resins containing α-olefins such as polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA) as a monomer component film; a plastic film composed of polyvinyl chloride (PVC); a plastic film composed of a vinyl acetate-based resin; plastic film composed of polycarbonate (PC); a plastic film composed of polyphenylene sulfide (PPS); plastic films composed of amide-based resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); a plastic film composed of a polyimide-based resin; plastic film composed of polyetheretherketone (PEEK); plastic films composed of olefin-based resins such as polyethylene (PE) and polypropylene (PP); Fluorine resins such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. made up of plastic film; and the like.

The base material layer 2 may contain arbitrary appropriate additives according to the objective in the range which does not impair the effect of this invention.

<Adhesive layer (2)>

As the pressure-sensitive adhesive layer 2, any appropriate pressure-sensitive adhesive layer can be employed within a range that does not impair the effects of the present invention. One layer may be sufficient as the adhesive layer 2, and two or more layers may be sufficient as it.

The thickness of the pressure-sensitive adhesive layer 2 is preferably from 0.5 µm to 150 µm, more preferably from 1 µm to 100 µm, further preferably from 3 µm to the point which can further express the effect of the present invention. 80 µm, particularly preferably 5 µm to 50 µm, and most preferably 10 µm to 30 µm.

The pressure-sensitive adhesive layer 2 is preferably composed of at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive. is composed of at least one selected from the group consisting of acrylic pressure-sensitive adhesives and urethane pressure-sensitive adhesives, and more preferably composed of acrylic pressure-sensitive adhesives. Since the pressure-sensitive adhesive layer 2 is composed of at least one selected from the group consisting of an acrylic pressure-sensitive adhesive and a urethane-based pressure-sensitive adhesive, the instrument peel force P tends to be larger than the instrument peel force Q, and the pressure-sensitive adhesive layer 2 is composed of an acrylic pressure sensitive adhesive, The peeling force P tends to become larger than the instrumental peeling force Q (that is, the value of (PQ) may tend to become large).

The adhesive layer 2 can be formed by arbitrary appropriate methods. As such a method, for example, a pressure-sensitive adhesive composition (at least one selected from the group consisting of an acrylic pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a rubber pressure-sensitive adhesive composition, and a silicone pressure-sensitive adhesive composition) is applied on any appropriate substrate, and, if necessary, The method of heating and drying, making it harden|cure as needed, and forming an adhesive layer on the said base material is mentioned. As such a coating method, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater, a roll brush coater, etc. method can be mentioned.

The detailed description of each of the acrylic pressure-sensitive adhesive, the urethane pressure-sensitive adhesive, the rubber-based pressure-sensitive adhesive, and the silicone pressure-sensitive adhesive is the same as the detailed description of each of the acrylic pressure-sensitive adhesive, the urethane pressure-sensitive adhesive, the rubber-based pressure-sensitive adhesive, and the silicone pressure-sensitive adhesive in the description of the pressure-sensitive adhesive layer 1 described above. can be used However, regarding the acrylic adhesive which can comprise the adhesive layer 2, the following "acrylic adhesive for the adhesive layer 2" is preferable at the point which can further express the effect of this invention.

The acrylic pressure-sensitive adhesive for the pressure-sensitive adhesive layer (2) is formed from the acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer (2).

The acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer 2 preferably contains an acryl-type polymer and a crosslinking agent from the viewpoint of further expressing the effect of the present invention.

The acrylic polymer may be referred to as a so-called base polymer in the field of acrylic pressure-sensitive adhesives. The number of acrylic polymers may be one, and 2 or more types may be sufficient as them.

The content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer 2 is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, still more preferably in terms of solid content. 70% to 100% by weight, particularly preferably 80% to 100% by weight, and most preferably 90% to 100% by weight.

As the acrylic polymer, any appropriate acrylic polymer can be employed as long as the effects of the present invention are not impaired.

The weight average molecular weight of the acrylic polymer is preferably 100,000 to 3,000,000, more preferably 150,000 to 2,000,000, still more preferably 200,000 to 1,500,000, particularly preferably from the viewpoint of further expressing the effect of the present invention. is 250,000 to 1,000,000.

As an acrylic polymer, from the point which can further express the effect of this invention, Preferably (meth)acrylic acid alkylester whose carbon number of the alkyl group of the alkylester part (p component) is 4-12, (q component) OH group It is an acrylic polymer formed by polymerization from the composition (B) containing at least 1 sort(s) selected from the group which consists of (meth)acrylic acid ester and (meth)acrylic acid which has. (component p) and (component q) may each independently be 1 type or 2 or more types may be sufficient as them.

As the (meth)acrylic acid alkyl ester (p component) having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, for example, (meth) acrylate n-butyl, (meth) acrylate isobutyl, (meth) acrylate s-butyl, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate octyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate isooctyl, (meth) acrylate ) Nonyl acrylate, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate isodecyl, (meth) acrylate undecyl, (meth) acrylate dodecyl, etc. are mentioned. Among these, from the viewpoint that the effect of the present invention can be further expressed, (meth)acrylic acid n-butyl and (meth)acrylic acid 2-ethylhexyl are preferable, More preferably, acrylic acid n-butyl and acrylic acid 2- It is ethylhexyl, More preferably, it is acrylic acid 2-ethylhexyl.

As at least one member (q component) selected from the group consisting of (meth)acrylic acid ester and (meth)acrylic acid having an OH group, for example, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid hydroxypropyl, ( (meth)acrylic acid ester, (meth)acrylic acid, etc. which have OH groups, such as meth)acrylic-acid hydroxybutyl, are mentioned. Among these, from the viewpoint that the effect of the present invention can be further expressed, (meth)acrylic acid 2-hydroxyethyl and (meth)acrylic acid are preferable, and more preferably, they are 2-hydroxyethyl acrylate and acrylic acid, More preferably, it is 2-hydroxyethyl acrylate.

The composition (B) may contain copolymerizable monomers other than the component (p) and the component (q). The number of copolymerizable monomers may be one, and 2 or more types may be sufficient as them. Examples of such a copolymerizable monomer include itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (eg, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride). of carboxyl group-containing monomers (with the exception of (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N -amide group containing monomers, such as hydroxyethyl (meth)acrylamide; amino group-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate; Epoxy group-containing monomers, such as (meth)acrylic-acid glycidyl and (meth)acrylic-acid methylglycidyl; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, Heterocyclic containing vinyl-type monomers, such as vinyloxazole; Sulfonic acid group-containing monomers, such as sodium vinylsulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; imide group-containing monomers such as cyclohexyl maleimide and isopropyl maleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth)acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; (meth)acrylic acid ester which has aromatic hydrocarbon groups, such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; olefins and dienes such as ethylene, butadiene, isoprene, and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and the like.

As a copolymerizable monomer, a polyfunctional monomer can also be employ|adopted. A polyfunctional monomer means the monomer which has two or more ethylenically unsaturated groups in 1 molecule. As an ethylenically unsaturated group, any suitable ethylenically unsaturated group can be employ|adopted in the range which does not impair the effect of this invention. As such an ethylenically unsaturated group, radically polymerizable functional groups, such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group), are mentioned, for example. Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neo Pentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol propane tri (meth) acrylate, Tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, etc. are mentioned. The number of such polyfunctional monomers may be one, and 2 or more types may be sufficient as them.

As a copolymerizable monomer, (meth)acrylic-acid alkoxyalkyl ester is also employable. As the (meth)acrylic acid alkoxyalkyl ester, for example, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid methoxytriethylene glycol, (meth)acrylic acid 3-methoxy propyl, (meth)acrylic acid 3-ethoxypropyl, (meth)acrylic acid 4-methoxybutyl, (meth)acrylic acid 4-ethoxybutyl, etc. are mentioned. The number of (meth)acrylic acid alkoxyalkyl esters may be one, and 2 or more types may be sufficient as them.

The content of the (meth)acrylic acid alkyl ester (component p) having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety is the total amount of the monomer components constituting the acrylic polymer (100 weights) from the viewpoint that the effect of the present invention can be further expressed. %), preferably 50 wt% or more, more preferably 60 wt% to 100 wt%, still more preferably 70 wt% to 100 wt%, particularly preferably 80 wt% to 100 wt% %am.

The content of at least one (component q) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid is a monomer component constituting the acrylic polymer from the viewpoint that the effect of the present invention can be further expressed. To the whole amount (100 weight%), Preferably it is 0.1 weight% or more, More preferably, it is 1.0 weight% - 50 weight%, More preferably, it is 1.5 weight% - 40 weight%, More preferably, it is 2.0 weight%. % to 30 wt%, more preferably 2.0 wt% to 20 wt%, particularly preferably 2.0 wt% to 10 wt%, and most preferably 2.0 wt% to 5 wt%.

The composition (B) may contain any appropriate other component in the range which does not impair the effect of this invention. As such other components, a polymerization initiator, a chain transfer agent, a solvent, etc. are mentioned, for example. Any suitable content can be employ|adopted for content of these other components in the range which does not impair the effect of this invention. About these other components, the description in "composition (A)" in the item of << adhesive layer (1) >> can be used as it is.

The acrylic adhesive composition for adhesive layers 2 may contain the crosslinking agent. By using a crosslinking agent, the cohesive force of an acrylic adhesive can be improved, and the effect of this invention can be expressed further. The number of crosslinking agents may be one, and 2 or more types may be sufficient as them.

Examples of the crosslinking agent include polyfunctional isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents. , an aziridine-based crosslinking agent, an amine-based crosslinking agent, and the like. Among these, at least one selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent (component r), more preferably, a polyfunctional It is an isocyanate type crosslinking agent.

Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; and aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Kogyo Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane) Urethane Kogyo Co., Ltd. make, trade name "Coronate HL"), trade name "Coronate HX" (Nippon Polyurethane Kogyo Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemical Co., Ltd. make, Commercial items, such as a brand name "Takenate 110N"), are also mentioned. Among these, at least one selected from trimethylolpropane/tolylene diisocyanate adduct and trimethylolpropane/hexamethylene diisocyanate adduct, more preferably is a trimethylolpropane/tolylene diisocyanate adduct. As the crosslinking agent, by using at least one selected from trimethylolpropane/tolylene diisocyanate adduct and trimethylolpropane/hexamethylene diisocyanate adduct, the instrument peel force P becomes larger than the instrument peel force Q, and as a crosslinking agent, By using the trimethylolpropane/tolylene diisocyanate adduct, the instrument peel force P tends to become larger than the instrument peel force Q (that is, the value of (PQ) may tend to become larger).

As the epoxy crosslinking agent (polyfunctional epoxy compound), for example, 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 di Glycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether Dil ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2-hydroxyethyl) isocyanurate, resorcindiglycidyl ester In addition to cidyl ether and bisphenol-S-diglycidyl ether, an epoxy-based resin having two or more epoxy groups in the molecule may be mentioned. As an epoxy-type crosslinking agent, commercial items, such as a brand name "Tetrad C" (made by Mitsubishi Gas Chemical Co., Ltd.), are also mentioned.

Any suitable content can be employ|adopted for content of the crosslinking agent in the acrylic adhesive composition for adhesive layers 2 in the range which does not impair the effect of this invention. As such content, for example, from the viewpoint that the effect of the present invention can be further expressed, with respect to the solid content (100 parts by weight) of the acrylic polymer, it is preferably 0.1 parts by weight to 10.0 parts by weight, more preferably 0.2 It is a weight part - 8.0 weight part, More preferably, it is 0.3 weight part - 6.0 weight part, Especially preferably, it is 0.4 weight part - 5.0 weight part, Most preferably, it is 0.5 weight part - 4.5 weight part.

The acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer 2 can contain any appropriate other components within a range that does not impair the effects of the present invention. Examples of such other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antioxidants, and inorganic fillers. , organic fillers, metal powders, colorants (pigments or dyes, etc.), thin materials, ultraviolet absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents , a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all to these Examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when it describes as "part", unless there is a special note, "part by weight" is meant, and when it describes as "%", it means "weight%" unless there is a special note.

<Measurement of Weight Average Molecular Weight>

The weight average molecular weight was measured by the gel permeation chromatography (GPC) method. Specifically, as a GPC measuring apparatus, using a brand name "HLC-8120GPC" (manufactured by Tosoh Corporation), it measured under the following conditions, and calculated according to a standard polystyrene conversion value.

(Molecular weight measurement conditions)

-Sample concentration: 0.2% by weight (tetrahydrofuran solution)

・Sample injection volume: 10 μL

・Column: Product name “TSKguardcolumn SuperHZ-H (1 pc.) + TSKgel SuperHZM-H (2 pcs.)” (manufactured by Tosoh Corporation)

・Reference column: trade name "TSKgel SuperH-RC (1 pc)" (manufactured by Tosoh Corporation)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.6 mL/min

Detector: Differential Refractometer (RI)

·Column temperature (measured temperature): 40℃

<Measurement of instrument peel force P>

The laminated film for reinforcement was cut to the size of 25 mm in width and 80 mm in length.

After leaving it to stand in the environment of 23 degreeC x 50%RH for 24 hours, the separator was peeled and the adhesive layer 1 was exposed. Next, a single-sided adhesive tape cut to a size of 25 mm in width and 50 mm in length (manufactured by Nichi Reflection, trade name "Cellotape (registered trademark)") was applied to the adhesive layer of the laminated film for reinforcing so that the end surface was exposed by 1 mm. It was press-bonded to the surface of (1) and left to stand for about 10 seconds.

Thereafter, using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB), the maximum stress applied at the initial stage of peeling when peeling the single-sided adhesive tape at a peeling rate of 300 mm/min and a peeling angle of 180 degrees was taken as the instrument peel force P (N/25 mm). The measurement was performed in the environment of 23 degreeC x 50%RH.

<Measurement of instrument peel force Q>

The laminated film for reinforcement was cut to the size of 25 mm in width and 80 mm in length.

After leaving it to stand for 24 hours in an environment of 23°C x 50%RH, a single-sided adhesive tape (manufactured by Nichi Reflection, trade name “Cellotape (registered trademark)”) cut to a size of 25 mm in width and 50 mm in length was applied to the end face. It was press-bonded to the separator surface of the laminated|multilayer film for reinforcement so that it might come out 1 mm, and it was left to stand for about 10 seconds.

Thereafter, using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB), the maximum stress applied at the initial stage of peeling when peeling the single-sided adhesive tape at a peeling rate of 300 mm/min and a peeling angle of 180 degrees was taken as the gauge peel force Q (N/25 mm). The measurement was performed in the environment of 23 degreeC x 50%RH.

<Measurement of the initial adhesive force of the pressure-sensitive adhesive layer (1) to the glass plate>

The laminated film for reinforcement was cut|disconnected by width 25mm and length 150mm, and it was set as the sample for evaluation.

In the environment of 23 degreeC x 50 %RH, the surface of the adhesive layer of the sample for evaluation was affixed to the glass plate (Matsunami Glass Kogyo Co., Ltd. make, brand name: Microslide Glass S) by one reciprocation of a 2.0 kg roller. After curing for 30 minutes in an environment of 23°C x 50%RH, using a universal tensile tester (manufactured by Minebea Corporation, product name: TCM-1kNB), peeled at a peeling angle of 180 degrees and a tensile rate of 300 mm/min. , the adhesive force was measured.

<Evaluation of the peelability of the separator>

In the reinforcing laminated film having a surface protection film and a separator, when the separator is peeled from the surface of the pressure-sensitive adhesive layer, it is not peeled off at the interface between the surface protection film and the reinforcing film, etc., and the separator can be peeled smoothly from the surface of the pressure-sensitive adhesive layer was evaluated.

○: When the separator is peeled from the surface of the pressure-sensitive adhesive layer (1), it is not peeled off at an unintended location such as the interface between the surface protection film and the reinforcing film, and the separator can be smoothly peeled from the surface of the pressure-sensitive adhesive layer (1) there was.

x: When peeling a separator from the surface of the adhesive layer 1, it peeled at unintentional locations, such as the interface of a surface protection film and a reinforcement film.

[Production Example 1]: Preparation of acrylic pressure-sensitive adhesive composition (1)

In a four-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 95 parts by weight, acrylic acid (manufactured by Toagosei Co., Ltd.): 5 parts by weight, 2 as a polymerization initiator, 2'-azobisisobutyronitrile (manufactured by Wako Junyaku Kogyo Co., Ltd.): 0.2 parts by weight, ethyl acetate: 156 parts by weight were added, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was maintained around 63 ° C. Polymerization reaction was performed for 10 hours, and the solution (40 weight%) of an acrylic polymer with a weight average molecular weight of 700,000 was prepared.

Next, 0.1 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent in terms of solid content is added to the obtained acrylic polymer solution in terms of solid content to 100 parts by weight of the solid content, and acetic acid so that the total solid content is 25% by weight. It diluted with ethyl and stirred with a disper, and obtained the acrylic adhesive composition (1).

[Production Example 2]: Preparation of the acrylic pressure-sensitive adhesive composition (2)

In a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 100 parts by weight, 2-hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.): 4 parts by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.2 parts by weight, ethyl acetate: 156 parts by weight, nitrogen gas was introduced while gently stirring, and a flask Polymerization reaction was performed for 6 hours by maintaining the liquid temperature inside 65 degreeC vicinity, and the solution (40 weight%) of the acrylic polymer with a weight average molecular weight of 550,000 was prepared.

Next, to the obtained acrylic polymer solution, 4 parts by weight of Coronate L (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) in terms of solid content as a crosslinking agent with respect to 100 parts by weight of the solid content, Envirizer OL-1 (Tokyo Fine Chemical) as a crosslinking catalyst 0.03 weight part in conversion of solid content was added, it diluted with ethyl acetate so that total solid might be 25 weight%, and it stirred with a disper, and obtained the acrylic adhesive composition (2).

[Production Example 3]: Preparation of acrylic pressure-sensitive adhesive composition (3)

In a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 100 parts by weight, 2-hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.): 4 parts by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.2 parts by weight, ethyl acetate: 156 parts by weight, nitrogen gas was introduced while gently stirring, and a flask Polymerization reaction was performed for 6 hours by maintaining the liquid temperature inside 65 degreeC vicinity, and the solution (40 weight%) of the acrylic polymer with a weight average molecular weight of 550,000 was prepared.

Next, 4 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) in terms of solid content as a crosslinking agent with respect to 100 parts by weight of the solid content of the obtained acrylic polymer solution, Envirizer OL-1 (Tokyo Fine Chemical) as a crosslinking catalyst company) was added in conversion of solid content, 0.03 weight part was diluted, it diluted with ethyl acetate so that the whole solid might be 25 weight%, it stirred with a disper, and the acrylic adhesive composition (3) was obtained.

[Production Example 4]: Preparation of urethane-based pressure-sensitive adhesive composition (4)

As a polyfunctional polyol, 100 parts by weight of Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000) in terms of solid content, 18 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) as a crosslinking agent in terms of solid content, crosslinking 0.04 parts by weight of Nasem ferric iron (manufactured by Nippon Chemical Industries, Ltd.) as a catalyst in terms of solid content and 0.5 parts by weight of Irganox 1010 (manufactured by BASF Corporation) as a deterioration inhibitor in terms of solid content were added, and ethyl acetate so that the total solid content was 35% by weight. was diluted with and stirred with a disper to obtain a urethane pressure-sensitive adhesive composition (4).

[Production Example 5]: Preparation of surface protection film (A)

The acrylic pressure-sensitive adhesive composition (2) obtained in Production Example 2 was applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying with a fountain roll was 23 µm, drying temperature 130 Cure and dried under the conditions of 30 seconds of drying time. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material containing the 25-micrometer-thick polyester resin which silicone-treated to the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the surface protection film (A) was obtained.

[Production Example 6]: Preparation of surface protection film (B)

The acrylic pressure-sensitive adhesive composition (3) obtained in Production Example 3 was applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying with a fountain roll was 21 µm, drying temperature 130 Cure and dried under the conditions of 30 seconds of drying time. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material containing the 25-micrometer-thick polyester resin which silicone-treated to the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the surface protection film (B) was obtained.

[Production Example 7]: Preparation of surface protection film (C)

The urethane-based pressure-sensitive adhesive composition (4) obtained in Production Example 4 was applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying with a fountain roll was 12 µm, drying temperature 130 Cure and dried under the conditions of 30 seconds of drying time. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material containing the 25-micrometer-thick polyester resin which silicone-treated on the one surface was bonded to the surface of the adhesive layer, and the surface protection film (C) was obtained.

[Example 1]

The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 1 was applied to a 125 μm thick “Lumiror S10” (manufactured by Toray Corporation) as a reinforcing base material containing a polyester resin so that the thickness after drying with a fountain roll became 25 μm, , and dried by curing under conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the adhesive layer was formed on the base material for reinforcement.

Next, the silicone-treated surface of the separator containing the polyester resin with a thickness of 75 micrometers which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the film (1) for reinforcement with a separator was obtained.

Next, the adhesive layer side of the surface protection film (A) obtained in manufacture example 5 was bonded to the base material surface for reinforcement of the reinforcing film (1) with a separator, and the laminated|multilayer film (1) for reinforcement was obtained.

The results are shown in Table 1.

[Examples 2 to 12, Comparative Examples 1 to 2]

As in Example 1, except having changed the thickness of "Lumiror S10" (made by Toray Corporation) as a base material for reinforcement, the thickness of the adhesive layer formed on the base material for reinforcement, and the thickness of a separator as shown in Table 1, It carried out and obtained laminated|multilayer film for reinforcement (2)-(12), (C1)-(C2).

The results are shown in Table 1.

[Example 13]

The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 1 is applied to a 125 μm thick “Lumi-Rer S10” (made by Toray Corporation) as a reinforcing substrate containing a polyester resin, so that the thickness after drying with a fountain roll becomes 25 μm, It was cured and dried under the conditions of a drying temperature of 130°C and a drying time of 30 seconds. In this way, the adhesive layer was formed on the base material for reinforcement.

Next, the silicone-treated surface of the separator containing the polyester resin with a thickness of 75 micrometers which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the film (1) for reinforcement with a separator was obtained.

Next, the adhesive layer side of the surface protection film (B) obtained in manufacture example 6 was bonded to the base material surface for reinforcement of the reinforcement film 1 with a separator, and the laminated film 13 for reinforcement was obtained.

The results are shown in Table 2.

[Examples 14 to 24, Comparative Examples 3 to 4]

The same as in Example 13, except that the thickness of "Lumiror S10" (manufactured by Toray Corporation) as the reinforcing base material, the thickness of the pressure-sensitive adhesive layer formed on the reinforcing base material, and the thickness of the separator were changed as shown in Table 2 It carried out and obtained the laminated|multilayer film for reinforcement (14)-(24), (C3)-(C4).

The results are shown in Table 2.

[Example 25]

The acrylic pressure-sensitive adhesive composition (1) obtained in Production Example 1 was applied to a 125 μm thick “Lumiror S10” (manufactured by Toray Corporation) as a reinforcing base material containing a polyester resin so that the thickness after drying with a fountain roll became 25 μm, , and dried by curing under conditions of a drying temperature of 130° C. and a drying time of 30 seconds. In this way, the adhesive layer was formed on the base material for reinforcement.

Next, the silicone-treated surface of the separator containing the polyester resin with a thickness of 75 micrometers which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the film (1) for reinforcement with a separator was obtained.

Next, the adhesive layer side of the surface protection film (C) obtained in manufacture example 7 was bonded to the base material surface for reinforcement of the reinforcing film 1 with a separator, and the laminated film 25 for reinforcement was obtained.

The results are shown in Table 3.

[Examples 26 to 36, Comparative Examples 5 to 6]

As in Example 25, except having changed the thickness of "Lumiror S10" (made by Toray Corporation) as a base material for reinforcement, the thickness of the adhesive layer formed on the base material for reinforcement, and the thickness of a separator as shown in Table 3, It carried out and obtained the laminated|multilayer film for reinforcement (26)-(36), (C5)-(C6).

The results are shown in Table 3.

From Tables 1 to 3, when the gauge peeling force P of the reinforcing substrate in the reinforcing laminated film is larger than the gauge peeling force Q of the separator, it can be seen that the separator can be smoothly peeled from the surface of the pressure-sensitive adhesive layer. can

Moreover, when the surface protection film employ|adopted is compared, the tendency for the value of (P-Q) to become large is seen in order of a surface protection film (C), a surface protection film (B), and a surface protection film (A). This shows that the surface protection film employed can more smoothly peel the separator from the surface of the pressure-sensitive adhesive layer in the order of the surface protection film (C), the surface protection film (B), and the surface protection film (A). have. That is, it turns out that when the surface protection film which has an adhesive layer comprised from a specific acrylic adhesive is employ|adopted as a surface protection film, a separator can be peeled more smoothly from the surface of an adhesive layer.

In addition, as described above, the thinner the thickness of the reinforcing base material is, the more unintentional (typically, the interface between the surface protection film and the reinforcing film) in the case of peeling the separator from the reinforcing laminated film. There is a possibility that interfacial peeling may occur in the The risk of interfacial peeling in an unintentional location when it intends to peel off a separator becomes high, especially when the instrument peeling force P is small, the risk becomes higher. Therefore, when designing the laminated film for reinforcement of this invention by making the thickness of the base material for reinforcement thin, in order to reduce the said risk as much as possible, as mentioned above, a surface protection film (A) or a surface protection film (B) As shown in ), it is preferable to employ|adopt the surface protection film which has an adhesive layer comprised from a specific acrylic adhesive.

The laminated film for reinforcement of this invention can be used suitably in order to provide rigidity and impact resistance to an optical member, an electronic member, etc.

1000: laminated film for reinforcement
100: separator
200: adhesive layer (1)
300: reinforcing substrate
400: surface protection film
410: base layer (2)
420: adhesive layer (2)

Claims (13)

It is a laminated film for reinforcement having a separator, an adhesive layer (1), a substrate for reinforcement, and a surface protection film in this order,
The separator and the pressure-sensitive adhesive layer 1 are directly laminated,
The reinforcing substrate and the surface protection film are directly laminated,
The separator includes a base layer (1),
The surface protection film includes a base material layer (2) and an adhesive layer (2), and the pressure-sensitive adhesive layer (2) is directly laminated on the reinforcing substrate,
The laminated film for reinforcement in which the gauge peeling force P of the said base material for reinforcement in this laminated|multilayer film for reinforcement is larger than the gauge peeling force Q of the said separator in this laminated|multilayer film for reinforcement. According to claim 1,
The reinforcing base material is a plastic film, the reinforcing laminated film. 3. The method of claim 1 or 2,
A thickness of the reinforcing substrate is 25 μm to 500 μm, a reinforcing laminated film. 4. The method according to any one of claims 1 to 3,
The thickness of the separator is 1 μm to 100 μm, the reinforcing laminated film. 5. The method according to any one of claims 1 to 4,
The thickness of the surface protection film is 5㎛ to 500㎛, Reinforcing laminated film. 6. The method according to any one of claims 1 to 5,
The pressure-sensitive adhesive layer (1) is composed of at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, laminated film for reinforcement. 7. The method of claim 6,
The acrylic pressure-sensitive adhesive is formed of an acrylic pressure-sensitive adhesive composition, and the acrylic pressure-sensitive adhesive composition is (a component) (meth)acrylic acid alkylester having 4 to 12 carbon atoms in the alkyl group of the alkylester portion, (b component) having an OH group (meth) From the group consisting of an acrylic polymer formed by polymerization from a composition (A) comprising at least one selected from the group consisting of acrylic acid ester and (meth)acrylic acid, and (c component) a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent. The laminated|multilayer film for reinforcement containing at least 1 sort(s) selected. 8. The method according to any one of claims 1 to 7,
The pressure-sensitive adhesive layer (2) is composed of at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, laminated film for reinforcement. 8. The method according to any one of claims 1 to 7,
The said pressure-sensitive adhesive layer (2) is composed of at least one selected from the group consisting of an acrylic pressure-sensitive adhesive and a urethane-based pressure-sensitive adhesive, laminated film for reinforcement. 9. The method of claim 8,
The acrylic pressure-sensitive adhesive is formed of an acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer (2), and the acrylic pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer (2) has 4 to 12 carbon atoms in the alkyl group of the alkyl ester (component p) (meth)alkyl (meth)acrylate. An acrylic polymer formed by polymerization from a composition (B) comprising at least one selected from the group consisting of an ester, (q component) an OH group (meth)acrylic acid ester, and (meth)acrylic acid, (r component) C A laminated film for reinforcement comprising at least one selected from the group consisting of a functional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent. 11. The method of claim 10,
(component p) is 2-ethylhexyl acrylate, (component q) is 2-hydroxyethyl acrylate, and (component r) is a polyfunctional isocyanate-based crosslinking agent. 12. The method of claim 11,
The reinforcing laminated film wherein the (r component) is a trimethylolpropane/tolylene diisocyanate adduct. 13. The method according to any one of claims 1 to 12,
Temperature 23°C, humidity 50%RH, peel angle 150°C, peeling angle 180°C, peeling angle of the pressure-sensitive adhesive layer 1 exposed by peeling the separator at a temperature of 23°C, humidity 50%RH, peeling rate 10m/min. The laminated film for reinforcement whose initial stage adhesive force with respect to the glass plate in speed|rate 300 mm/min is 1.0 N/25 mm or more.

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