CN113382859A - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
CN113382859A
CN113382859A CN202080012087.8A CN202080012087A CN113382859A CN 113382859 A CN113382859 A CN 113382859A CN 202080012087 A CN202080012087 A CN 202080012087A CN 113382859 A CN113382859 A CN 113382859A
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meth
cation
weight
acrylate
imide
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CN202080012087.8A
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CN113382859B (en
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越智元气
山形真人
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Abstract

Provided is a surface protection film which has high adhesion force and high light peelability and can suppress the generation of bubbles even when the surface protection film is subjected to high-temperature high-pressure treatment by an autoclave or the like after being attached to an adherend (preferably, an adherend having a surface water contact angle of a certain level or more) and then returned to normal temperature and normal pressure. The surface protection film comprises a pressure-sensitive adhesive layer and a base material layer, wherein when the free induction decay signal obtained by pulse NMR measurement of the pressure-sensitive adhesive layer is separated into 2 components by a nonlinear least square method, the component with a short relaxation time is a hard component (S), the component with a long relaxation time is a soft component (L), and the spin-spin relaxation time T2(L) of the proton of the soft component (L) measured at 30 DEG C30With the spin-spin relaxation time T2(L) of the protons of the soft component (L) measured at 60 DEG C60Ratio of (A) T2(L)60/T2(L)302.15 to 3.05, and the shear adhesion of the surface protective film is 10N/cm2The surface protection film has a high-speed peeling force of 0.8N/25mm or less.

Description

Surface protective film
Technical Field
The present invention relates to a surface protective film.
Background
In the manufacturing process of optical members and electronic members, a surface protective film is generally bonded to an exposed surface in order to prevent damage to the surface during processing, assembly, inspection, transportation, and the like. Such a surface protection film is peeled off from an optical member or an electronic member at a timing when surface protection is not required (patent document 1).
In order to pressure bond the surface protective film to an adherend, high-temperature high-pressure treatment using an autoclave or the like may be performed. After such high-temperature and high-pressure treatment, the temperature and pressure must be returned to normal temperature and pressure.
However, the conventional surface protection film has the following problems: when the pressure is increased after the adhesive is attached to an adherend and then returned to normal temperature and pressure, air bubbles are likely to be generated. Particularly, a surface protective film designed in such a manner that an adhesive agent becomes hard in consideration of its application in an application requiring light peelability has the following problems: fine bubbles (typically, bubbles having a diameter of approximately several millimeters) due to foreign matter, rough machined end portions (burrs), and the like are easily generated.
Therefore, surface protection films have been proposed to solve such problems (patent documents 2 and 3).
The surface protection film described in patent document 2 has a problem that it is heavy in peeling and cannot be applied to applications requiring light peeling property.
The surface protection film for a polarizing plate described in patent document 3 has a problem of preventing the floating in a tunnel shape, and has an insufficient level of light peelability.
In particular, in the case of an application in which the surface-protecting film is attached to an adherend having a surface with a water contact angle of a certain level or more, the above-mentioned problem of the generation of bubbles is remarkably recognized.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-
Patent document 2: japanese laid-open patent publication No. 11-961
Patent document 3: japanese laid-open patent publication No. 2007-304317
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a surface protection film that has high adhesion and high light peelability, and that can suppress the generation of bubbles even when the film is subjected to high-temperature high-pressure treatment such as an autoclave after being attached to an adherend (preferably, an adherend having a surface water contact angle of a certain level or more) and thereafter returned to normal temperature and pressure.
Means for solving the problems
The surface protection film of the present invention comprises an adhesive layer and a substrate layer,
when the free induction decay signal obtained by pulse NMR measurement of the pressure-sensitive adhesive layer is separated into 2 components by the nonlinear least squares method, the component with a short relaxation time is a hard component (S), the component with a long relaxation time is a soft component (L), and the spin-spin relaxation time T2(L) of the proton of the soft component (L) measured at 30 ℃ is determined30With the spin-spin relaxation time T2(L) of the protons of the soft component (L) measured at 60 DEG C60Ratio of (A) T2(L)60/T2(L)30Is 2.15 to 3.05,
the surface protective film had a shear adhesion of 10N/cm2In the above-mentioned manner,
the surface protective film has a high-speed peeling force of 0.8N/25mm or less.
In one embodiment, the adhesive layer has a thickness of 1 to 500 μm.
In one embodiment, the thickness of the substrate layer is 1 μm to 500 μm.
In one embodiment, the adhesive layer is composed of an adhesive formed by an adhesive composition comprising: a (meth) acrylic copolymer (A), a polyfunctional alcohol (C), and a crosslinking agent (D).
In one embodiment, the (meth) acrylic copolymer (a) is formed by polymerization from a composition (a) comprising: alkyl (meth) acrylate in which the alkyl group of the alkyl ester part (component a1) has 4 to 12 carbon atoms, and (meth) acrylate having an OH group (component a 2).
In one embodiment, the above composition (a) comprises (meth) acrylic acid.
In one embodiment, the number of functional groups of the polyfunctional alcohol (C) is 3 to 6.
In one embodiment, the number average molecular weight of the polyfunctional alcohol (C) is 50 to 10000.
In one embodiment, the adhesive composition includes a (meth) acrylic copolymer (B) formed by polymerizing a composition (B) including an alkyl (meth) acrylate in which an alkyl group of an alkyl ester portion is an alicyclic hydrocarbon group (component B1).
In one embodiment, the composition (b) contains (b2 component) an alkyl (meth) acrylate in which the alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms.
In one embodiment, the above composition (b) comprises a thiol.
In one embodiment, the Tg of the (meth) acrylic copolymer (B) is 50 to 250 ℃.
In one embodiment, the weight average molecular weight of the (meth) acrylic copolymer (B) is 1000 to 30000.
In one embodiment, the adhesive composition comprises an ionic liquid.
In one embodiment, the surface protection film of the present invention has a bubble generation number of 10 or less after the high-temperature and high-pressure treatment.
In one embodiment, the surface protection film of the present invention is used for protecting a surface of an adherend, the surface having a water contact angle of 60 degrees or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a surface protection film which has high adhesive force and high light peelability and can suppress the generation of bubbles even when the surface protection film is subjected to high-temperature high-pressure treatment such as an autoclave after being attached to an adherend (preferably, an adherend having a surface water contact angle of a certain level or more) and thereafter returned to normal temperature and normal pressure.
Drawings
FIG. 1 is a schematic cross-sectional view of one embodiment of the surface protective film of the present invention.
Fig. 2 is a schematic cross-sectional view showing a method for producing the polarizing plate (a) used for the adherend (a).
Fig. 3 is a schematic cross-sectional view showing a method for manufacturing a polarizing plate used for the adherend (C).
Detailed Description
In the present specification, when the expression "weight" is used, the expression "mass" may be used in place of the "mass" which is usually used as an SI-based unit indicating the weight.
In the present specification, the expression "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", the expression "(meth) acrylate" means "acrylate and/or methacrylate", the expression "(meth) allyl" means "allyl and/or methallyl", and the expression "(meth) acrolein" means "acrolein and/or methacrolein".
Surface protective film
The surface protection film of the present invention comprises an adhesive layer and a substrate layer.
The surface protection film of the present invention may be provided with any other suitable member as long as it has a pressure-sensitive adhesive layer and a base material layer, within a range not impairing the effects of the present invention. Typically, the surface protection film of the present invention is formed of a base material layer and an adhesive layer.
Fig. 1 is a schematic cross-sectional view of a surface protective film according to an embodiment of the present invention. In fig. 1, the surface protection film 10 includes a base layer 1 and a pressure-sensitive adhesive layer 2. In fig. 1, a base material layer 1 and an adhesive layer 2 are directly laminated.
In fig. 1, the surface of the pressure-sensitive adhesive layer 2 opposite to the base material layer 1 may be provided with any suitable release liner (not shown) for protection or the like until use. Examples of the release liner include release liners obtained by subjecting the surface of a substrate (liner substrate) such as paper or a plastic film to a silicone treatment; and release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is laminated with a polyolefin resin. Examples of the plastic film as the spacer base material include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, and the like. The plastic film as the base material of the gasket is preferably a polyethylene film.
The thickness of the release liner is preferably 1 to 500. mu.m, more preferably 3 to 450. mu.m, still more preferably 5 to 400. mu.m, and particularly preferably 10 to 300. mu.m.
The thickness of the surface-protecting film of the present invention is preferably 10 μm to 500. mu.m, more preferably 15 μm to 400. mu.m, still more preferably 20 μm to 350. mu.m, particularly preferably 25 μm to 300. mu.m, most preferably 30 μm to 250. mu.m.
The surface protection film of the present invention was cut into a size of 10mm in width and 100mm in length, and after the separator was peeled off, the adhesive (bonding) area of the exposed adhesive layer was 1cm2The pressure-sensitive adhesive sheet is adhered to an adherend having a surface with a water contact angle of 60 degrees or more (for example, an unsaponifiable TAC polarizing plate (width 70mm, length 100mm, water contact angle 69.9 degrees) obtained in production example 5 described later), left to stand in an environment of 23 ℃ X50% RH for 30 minutes, and then peeled off in the shear direction at a peeling speed of 0.06 mm/minute, and the maximum load (N/cm) at that time is measured2) As the shear adhesion, the shear adhesion measured under the above conditions is preferably 10N/cm2Above, more preferably 10N/cm2～80N/cm2More preferably 10N/cm2～50N/cm2Particularly preferably 15N/cm2～45N/cm2Most preferably 20N/cm2～40N/cm2. When the shear adhesion is within the above range, the surface protective film of the present invention can exhibit high adhesion.
The surface protective film of the present invention is obtained by cutting a surface protective film into a size of 25mm in width and 100mm in length, peeling off a separator, pressing the separator against the surface of an adherend having a water contact angle of 60 degrees or more (for example, an unsaponifiable TAC polarizing plate (width 70mm, length 100mm, water contact angle 69.9 degrees) obtained in production example 5 described later) by a hand press under a pressure bonding condition of 0.25MPa and 0.3 m/min to prepare an evaluation sample, peeling off the separator on the polarizing plate side of the evaluation sample, pressing the separator against a glass substrate having a thickness of 1.3mm, width 65mm, and length 165mm by a hand press under an environment of 23 ℃ x 50% RH for 30 minutes, and then peeling off one end portion of the surface protective film at a peeling angle of 180 ° at a stretching speed of 30 m/min under an environment of 23 ℃ x 50% RH by a universal tensile tester, and setting the adhesive force at this time as a high-speed peeling force, the high-speed peel force measured under the above conditions is preferably 10N/25mm or less, more preferably 0.01N/25mm to 10N/25mm, still more preferably 0.01N/25mm to 5N/25mm, particularly preferably 0.05N/25mm to 3N/25mm, and most preferably 0.05N/25mm to 2N/25 mm. When the high-speed peeling force is within the above range, the surface protection film of the present invention can exhibit high light peelability.
The surface protective film of the present invention is obtained by cutting a surface protective film into a size of 65mm in width and 90mm in length, peeling off a separator, pressing the surface of an adherend having a water contact angle of 60 degrees or more (for example, unsaponifiable TAC polarizing plate (70 mm in width, 100mm in length, and 69.9 degrees in water contact angle) obtained in production example 5 described later) with a hand press roll, laminating the surface protective film under a pressure bonding condition of 0.25MPa and 0.3 m/min, cutting 4 sides from the surface protective film side with a cutter to a width of 50mm and a length of 80mm, peeling off the separator on the polarizing plate side, pressing the surface protective film to a piece of glass having a thickness of 1.3mm, a width of 65mm, and a length of 165mm with a hand press roll, leaving the surface protective film in an environment of 23 ℃ x 50% RH for 30 minutes, subjecting the surface protective film to autoclave treatment at an environment of 50 ℃ and 5atm for 40 minutes, and then returning the surface protective film to normal pressure, the number of bubbles generated at the end of the polarizing plate after the above process is counted as the number of bubbles generated (the number of bubbles generated after the high-temperature and high-pressure treatment), and the number of bubbles generated is preferably 10 or less, more preferably 8 or less, further preferably 5 or less, particularly preferably 3 or less, and most preferably 0. As described above, the surface protection film of the present invention can suppress the generation of bubbles even when the surface protection film is subjected to a high-temperature high-pressure treatment such as an autoclave after being attached to an adherend and then returned to normal temperature and normal pressure.
The surface protective film of the present invention can be produced by any suitable method. Such a production method can be carried out by any appropriate production method such as the following method.
(1) Method for coating solution or hot melt of material for forming adhesive layer on base layer,
(2) A method of applying a solution or hot melt of a material for forming an adhesive layer on a separator and transferring the formed adhesive layer to a base layer,
(3) A method of extruding a material for forming the adhesive layer to form a coating on the base material layer,
(4) A method of extruding the substrate layer and the adhesive layer in two or more layers,
(5) A method of laminating an adhesive layer on a substrate layer in a single layer or a method of laminating an adhesive layer and a laminate layer in two layers,
(6) A method of laminating two or more layers of an adhesive layer and a substrate layer-forming material such as a film or a laminate layer.
As a method of coating, for example, a roll coating method, a comma coating method, a die coating method, a reverse coating method, a screen printing method, a gravure coating method, or the like can be used.
Adhesive layer
The adhesive layer is composed of an adhesive formed by an adhesive composition. The pressure-sensitive adhesive layer can be produced by any suitable production method. Examples of such a production method include the following methods: the pressure-sensitive adhesive composition is applied to a base material layer, and if necessary, heated and dried to form a pressure-sensitive adhesive layer on the base material layer. Examples of the method for applying the adhesive composition of the present invention to the substrate layer include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
The thickness of the pressure-sensitive adhesive layer is preferably 1 to 500. mu.m, more preferably 2 to 300. mu.m, still more preferably 3 to 200. mu.m, particularly preferably 4 to 150. mu.m, and most preferably 5 to 100. mu.m.
The binder composition preferably includes at least 1 selected from the following binder compositions:
(1) adhesive composition comprising (meth) acrylic copolymer (A), polyfunctional alcohol (C) and crosslinking agent (D),
(2) An adhesive composition comprising a polyol and a polyfunctional isocyanate.
An acrylic adhesive was obtained from the above (1), and a urethane adhesive was obtained from the above (2).
More preferably, the adhesive composition comprises: a (meth) acrylic copolymer (A), a polyfunctional alcohol (C), and a crosslinking agent (D).
The adhesive layer is preferably formed by a characteristic crosslinking reaction by the adhesive composition. Specifically, it is presumed that, based on the results of various studies: the adhesive composition contains a polyfunctional alcohol (C), and the polyfunctional alcohol (C) is combined with a crosslinking agent (D), thereby imparting a characteristic highly crosslinked structure to a (meth) acrylic copolymer (a) obtained from a composition containing a specific type of monomer component as an essential component. It is thus presumed that the pressure-sensitive adhesive layer has high adhesive force and high light peelability, and the surface protection film of the present invention having the pressure-sensitive adhesive layer can suppress the generation of bubbles even when subjected to high-temperature high-pressure treatment such as autoclave after being attached to an adherend and thereafter returned to normal temperature and normal pressure.
Further, when the pressure-sensitive adhesive layer (or the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer) included in the surface protection film of the present invention is designed to have the characteristic highly crosslinked structure as described above, it is found that when the pressure-sensitive adhesive composition includes the characteristic (meth) acrylic copolymer (B) as described later, the increase in the adhesive strength with time can be effectively suppressed, and more excellent light peelability can be exhibited.
The adhesive layer having a highly crosslinked structure can be observed from several angles. As these angles, for example, relaxation times observed by pulse NMR can be cited.
The inverse of the spin-spin relaxation time shows a positive linear correlation with the crosslinking density (the degree of restriction of molecular motion) of the polymer, and the spin-spin relaxation time T2 can be used as an index of the crosslinking density of the polymer component constituting the adhesive layer. Specifically, when pulse NMR of the polymer is measured, 1 or more (for example, 2 or 3) kinds of spin-spin relaxation time T2 can be obtained, and the magnitude of the spin-spin relaxation time T2 corresponds to the level of the crosslinking density of the polymer component constituting the adhesive layer. The method of discriminating components according to the magnitude of the spin-spin relaxation time is a method of discriminating components by nonlinear two-fold multiplication, and when the analysis residue (offset) is less than 10%, it can be judged that the resolution is appropriate. When the component having a high crosslinking density is separated into 2 components, the component having a high crosslinking density is set as the S component, the component having a low crosslinking density is set as the L component, and the spin-spin relaxation times of the components are set as T2(S) and T2(L), the spin-spin relaxation time T2(S) of the polymer component having a high crosslinking density to which molecular motion is restricted can be made small, and the spin-spin relaxation time T2(L) of the polymer component L having a low crosslinking density can be made large.
When the free induction decay signal of the pressure-sensitive adhesive layer obtained by pulse NMR measurement is separated into 2 components by the nonlinear least squares method, the component with a short relaxation time is a hard component (S), the component with a long relaxation time is a soft component (L), and the spin-spin relaxation time T2(L) of the proton of the soft component (L) measured at 30 ℃ is30With the spin-spin relaxation time T2(L) of the protons of the soft component (L) measured at 60 DEG C60Ratio of (A) T2(L)60/T2(L)30Preferably 1 or more, more preferably 1 to 5, further preferably 1.5 to 4, particularly preferably 2 to 3.5, and most preferably 2.15 to 3.
The aforementioned T2(L)30Preferably 500 to 5000. mu.s, more preferably 700 to 4000. mu.s, still more preferably 800 to 3000. mu.s, particularly preferably 900 to 2500. mu.s, and most preferably 1000 to 2300. mu.s.
The aforementioned T2(L)60Preferably 500 to 9000. mu.s, more preferably 1000 to 8000. mu.s, still more preferably 1500 to 7000. mu.s, particularly preferably 2000 to 6500. mu.s, and most preferably 2500 to 6000. mu.s.
Sometimes the adhesive layer has a highly crosslinked structure and may also be reflected in the degree of swelling. When the pressure-sensitive adhesive layer has a highly crosslinked structure, the swelling degree of the pressure-sensitive adhesive layer is preferably 250% or less, more preferably 80% to 250%, further preferably 85% to 240%, particularly preferably 90% to 235%, most preferably 95% to 230%.
The swelling degree can be measured by the following method, for example. That is, about 0.1g of the polymer after the crosslinking reaction was taken out, wrapped in a porous tetrafluoroethylene sheet (trade name "NTF 1122", manufactured by Nindon electric Co., Ltd.) having an average pore diameter of 0.2 μm, and bound with kite string, and the weight at that time was measured and taken as the weight before impregnation (total weight of the polymer, the tetrafluoroethylene sheet and the kite string), and the total weight of the tetrafluoroethylene sheet and the kite string was measured in advance and taken as the bag weight. Next, the polymer described above was wrapped with a tetrafluoroethylene sheet and bound with kite string, the obtained object (referred to as "sample") was placed in a 50ml container filled with ethyl acetate, allowed to stand at 23 ℃ for 7 days, and thereafter, the ethyl acetate-impregnated sample was taken out of the container, ethyl acetate adhering to the sample was sufficiently wiped off with a waste cloth, and the weight was measured, and this weight was taken as the weight after impregnation, and further transferred to an aluminum cup, and dried in a dryer at 130 ℃ for 2 hours to remove ethyl acetate, and then the weight was measured, and this weight was taken as the weight after drying, and the swelling degree was calculated according to the following formula.
Degree of swelling (%) - (a-b)/(c-b) × 100(1)
In formula (1), a represents the weight after immersion, b represents the weight of the bag, and c represents the weight after drying.
In the case of using the crosslinked polymer, it may be used from the surface of the pressure-sensitive adhesive layer of the surface-protecting film, or it may be used by applying the same pressure-sensitive adhesive layer as that provided on the surface-protecting film to a silicone separator or the like and drying the same.
Adhesive composition
The adhesive composition contains a (meth) acrylic copolymer (A). The number of the (meth) acrylic copolymers (a) may be only 1, or may be 2 or more.
The content of the (meth) acrylic copolymer (a) in the pressure-sensitive adhesive composition is preferably 50 to 99.9% by weight, more preferably 60 to 99.5% by weight, still more preferably 70 to 99% by weight, particularly preferably 80 to 99% by weight, and most preferably 85 to 99% by weight, in order to further exhibit the effects of the present invention.
The adhesive composition comprises a polyfunctional alcohol (C). The number of the polyfunctional alcohols (C) may be only 1, or may be 2 or more.
The content of the polyfunctional alcohol (C) in the adhesive composition may be any suitable content within a range not impairing the effects of the present invention. Such a content is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, further preferably 0.1 to 5 parts by weight, and particularly preferably 0.2 to 3 parts by weight, based on the solid content (100 parts by weight) of the (meth) acrylic copolymer (a), from the viewpoint of further exhibiting the effects of the present invention.
The adhesive composition contains a crosslinking agent (D). The number of the crosslinking agents (D) may be only 1, or may be 2 or more.
As for the content of the crosslinking agent (D) in the adhesive composition, any appropriate content may be employed within a range not impairing the effects of the present invention. Such a content is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 30 parts by weight, further preferably 0.01 to 20 parts by weight, and particularly preferably 0.01 to 10 parts by weight, based on the solid content (100 parts by weight) of the (meth) acrylic copolymer (a), from the viewpoint of further exhibiting the effects of the present invention.
The adhesive composition contains the (meth) acrylic copolymer (a), the polyfunctional alcohol (C), and the crosslinking agent (D), and may contain any appropriate other component within a range not impairing the effects of the present invention. The number of such other components may be only 1, or may be 2 or more.
The adhesive composition may be prepared by compounding its constituent ingredients by any suitable method.
[ meth (acrylic) copolymer (A) >
As the (meth) acrylic copolymer (a), any suitable (meth) acrylic copolymer can be used within a range not impairing the effects of the present invention.
The weight average molecular weight of the (meth) acrylic copolymer (a) is preferably 10 to 500 ten thousand, more preferably 20 to 400 ten thousand, further preferably 25 to 350 ten thousand, and particularly preferably 30 to 300 ten thousand, from the viewpoint of further exhibiting the effects of the present invention.
The (meth) acrylic copolymer (a) is preferably a (meth) acrylic copolymer formed by polymerizing a composition (a) containing: alkyl (meth) acrylate in which the alkyl group of the alkyl ester part (component a1) has 4 to 12 carbon atoms, and (meth) acrylate having an OH group (component a 2).
The number of the (a1 component) may be only 1, or may be 2 or more. The number of the (a2 component) may be only 1, or may be 2 or more.
Examples of the alkyl (meth) acrylate (component a1) having an alkyl group of an alkyl ester portion having 4 to 12 carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate. Among these, 2-ethylhexyl (meth) acrylate is preferable, and 2-ethylhexyl acrylate (2EHA) is more preferable, from the viewpoint that the effect of the present invention can be further exhibited.
From the viewpoint of further exhibiting the effects of the present invention, the content ratio of the alkyl (meth) acrylate (component a1) having an alkyl group with 4 to 12 carbon atoms in the alkyl ester moiety is preferably 50 to 99.9 wt%, more preferably 60 to 99.9 wt%, even more preferably 70 to 99.9 wt%, particularly preferably 80 to 99.9 wt%, and most preferably 85 to 99.9 wt%, based on the total amount (100 wt%) of the monomer components constituting the (meth) acrylic copolymer (a).
Examples of the (meth) acrylate having an OH group (component a 2) include (meth) acrylates having an OH group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA) are more preferable, and 4-hydroxybutyl acrylate (4HBA) is particularly preferable, from the viewpoint of further exhibiting the effects of the present invention.
From the viewpoint of further exhibiting the effects of the present invention, the content ratio of the (meth) acrylate having an OH group (a2 component) relative to the total amount (100 wt%) of the monomer components constituting the (meth) acrylic copolymer (a) is preferably 0.1 to 50 wt%, more preferably 0.1 to 40 wt%, still more preferably 0.2 to 30 wt%, particularly preferably 0.5 to 20 wt%, and most preferably 1 to 10 wt%.
The composition (a) may contain a copolymerizable monomer other than the components (a1) and (a 2). The number of the copolymerizable monomer may be only 1, or may be 2 or more.
The composition (a) may contain (meth) acrylic acid as a copolymerizable monomer. The (meth) acrylic acid includes at least 1 kind selected from the group consisting of acrylic acid and methacrylic acid, and acrylic acid is preferable in terms of further exhibiting the effects of the present invention.
From the viewpoint of further exhibiting the effects of the present invention, the content ratio of (meth) acrylic acid is preferably 0 to 10% by weight, more preferably 0 to 8% by weight, even more preferably 0 to 5% by weight, particularly preferably 0 to 2% by weight, and most preferably 0 to 1% by weight, based on the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (a).
Examples of the copolymerizable monomer other than (meth) acrylic acid include carboxyl group-containing monomers such as itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride) (with the exception of (meth) acrylic acid); amide group-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-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 glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; heterocyclic ring-containing vinyl monomers such as N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine and 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 cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth) acrylates having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentadienyl (meth) acrylate; aromatic hydrocarbon group-containing (meth) acrylates 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 vinyl toluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and the like.
As the copolymerizable monomer, a polyfunctional monomer may be used. The polyfunctional monomer is a monomer having 2 or more ethylenically unsaturated groups in 1 molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group may be employed within a range not impairing the effects of the present invention. Examples of such an ethylenically unsaturated group include a radical polymerizable functional group such as a vinyl group, an propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group). 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, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Such polyfunctional monomers may be 1 type or 2 or more types.
As the copolymerizable monomer, alkoxyalkyl (meth) acrylate may also be used. Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. The number of the alkoxyalkyl (meth) acrylates may be only 1, or may be 2 or more.
The composition (a) may contain any other suitable component within a range not impairing the effects of the present invention. Examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent. The content of these other components may be any suitable content within a range not impairing the effect of the present invention.
The polymerization initiator may be a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like, depending on the kind of the polymerization reaction. The number of polymerization initiators may be only 1, or may be 2 or more.
The thermal polymerization initiator can be preferably used when the acrylic polymer is obtained by solution polymerization. Examples of such a thermal polymerization initiator include azo polymerization initiators, peroxide polymerization initiators (e.g., dibenzoyl peroxide, t-butyl peroxymaleate, etc.), redox polymerization initiators, and the like. Among these thermal polymerization initiators, the azo polymerization initiators disclosed in Japanese patent application laid-open No. 2002-69411 are particularly preferable. Such an azo polymerization initiator is preferable in that the decomposition product of the polymerization initiator is less likely to remain in the acrylic polymer as a portion that causes generation of gas (outgas) by heating. Examples of the azo polymerization initiator include 2,2 '-azobisisobutyronitrile (hereinafter, sometimes referred to as AIBN), 2' -azobis-2-methylbutyronitrile (hereinafter, sometimes referred to as AMBN), dimethyl 2,2 '-azobis (2-methylpropionate), and 4, 4' -azobis-4-cyanovaleric acid. The amount of the azo polymerization initiator to be used is preferably 0.001 to 1 part by weight, more preferably 0.005 to 1 part by weight, still more preferably 0.005 to 0.8 part by weight, particularly preferably 0.01 to 0.8 part by weight, and most preferably 0.01 to 0.7 part by weight, based on the total amount (100 parts by weight) of the monomer components constituting the (meth) acrylic copolymer (a).
The photopolymerization initiator can be preferably used when the (meth) acrylic copolymer (a) is obtained by active energy ray polymerization. Examples of the photopolymerization initiator include benzoin ether type photopolymerization initiators, acetophenone type photopolymerization initiators, α -ketol type photopolymerization initiators, aromatic sulfonyl chloride type photopolymerization initiators, photoactive oxime type photopolymerization initiators, benzoin type photopolymerization initiators, benzil type photopolymerization initiators, benzophenone type photopolymerization initiators, ketal type photopolymerization initiators, and thioxanthone type photopolymerization initiators.
Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-dimethoxy-1, 2-diphenylethan-1-one, and anisole methyl ether. Examples of the acetophenone photopolymerization initiator include 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone and 4- (tert-butyl) dichloroacetophenone. Examples of the α -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl ] -2-methylpropan-1-one. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the optically active oxime-based photopolymerization initiator include 1-phenyl-1, 1-propanedione-2- (O-ethoxycarbonyl) -oxime and the like. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzil-based photopolymerization initiator include benzil and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3' -dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α -hydroxycyclohexylphenylketone. Examples of the ketal-based photopolymerization initiator include benzildimethylketal. Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-diisopropylthioxanthone, and dodecylthioxanthone.
The amount of the photopolymerization initiator to be used is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 8 parts by weight, still more preferably 0.01 to 5 parts by weight, particularly preferably 0.02 to 5 parts by weight, and most preferably 0.05 to 3 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the (meth) acrylic copolymer (a).
As a method for obtaining the (meth) acrylic copolymer (a), for example, various polymerization methods known as a method for synthesizing a (meth) acrylic copolymer, such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization, can be suitably used.
< polyfunctional alcohol (C) >
As the polyfunctional alcohol (C), any suitable polyfunctional alcohol may be used within a range not impairing the effects of the present invention.
The number of functional groups of the polyfunctional alcohol (C) is preferably 2 or more, more preferably 3 to 6, further preferably 3 to 5, particularly preferably 3 to 4, and most preferably 3, from the viewpoint of further exhibiting the effects of the present invention.
Examples of the polyfunctional alcohol (C) include polyether polyols and polyester polyols.
Examples of the polyether polyol include polypropylene glycol (2-functional), a diol (2-functional) obtained by adding propylene oxide to bisphenol a, a triol (3-functional) obtained by adding propylene oxide to glycerin, a triol (3-functional) obtained by adding propylene oxide to trimethylolpropane, a tetraol (4-functional) obtained by adding propylene oxide to active hydrogen of ethylenediamine, a polyol (polyfunctional) obtained by adding propylene oxide to sorbitol or sucrose, a triol (3-functional) obtained by adding propylene oxide and ethylene oxide to glycerin and having an ethylene oxide-terminated end, a tetraol (4-functional) obtained by adding propylene oxide and ethylene oxide to active hydrogen of ethylenediamine and having an ethylene oxide-terminated end, a polypropylene-based polyethylene glycol (2-functional) obtained by adding polypropylene-based polyethylene glycol and having an ethylene oxide-terminated end, and a polyether polyol (2-functional) obtained by adding propylene oxide and ethylene oxide-terminated end to active hydrogen of ethylene diamine, A diol (2-functional) obtained by adding propylene oxide and ethylene oxide to bisphenol a and having an end capped with ethylene oxide, a triol (3-functional) obtained by adding ethylene oxide to trimethylolpropane, a polypropylene-based polyethylene glycol (2-functional) obtained by randomly adding ethylene oxide and propylene oxide to polypropylene-based polyethylene glycol, a triol (3-functional) obtained by adding propylene oxide and ethylene oxide to glycerin and randomly adding ethylene oxide and propylene oxide to propylene oxide, and a flame retardant polyol (2-functional).
Examples of commercially available products of polyether polyols include Adeka Polyol (for example, P series, BPX series, G series, T series, EDP series, SP series, SC series, R series, RD series, AM series, BM series, CM series, EM series, GM series, PR series, GR series, flame retardant Polyol and the like) available from ADEKA, and polyols (for example, SANNIX GP series, SANNIX PP series, SANNIX TP-400 series, SANNIX SP-750 series, SANNIX PL-2100. PP series, SANESETER series, Primepol series, NEWPOL series, MELPOL series, PEG series, ROMACGOL series and the like) available from Sanyo chemical industries.
As the polyether polyol, from the viewpoint that the effect of the present invention can be further exhibited, preferred are: a triol (3-functional) obtained by adding propylene oxide to glycerin, a triol (3-functional) obtained by adding propylene oxide to trimethylolpropane, a triol (3-functional) obtained by adding propylene oxide and ethylene oxide to glycerin and having an end capped with ethylene oxide, a triol (3-functional) obtained by adding ethylene oxide to trimethylolpropane, a triol (3-functional) obtained by adding propylene oxide and ethylene oxide to glycerin and a triol (3-functional) obtained by randomly adding ethylene oxide and propylene oxide to glycerin are more preferable: a triol (3-functional) obtained by adding propylene oxide to glycerin, a triol (3-functional) obtained by adding propylene oxide and ethylene oxide to glycerin and having an ethylene oxide end capped, a triol (3-functional) obtained by adding propylene oxide and ethylene oxide to glycerin and obtained by randomly adding ethylene oxide and propylene oxide to glycerin, and a triol (3-functional) obtained by adding propylene oxide to glycerin is more preferable.
Examples of the polyester polyol include polyester polyols obtained by reacting an acid component with a diol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of the diol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 3' -dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1, 4-butanediol, neopentyl glycol, and butylethylpentanediol, and examples of the polyol component include glycerin, trimethylolpropane, and pentaerythritol. The polyester polyol (a1) may be a polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (. beta. -methyl-. gamma. -valerolactone) and polycaprolactone.
Examples of commercially available polyester polyols include ADEKA NEWACE (e.g., F18-62, F7-67, Y9-10, Y4-5, Y52-13, Y52-21, V14-90, YG-108, F1212-29, #50, Y65-55, YT-101, YT-651, NS-2400, etc.) from ADEKA, Inc.
The number average molecular weight of the polyfunctional alcohol (C) is preferably 50 to 10000, more preferably 60 to 5000, still more preferably 70 to 2500, particularly preferably 75 to 2000, and most preferably 80 to 1000, from the viewpoint of further exhibiting the effects of the present invention.
< crosslinking agent (D) >
As the crosslinking agent (D), any suitable crosslinking agent may be used within a range not impairing the effects of the present invention.
Examples of the crosslinking agent (D) include a polyfunctional isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, and a peroxide crosslinking agent, and further include a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent, a metal salt crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and an amine crosslinking agent. Among these, at least 1 selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent is preferable from the viewpoint of further exhibiting the effects of the present invention.
Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as 1, 2-ethylenediisocyanate, 1, 4-butylidenediisocyanate and 1, 6-hexamethylenediisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd., product name "CORONATE L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd., product name "CORONATE HL"), product name "CORONATE" (Nippon Polyurethane Industry Co., Ltd., product name "TAKENATE 110N"), and product name "TAKENATE 600" (product name, Mitsui chemical Co., Ltd.).
Examples of the epoxy-based crosslinking agent (polyfunctional epoxy compound) include N, N, N ', N' -tetraglycidyl m-xylylenediamine, diglycidylaniline, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol anhydride polyglycidyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, Resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having 2 or more epoxy groups in the molecule. Examples of the epoxy-based crosslinking agent include commercially available products such as "TETRAD C" (manufactured by Mitsubishi gas chemical Co., Ltd.).
[ meth (acrylic) copolymer (B) >
The adhesive composition may further contain a (meth) acrylic copolymer (B) formed by polymerizing a composition (B) containing an alkyl (meth) acrylate in which an alkyl group of an alkyl ester portion is an alicyclic hydrocarbon group (component B1), from the viewpoint of further exhibiting the effects of the present invention. The number of the (meth) acrylic copolymers (B) may be only 1, or may be 2 or more.
The content of the (meth) acrylic copolymer (B) in the adhesive composition may be any appropriate content within a range not impairing the effects of the present invention. Such a content is preferably 0.01 to 30 parts by weight, more preferably 0.01 to 20 parts by weight, further preferably 0.01 to 10 parts by weight, and particularly preferably 0.01 to 5 parts by weight, based on the solid content (100 parts by weight) of the (meth) acrylic copolymer (a), from the viewpoint of further exhibiting the effects of the present invention.
The (meth) acrylic copolymer (B) is formed by polymerizing a composition (B) containing (component B1) an alkyl (meth) acrylate in which the alkyl group of the alkyl ester moiety is an alicyclic hydrocarbon group.
The number of (b1 components) may be only 1, or may be 2 or more.
Examples of the alkyl (meth) acrylate (component b1) in which the alkyl group of the alkyl ester portion is an alicyclic hydrocarbon group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentadienyl (meth) acrylate, and in view of further exhibiting the effects of the present invention, dicyclopentadienyl (meth) acrylate is preferable, and dicyclopentadienyl (meth) acrylate is more preferable.
From the viewpoint of further exhibiting the effects of the present invention, the content ratio of the alkyl (meth) acrylate (component B1) in which the alkyl group in the alkyl ester portion is an alicyclic hydrocarbon group is preferably 5% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, particularly preferably 30% by weight or more, and most preferably 30% by weight to 99.9% by weight, based on the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (B).
The composition (b) contains a copolymerizable monomer other than the component (b 1). The number of the copolymerizable monomer may be only 1, or may be 2 or more.
The composition (b) preferably contains, as a copolymerizable monomer, an alkyl (meth) acrylate having 1 to 3 carbon atoms in the alkyl group of the alkyl ester moiety (component b2) from the viewpoint of further exhibiting the effects of the present invention.
Examples of the alkyl (meth) acrylate (component b2) in which the number of carbon atoms in the alkyl group of the alkyl ester portion is 1 to 3 include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. In order to further exhibit the effects of the present invention, the alkyl (meth) acrylate in which the alkyl group as the alkyl ester portion has 1 to 3 carbon atoms is preferably methyl (meth) acrylate, and more preferably methyl methacrylate.
From the viewpoint of further exhibiting the effects of the present invention, the content ratio of the alkyl (meth) acrylate (component B2) in which the number of carbon atoms in the alkyl group of the alkyl ester moiety is 1 to 3 is preferably 10 to 90 wt%, more preferably 15 to 85 wt%, even more preferably 20 to 80 wt%, particularly preferably 25 to 75 wt%, and most preferably 30 to 70 wt%, relative to the total amount (100 wt%) of the monomer components constituting the (meth) acrylic copolymer (B).
Examples of the copolymerizable monomer other than the alkyl (meth) acrylate (component b2) in which the number of carbon atoms in the alkyl group of the alkyl ester moiety is 1 to 3 include carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and anhydrides thereof (for example, anhydride-containing monomers such as maleic anhydride and itaconic anhydride); (meth) acrylates having an OH group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like; amide group-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-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 glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; heterocyclic ring-containing vinyl monomers such as N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine and 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 cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth) acrylates having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentadienyl (meth) acrylate; aromatic hydrocarbon group-containing (meth) acrylates 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 vinyl toluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and the like.
As the copolymerizable monomer, a polyfunctional monomer may be used. The polyfunctional monomer is a monomer having 2 or more ethylenically unsaturated groups in 1 molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group may be employed within a range not impairing the effects of the present invention. Examples of such an ethylenically unsaturated group include a radical polymerizable functional group such as a vinyl group, an propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group). 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, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Such polyfunctional monomers may be 1 type or 2 or more types.
As the copolymerizable monomer, alkoxyalkyl (meth) acrylate may also be used. Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. The number of the alkoxyalkyl (meth) acrylates may be only 1, or may be 2 or more.
From the viewpoint that the effects of the present invention can be further exhibited, the composition (b) preferably contains a thiol as a chain transfer agent. Examples of the thiol include alkyl thioglycolates, specifically, methyl thioglycolate and ethyl thioglycolate.
The content of the chain transfer agent in the composition (b) may be any suitable content within a range not impairing the effects of the present invention. Such a content is preferably 0.01 to 25 parts by weight, more preferably 0.02 to 20 parts by weight, further preferably 0.05 to 15 parts by weight, and particularly preferably 0.1 to 15 parts by weight, based on the total amount (100 parts by weight) of the monomer components constituting the (meth) acrylic copolymer (B), from the viewpoint of further exhibiting the effects of the present invention.
The Tg of the (meth) acrylic copolymer (B) is preferably 50 to 250 ℃, more preferably 70 to 230 ℃, still more preferably 80 to 220 ℃, particularly preferably 90 to 210 ℃, and most preferably 100 to 200 ℃ in order to further exhibit the effects of the present invention.
The Tg of the (meth) acrylic copolymer (B) is a value obtained from the Fox equation based on the Tg of a homopolymer (homopolymer) of each monomer constituting the (meth) acrylic copolymer (B) and the weight fraction (copolymerization ratio on a weight basis) of the monomer. The Fox formula is a relational expression between Tg of a copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each monomer constituting the copolymer, as shown below.
1/Tg＝Σ(Wi/Tgi)
In the above Fox formula, Tg represents the glass transition temperature (unit: K) of a copolymer, Wi represents the weight fraction (copolymerization ratio on the weight basis) of the monomer i in the copolymer, and Tgi represents the glass transition temperature (unit: K) of a homopolymer of the monomer i. The Tg of the homopolymer is as described in the literature.
As the Tg of the homopolymer, for example, the following values can be specifically used.
175 ℃ of dicyclopentadienyl methacrylate
105 ℃ methyl methacrylate
For the Tg of the homopolymers other than those exemplified above, the values described in "Polymer Handbook" (3 rd edition, john wiley & Sons, inc., 1989) can be used. When a plurality of numerical values are described in the above "Polymer Handbook", the conventional values are used. For the monomers not described in the above "Polymer Handbook", catalog values of the monomer manufacturers were used. As the Tg of the homopolymer of the monomer which is not described in the above-mentioned "Polymer Handbook" and does not provide the catalog value of the monomer manufacturing company, a value obtained by the measurement method described in Japanese patent laid-open No. 2007-and-51271 was used.
The weight average molecular weight of the (meth) acrylic copolymer (B) is preferably 1000 to 30000, more preferably 1250 to 25000, still more preferably 1500 to 20000, particularly preferably 2000 to 15000, and most preferably 2000 to 10000, from the viewpoint of further exhibiting the effects of the present invention.
The composition (b) may contain any other suitable component within a range not impairing the effects of the present invention. Examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent. The content of these other components may be any suitable content within a range not impairing the effect of the present invention. As for details thereof, the description in the section of (meth) acrylic copolymer (A) > can be cited.
As a method for obtaining the (meth) acrylic copolymer (B), for example, various polymerization methods known as a method for synthesizing a (meth) acrylic copolymer, such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization, can be suitably used.
< Ionic liquid >
The adhesive composition may comprise an ionic liquid. By including the ionic liquid in the adhesive composition, an adhesive composition having very excellent antistatic properties can be provided. Such ionic liquids may be only 1 type, or may be 2 or more types.
In the present invention, the ionic liquid is a molten salt (ionic compound) that is in a liquid state at 25 ℃.
The ionic liquid is preferably an ionic liquid containing a fluoroorganic anion. The ionic liquid containing a fluoroorganic anion is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By using an ionic liquid composed of a fluorine organic anion and an onium cation as the ionic liquid, an adhesive composition having extremely excellent antistatic properties can be provided.
As the onium cation which can constitute the ionic liquid, any suitable onium cation may be used within a range not impairing the effects of the present invention. The onium cation is preferably at least 1 selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations. By selecting these onium cations, an adhesive composition extremely excellent in antistatic property can be provided.
The onium cation capable of constituting the ionic liquid is preferably at least 1 kind selected from cations having structures represented by general formulae (1) to (5).
Figure BDA0003188433480000251
In the general formula (1), Ra represents a C4-20 hydrocarbon group and may contain a hetero atom, and Rb and Rc may be the same or different and represent hydrogen or a C1-16 hydrocarbon group and may contain a hetero atom. In the case where the nitrogen atom contains a double bond, there is no Rc.
In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and Re, Rf and Rg may be the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and may contain a hetero atom.
In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and Ri, Rj and Rk are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and may contain a hetero atom.
In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, and Rl, Rm, Rn, and Ro are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms and may contain a hetero atom. Wherein, when Z is a sulfur atom, Ro is absent.
In the general formula (5), X represents a Li atom, a Na atom, or a K atom.
Examples of the cation represented by the general formula (1) include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, and the like.
Specific examples of the cation represented by the general formula (1) include pyridinium cations such as 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3, 4-dimethylpyridinium cation, and 1, 1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1-dipropylpyrrolidinium cation, 1-propylpyrrolidinium cation, 1-ethylpyrrolidinium cation, 1-propylpyrrolidinium cation, and mixtures thereof, Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1, 1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-ethyl-heptylpiperidinium cation, 1-pentylpiperidinium cation, 1-propylpiperidinium cation, 1-pentylpiperidinium cation, and the like, Piperidinium cations such as 1-propyl-1-butylpiperidinium cation, 1-dimethylpiperidinium cation, 1-dipropylpiperidinium cation and 1, 1-dibutylpiperidinium cation; 2-methyl-1-pyrroline cation; 1-ethyl-2-phenylindole cation; 1, 2-dimethylindole cation; a 1-ethyl carbazole cation; and the like.
Among these, from the viewpoint of further exhibiting the effect of the present invention, preferred examples include pyridinium cations such as 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, pyrrolidinium cations such as 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, piperidinium cations such as 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, and 1-propyl-1-butylpiperidinium cation; and the like, more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.
Examples of the cation represented by the general formula (2) include an imidazolium cation, a tetrahydropyrimidium cation, and a dihydropyrimidinium cation.
Specific examples of the cation represented by the general formula (2) include, for example, a1, 3-dimethylimidazolium cation, a1, 3-diethylimidazolium cation, a 1-ethyl-3-methylimidazolium cation, a 1-butyl-3-methylimidazolium cation, a 1-hexyl-3-methylimidazolium cation, a 1-octyl-3-methylimidazolium cation, a 1-decyl-3-methylimidazolium cation, a 1-dodecyl-3-methylimidazolium cation, a 1-tetradecyl-3-methylimidazolium cation, a1, 2-dimethyl-3-propylimidazolium cation, a 1-ethyl-2, 3-dimethylimidazolium cation, a, Imidazolium cations such as 1-butyl-2, 3-dimethylimidazolium cation and 1-hexyl-2, 3-dimethylimidazolium cation; tetrahydropyrimidinium cations such as 1, 3-dimethyl-1, 4,5, 6-tetrahydropyrimidinium cation, 1,2, 3-trimethyl-1, 4,5, 6-tetrahydropyrimidinium cation, 1,2,3, 4-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cation, 1,2,3, 5-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cation; dihydropyrimidinium cations such as 1, 3-dimethyl-1, 4-dihydropyrimidinium cation, 1, 3-dimethyl-1, 6-dihydropyrimidinium cation, 1,2, 3-trimethyl-1, 4-dihydropyrimidinium cation, 1,2, 3-trimethyl-1, 6-dihydropyrimidinium cation, 1,2,3, 4-tetramethyl-1, 4-dihydropyrimidinium cation, and 1,2,3, 4-tetramethyl-1, 6-dihydropyrimidinium cation; and the like.
Among these, from the viewpoint of further exhibiting the effect of the present invention, 1, 3-dimethylimidazolium cation, 1, 3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation are preferable, imidazolium cations such as 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, and 1-tetradecyl-3-methylimidazolium cation, and more preferably 1-ethyl-3-methylimidazolium cation and 1-hexyl-3-methylimidazolium cation.
Examples of the cation represented by the general formula (3) include pyrazolium (pyrazolium) cation, pyrazolinium (pyrazolinium) cation, and the like.
Specific examples of the cation represented by the general formula (3) include pyrazolium cations such as 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2, 3, 5-trimethylpyrazolium cation, 1-propyl-2, 3, 5-trimethylpyrazolium cation, and 1-butyl-2, 3, 5-trimethylpyrazolium cation; pyrazolinium cations such as 1-ethyl-2, 3, 5-trimethylpyrazolinium cation, 1-propyl-2, 3, 5-trimethylpyrazolinium cation, and 1-butyl-2, 3, 5-trimethylpyrazolinium cation; and the like.
Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a cation in which a part of the alkyl group is substituted with an alkenyl group, an alkoxy group, and an epoxy group.
Specific examples of the cation represented by the general formula (4) include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetrabutylphosphonium cation, tetrabutylammonium cation, tetrabutylphosphonium cation, tetramethylphosphonium cation, and the like, Tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and the like.
Among these, from the viewpoint of further exhibiting the effect of the present invention, preferable examples thereof include asymmetric tetraalkylammonium cations such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation and trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N-dimethyl-N-ethyl-N-propylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, and the like, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N-dimethyl-N-ethyl-N-hexylammonium cation, N-dimethyl-N-ethyl-N-heptylammonium cation, N-dimethyl-N-ethyl-N-nonylammonium cation, N-dimethyl-N, N-dipropylammonium cation, N-diethyl-N-propyl-N-butylammonium cation, N-dimethyl-N-propyl-N-pentylammonium cation, N-dimethyl-N-propyl-N-hexylammonium cation, N-dimethyl-N-propyl-N-heptylammonium cation, N-dimethyl-N-propyl-N-hexylammonium cation, N-heptyl ammonium cation, N-hexyl-propylammonium cation, N-propylhexyl-N-propylhexyl-phosphonium cation, N-propylheptyl-propylphosphonium cation, N-propylphosphonium cation, N-propylheptyl-propylphosphonium cation, N-propylphosphonium cation, or a salt of the corresponding salt, N, N-dimethyl-N-butyl-N-hexylammonium cation, N-diethyl-N-butyl-N-heptylammonium cation, N-dimethyl-N-pentyl-N-hexylammonium cation, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N-diethyl-N-methyl-N-propylammonium cation, N-diethyl-N-methyl-N-pentylammonium cation, N-diethyl-N-methyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, N-diethyl-N-pentyl-ammonium cation, N-diethyl-N-pentyl-N-hexylammonium cation, N-diethyl-N-hexylammonium cation, N-diethyl-butyl-N-heptylammonium cation, N-pentyl-ammonium cation, N-pentyl-cation, N-pentyl-cation, N-pentyl-cation, N-pentyl-alkyl-ammonium cation, N, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N-dipropyl-N-methyl-N-ethylammonium cation, N-dipropyl-N-methyl-N-pentylammonium cation, N-dipropyl-N-butyl-N-hexylammonium cation, N-dipropyl-N, N-dihexylammonium cation, N-dibutyl-N-methyl-N-pentylammonium cation, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and the like, more preferably the trimethyl propyl ammonium cation.
As the fluoroorganic anion that can constitute the ionic liquid, any suitable fluoroorganic anion can be used within a range that does not impair the effects of the present invention. Such fluoroorganic anions may be fully fluorinated (perfluorinated) or partially fluorinated.
Examples of such a fluorine organic anion include a fluorinated arylsulfonate, a perfluoroalkanesulfonate, a bis (fluorosulfonyl) imide, a bis (perfluoroalkanesulfonyl) imide, a cyano perfluoroalkanesulfonylamide, a bis (cyano) perfluoroalkanesulfonyl methide, a cyano-bis- (perfluoroalkanesulfonyl) methide, a tris (perfluoroalkanesulfonyl) methide, a trifluoroacetate, a perfluoroalkyl compound, a tris (perfluoroalkanesulfonyl) methide, and a (perfluoroalkanesulfonyl) trifluoroacetamide.
Among these fluorine organic anions, perfluoroalkyl sulfonate, bis (fluorosulfonyl) imide and bis (perfluoroalkanesulfonyl) imide are more preferable, and more specifically, trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis (fluorosulfonyl) imide and bis (trifluoromethanesulfonyl) imide are more preferable.
Specific examples of the ionic liquid may be suitably selected from combinations of the above-mentioned cationic components and the above-mentioned anionic components. Specific examples of such ionic liquids include 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethane sulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, and mixtures thereof, 1, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1, 1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, or, 1-Ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropane sulfonate, 1-ethyl-3-methylimidazolium nonafluorobutane sulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1, 2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N, N-propylammonium bis (trifluoromethanesulfonyl) imide, N, p, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-hexyl-ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-hexyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-propylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-propylammonium bis (trifluoromethanesulfonyl) imide), N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-amide, N-dimethylphosphonium bis (trifluoromethanesulfonyl) imide, N-amide, N-dimethylphosphonium chloride, N, p, n, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, N-methyl-amide, N-bis (pentafluoroethanesulfonyl) imide, N-methyl-N-methyl-amide, N-methyl-N-N-methyl-N-methyl-N-, Glycidyl trimethylammonium trifluoromethanesulfonate, glycidyl trimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyl trimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyl dimethylammonium bis (trifluoromethanesulfonyl) imide, diallyl dimethyl bis (pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, and the like.
Among these ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethane sulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, and the like, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, Lithium bis (fluorosulfonyl) imide.
The ionic liquid may be commercially available, or may be synthesized as described below. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and generally, a halide method, a hydroxide method, an acid ester method, a complexation method, a neutralization method, and the like, which are described in the literature "ionic liquid-first line and future of development" (published by CMC Group), can be used.
In the following, the halide method, the hydroxide method, the acid ester method, the complex method, and the neutralization method are exemplified by nitrogen-containing onium salts, and other ionic liquids such as other sulfur-containing onium salts and phosphorus-containing onium salts can be obtained by the same method.
The halide method is a method in which reactions such as those shown in reaction formulas (1) to (3) are performed. First, a tertiary amine is reacted with an alkyl halide to obtain a halide (reaction formula (1), and chlorine, bromine, or iodine can be used as a halogen).
The obtained halide is reacted with an acid (HA) or a salt (MA, M are cations forming a salt with a target anion such as ammonium, lithium, sodium, potassium) having an anion structure (A-) of the target ionic liquid to obtain a target ionic liquid (R)4NA)。
(1)R3N+RX→R4NX (X：Cl，Br，I)
(2)R4NX+HA→R4NA+HX
(3)R4NX+MA→R4NA+MX (M：NH4Li, Na, K, Ag, etc.)
The hydroxide method is a method performed by reactions shown in reaction formulas (4) to (8). First, a halide (R)4NX) is electrolyzed by an ion exchange membrane method (reaction formula (4)), an OH-type ion exchange resin method (reaction formula (5)), or with silver oxide (Ag)2O) (reaction formula (6)) to obtain a hydroxide (R)4NOH) (as halogen, chlorine, bromine, iodine were used).
The obtained hydroxide is subjected to the reaction of the reaction formulae (7) to (8) in the same manner as in the halogenation method described above, thereby obtaining the target ionic liquid (R)4NA)。
(4)R4NX+H2O→R4NOH+1/2H2+1/2X2 (X：Cl，Br，I)
(5)R4NX+P-OH→R4NOH + P-X (P-OH: OH type ion exchange resin)
(6)R4NX+1/2Ag2O+1/2H2O→R4NOH+AgX
(7)R4NOH+HA→R4NA+H2O
(8)R4NOH+MA→R4NA+MOH (M：NH4Li, Na, K, Ag, etc.)
The acid ester method is a method performed by reactions represented by reaction formulas (9) to (11). First, a tertiary amine (R)3N) with an acid ester to obtain an acid ester (reaction formula (9), and examples of the acid ester include esters of inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid, and esters of organic acids such as methanesulfonic acid, methylphosphonic acid, and formic acid).
The obtained acid ester compound is subjected to the reaction of the reaction formulae (10) to (11) in the same manner as in the halogenation method described above, thereby obtaining the target ionic liquid (R)4NA). Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as an acid ester, an ionic liquid can be obtained as it is.
(9)R3N+ROY→R4NOY
Figure BDA0003188433480000361
(10)R4NOY+HA→R4NA+HOY
Figure BDA0003188433480000362
(11)R4NOY+MA→R4NA+MOY (M：NH4Li, Na, K, Ag, etc.)
The neutralization method is a method performed by a reaction shown in reaction formula (12). Can be prepared by reacting a tertiary amine with CF3COOH、CF3SO3H、(CF3SO2)2NH、(CF3SO2)3CH、(C2F5SO2)2NH, etc.
(12)R3N+HZ→R3HN+Z-[HZ：CF3COOH，CF3SO3H，(CF3SO2)2NH，(CF3SO2)3CH，(C2F5SO2)2Organic acids such as NH]
R in the above reaction formulae (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom.
The content of the ionic liquid in the adhesive composition may be any suitable content within a range not impairing the effects of the present invention. Such a content is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, further preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight, based on the solid content (100 parts by weight) of the (meth) acrylic copolymer (a), from the viewpoint of further exhibiting the effects of the present invention. By adjusting the amount of the ionic liquid to be blended within the above range, an adhesive composition having very excellent antistatic properties can be provided. If the amount of the ionic liquid is less than 0.01 part by weight, sufficient antistatic properties may not be obtained. If the amount of the ionic liquid added exceeds 50 parts by weight, there is a concern that the adherend may be contaminated more.
< modified Silicone oil >
The adhesive composition may comprise a modified silicone oil. By including the modified silicone oil in the adhesive composition, the effect of antistatic properties can be further exhibited. In particular, the effect of antistatic properties can be more effectively exhibited by using the ionic liquid in combination.
The content of the modified silicone oil in the adhesive composition may be any appropriate content within a range not impairing the effects of the present invention. Such a content is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 40 parts by weight, further preferably 0.007 to 30 parts by weight, particularly preferably 0.008 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight, based on the solid content (100 parts by weight) of the (meth) acrylic copolymer (a), from the viewpoint of further exhibiting the effects of the present invention. By adjusting the content ratio of the modified silicone oil within the above range, the antistatic property can be more effectively exhibited.
As the modified silicone oil, any suitable modified silicone oil can be used within a range not impairing the effects of the present invention. Examples of such modified silicone oils include those available from shin-Etsu chemical industries, Ltd.
The modified silicone oil is preferably a polyether-modified silicone oil. By using the polyether-modified silicone oil, the antistatic property can be further effectively exhibited.
Examples of the polyether-modified silicone oil include a side chain type polyether-modified silicone oil and both terminal type polyether-modified silicone oil. Of these, both-end type polyether-modified silicone oils are preferable from the viewpoint of sufficiently exhibiting the effect of antistatic properties more effectively.
< other ingredients that can be contained in the adhesive composition >
The adhesive composition may contain any suitable other component within a range not impairing the effects of the present invention. Examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, and the like), anti-aging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, and the like), foils, ultraviolet absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, anticorrosion agents, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.
Substrate layer
The base material layer may be 1 layer only, or may be 2 or more layers. The substrate layer may be stretched.
The thickness of the substrate layer is preferably 1 to 500. mu.m, more preferably 5 to 400. mu.m, still more preferably 10 to 300. mu.m, and particularly preferably 15 to 200. mu.m.
For the purpose of forming a roll which is easy to unwind, for example, a surface of the substrate layer to which the pressure-sensitive adhesive layer is not attached may be subjected to a release treatment by adding a fatty acid amide, a polyethyleneimine, a long-chain alkyl additive, or the like to the substrate layer, or may be provided with a coating layer formed of any suitable release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent.
As the material of the base layer, any suitable material can be used depending on the application. Examples thereof include plastics, paper, metal films, and nonwoven fabrics. Preferably plastic. That is, the base material layer is preferably a plastic film. The base layer may be made of 1 kind of material, or may be made of 2 or more kinds of materials. For example, it may be made of 2 or more kinds of plastics.
Examples of the plastic include polyester resins, polyamide resins, and polyolefin resins. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin-based resin include homopolypropylene; propylene copolymers such as block, random and graft copolymers containing an ethylene component as a copolymer component; reactor TPO; low density, high density, linear low density, ultra low density, and other ethylene-based polymers; ethylene copolymers such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers; and the like.
The base layer may contain any suitable additive as required. Examples of additives that can be contained in the base layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, and pigments. The kind, number, and amount of the additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration and the like. From the viewpoint of improving weather resistance and the like, particularly preferred examples of the additives include an antioxidant, an ultraviolet absorber, a light stabilizer and a filler.
As the antioxidant, any suitable antioxidant can be used. Examples of such antioxidants include phenol antioxidants, phosphorus processing heat stabilizers, lactone processing heat stabilizers, sulfur heat stabilizers, and phenol/phosphorus antioxidants. The content ratio of the antioxidant is preferably 1 wt% or less, more preferably 0.5 wt% or less, and further preferably 0.01 wt% to 0.2 wt% with respect to the base resin of the base layer (when the base layer is a blend, the blend is the base resin).
As the ultraviolet absorber, any suitable ultraviolet absorber can be used. Examples of such an ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers. The content of the ultraviolet absorber is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 0.01% by weight to 0.5% by weight, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin).
As the light stabilizer, any suitable light stabilizer can be used. Examples of such a light stabilizer include a hindered amine light stabilizer and a benzoate light stabilizer. The content of the light stabilizer is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 0.01% by weight to 0.5% by weight, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin).
As the filler, any suitable filler can be used. Examples of such a filler include inorganic fillers. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 0.01% by weight to 10% by weight, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin).
Further, for the purpose of imparting antistatic properties, preferred examples of the additive include inorganic, low-molecular-weight and high-molecular-weight antistatic agents such as surfactants, inorganic salts, polyols, metal compounds and carbon. In particular, from the viewpoint of stain and maintenance of adhesiveness, a high molecular weight antistatic agent and carbon are preferable.
"uses" of
The surface protection film of the present invention has high adhesive force and high light peelability, and can suppress the generation of bubbles even when subjected to high-temperature high-pressure treatment such as autoclave after being attached to an adherend and thereafter returned to normal temperature and normal pressure. Therefore, the film can be suitably used for surface protection of an adherend for which the above-described performance is required of the surface protection film.
As such an adherend, an adherend having a surface water contact angle of 60 degrees or more is preferably cited. The water contact angle of the surface of such an adherend is preferably 65 degrees or more, more preferably 70 degrees or more, further preferably 75 degrees or more, and particularly preferably 80 degrees or more. An adherend having a surface water contact angle within the above range is likely to generate bubbles when subjected to a high-temperature high-pressure treatment using an autoclave or the like by being stuck with a conventional surface protective film and thereafter returned to normal temperature and pressure. When the surface protection film of the present invention is used, generation of bubbles can be suppressed even when the film is attached to an adherend having a surface water contact angle within the above range, and then the film is returned to normal temperature and normal pressure after high-temperature high-pressure treatment by an autoclave or the like.
Examples of such an adherend include unsaponifiable TAC (triacetylcellulose) films, barrier films usable for devices such as organic EL displays and OLEDs, and the like.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples at all. The test and evaluation methods in examples and the like are as follows. In the case of "part(s)", unless otherwise specified, it means "part(s) by weight", and in the case of "%" it means "% by weight", unless otherwise specified.
< measurement of weight average molecular weight >
The weight average molecular weight was measured by a Gel Permeation Chromatography (GPC) method. Specifically, the GPC measurement apparatus used was the product "HLC-8120 GPC" (manufactured by Tosoh corporation), and the measurement was performed under the following conditions, and the value was calculated from the standard polystyrene conversion value.
(conditions for measuring molecular weight)
Sample concentration: 0.2 wt% (tetrahydrofuran solution)
Sample injection amount: 10 μ L
Column: the trade name is "TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)" (manufactured by Tosoh Co., Ltd.)
Reference column: the trade name is "TSKgel SuperH-RC (1 root)" (manufactured by Tosoh corporation)
Eluent: tetrahydrofuran (THF)
Flow rate: 0.6 mL/min
The detector: differential Refractometer (RI)
Column temperature (measurement temperature): 40 deg.C
< measurement of pulse NMR of adhesive layer >
The pulse NMR was measured by the CPMG method. Specifically, the pulse NMR measurement apparatus used was a pulse NMR measurement apparatus having a trade name "TD-NMR thetiminepcmq 20" (manufactured by Brukar Co., Ltd.) under the following conditions.
(relaxation time measuring conditions)
The measurement method: CPMG method
90 ° pulse width: 2.1 mus
Repetition time: 1 second
Cumulative number of times: 64 times
Measurement temperature: 30 ℃ and 60 DEG C
Analysis method: non-linear least square method
< measurement of shear adhesion >
The surface protective film was cut into a size of 10mm in width and 100mm in length, and after the separator was peeled off, the adhesive (bonding) area of the exposed adhesive layer was 1cm2The sheet was attached to an unsaponifiable TAC polarizing plate (width: 70mm, length: 100mm, water contact angle: 69.9 degrees) obtained in production example 5 described later, left to stand in an environment of 23 ℃ X50% RH for 30 minutes, and then peeled off at a peeling speed of 0.06 mm/minute in the shear direction, and the maximum load (N/cm) at that time was measured2) As a shear adhesion.
< measurement of high-speed peeling force >
The surface protective film was cut into a size of 25mm in width and 100mm in length, and after peeling off the separator, the surface of an unsaponifiable TAC polarizing plate (70 mm in width, 100mm in length, and a water contact angle of 69.9 degrees) obtained in production example 5 described later was pressed with a hand pressure roller and then laminated under a pressure bonding condition of 0.25MPa and 0.3 m/min to prepare an evaluation sample. Subsequently, the separator on the polarizing plate side of the evaluation sample was peeled off, and was pressed against a glass plate having a thickness of 1.3mm, a width of 65mm and a length of 165mm by a hand pressure roller, and after leaving the film for 30 minutes in an environment of 23 ℃ C.. times.50% RH, one end portion of the surface protective film was peeled off at a peeling angle of 180 ℃ at a stretching speed of 30 m/min by a universal tensile testing machine, and the adhesive force at this time was measured. For the measurement, the measurement was performed under an atmosphere of 23 ℃ X50% RH.
< measurement of the number of blisters after high-temperature high-pressure treatment >
The surface protective film was cut into a size of 65mm in width and 90mm in length, the separator was peeled off, and then the surface of an adherend (70 mm in width and 100mm in length) was pressed by a hand press roll, and then laminated under a pressure bonding condition of 0.25MPa and 0.3 m/min, and 4 sides were cut from the surface protective film side by a cutter to 50mm in width and 80mm in length to obtain an evaluation sample. The separator on the polarizing plate side was peeled off, and was pressed against a piece of glass having a thickness of 1.3mm, a width of 65mm and a length of 165mm by a hand pressure roller, and after leaving the glass in an environment of 23 ℃ x 50% RH for 30 minutes, the glass was autoclave-treated at 50 ℃ and 5atm for 40 minutes, and then returned to normal temperature and pressure, and the number of bubbles generated at the end portion of the polarizing plate was counted as the number of bubbles generated.
As the adherend, the following adherend prepared in the production example described later was used.
Adherend (a): unsaponified TAC polarizer with adhesive layer (water contact angle 69.9 degree)
Adherend (B): anti-glare polarizing plate with adhesive layer (water contact angle 88.4 degree)
Adherend (C): saponified TAC polarizer with adhesive layer (Water contact Angle 53.1 degree)
< measurement of Water contact Angle >
Using DM-501, manufactured by Kyowa Kagaku K.K., ion-exchanged water was added dropwise in a volume of 2. mu.L using a syringe, and the measurement was carried out with a waiting time of 1000ms after the addition. The contact angle with water was measured at 5 points in the width direction at arbitrary plural locations on the adherend, and the average value was taken as the water contact angle with the adherend.
< measurement of swelling degree >
The swelling degree was measured by the following method. That is, about 0.1g of the polymer after the crosslinking reaction was taken out, wrapped in a porous tetrafluoroethylene sheet (trade name "NTF 1122", manufactured by Nindon electric Co., Ltd.) having an average pore diameter of 0.2 μm, and bound with kite string, and the weight at that time was measured and taken as the weight before impregnation (total weight of the polymer, the tetrafluoroethylene sheet and the kite string), and the total weight of the tetrafluoroethylene sheet and the kite string was measured in advance and taken as the bag weight. Next, the polymer was wrapped with a tetrafluoroethylene sheet and bound with kite string, the obtained object (referred to as "sample") was placed in a 50ml container filled with ethyl acetate, allowed to stand at 23 ℃ for 7 days, and thereafter, the ethyl acetate-impregnated sample was taken out of the container, ethyl acetate adhering to the sample was sufficiently wiped off with a waste cloth, and the weight was measured, and this weight was taken as the weight after impregnation, and further transferred to an aluminum cup, and dried in a dryer at 130 ℃ for 2 hours to remove ethyl acetate, and then the weight was measured, and this weight was taken as the weight after drying, and the swelling degree was calculated according to the following formula.
Degree of swelling (%) - (a-b)/(c-b) × 100(1)
In formula (1), a represents the weight after immersion, b represents the weight of the bag, and c represents the weight after drying.
In the case of using the crosslinked polymer, it may be used from the surface of the pressure-sensitive adhesive layer of the surface-protecting film, or it may be used by applying the same pressure-sensitive adhesive layer as that provided on the surface-protecting film to a silicone separator or the like and drying it.
[ production example 1 ]: production of acrylic copolymer (1)
2-ethylhexyl acrylate (2EHA) (Nippon Shokubai co., ltd.): 100 parts by weight of 4-hydroxybutyl acrylate (4HBA) (manufactured by Nippon Kasei Co., Ltd.): 10 parts by weight of Acrylic Acid (AA) (Nippon Shokubai co., ltd.): 0.02 part by weight of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.02 parts by weight, ethyl acetate: 180 parts by weight of an acrylic copolymer (1) having a weight-average molecular weight of 54 ten thousand was prepared as a solution (solid content: 35% by weight) by conducting polymerization for 6 hours while keeping the liquid temperature in the flask at about 65 ℃ by introducing nitrogen gas while gradually stirring.
[ production example 2 ]: production of acrylic copolymer (2)
2-ethylhexyl acrylate (2EHA) (Nippon Shokubai co., ltd.): 100 parts by weight of 2-hydroxyethyl acrylate (HEA) (manufactured by Toyo Synthesis Co., Ltd.): 4 parts by weight of 2, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.02 parts by weight, ethyl acetate: 180 parts by weight of an acrylic copolymer (2) having a weight-average molecular weight of 56 ten thousand was prepared in a solution (solid content: 35% by weight) by introducing nitrogen gas while gradually stirring and conducting polymerization for 6 hours while keeping the liquid temperature in the flask at about 65 ℃.
[ production example 3 ]: production of methacrylic copolymer (3)
100 parts by weight of toluene and dicyclopentadienyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi chemical Co., Ltd.) were put into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet, and a condenser: 60 parts by weight, Methyl Methacrylate (MMA) (manufactured by Mitsubishi gas chemical Co., Ltd.): 40 parts by weight and methyl thioglycolate as chain transfer agent: 3.5 parts by weight. Then, after stirring at 70 ℃ for 1 hour under a nitrogen atmosphere, 2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) was added as a polymerization initiator: 0.2 part by weight, a reaction was carried out at 70 ℃ for 2 hours, then at 80 ℃ for 4 hours, and then at 90 ℃ for 1 hour to prepare a methacrylic copolymer (3) solution (solid content: 60 wt%) having a weight average molecular weight of 4400 and a Tg of 144 ℃ (calculated according to the Fox equation).
[ production example 4 ]: production of acrylic pressure-sensitive adhesive composition (P1) for Forming pressure-sensitive adhesive for polarizing plate
(production of solution of acrylic Polymer (A1))
A 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser was charged with a solution containing Butyl Acrylate (BA): 94.9 parts by weight, Acrylic Acid (AA): 5 parts by weight, hydroxyethyl acrylate (HEA): 0.1 parts by weight of a monomer mixture. Further, with respect to the monomer mixture: 100 parts by weight of 2, 2' -Azobisisobutyronitrile (AIBN): 0.1 part by weight of a polymer was charged together with ethyl acetate, and nitrogen gas was introduced while stirring slowly to replace nitrogen gas, and then polymerization was carried out for 7 hours while keeping the liquid temperature in the flask at about 55 ℃. Then, ethyl acetate was added to the obtained reaction solution to prepare a solution of an acrylic polymer (a1) having a weight average molecular weight of 200 ten thousand adjusted to a solid content concentration of 20%.
(acrylic adhesive composition (P1))
An isocyanate-based crosslinking agent (trade name: CORONATE L, trimethylolpropane/toluene diisocyanate, Nippon Polyurethane Industry co., ltd.) was added to 100 parts by weight of the solid content of the obtained acrylic polymer (a1) solution: 0.6 part by weight of a silane coupling agent (trade name "KBM-403", manufactured by shin-Etsu chemical Co., Ltd.): 0.1 part by weight, an acrylic adhesive composition (P1) was prepared.
[ production example 5 ]: production of adherend (A)
(preparation of polarizing Member)
A polyvinyl alcohol film (KURARAAY CO., LTD: VF-PS7500, manufactured by LTD, width 1000mm) having a thickness of 75 μm was immersed in pure water at 30 ℃ for 60 seconds while being stretched to a stretching ratio of 2.5 times, dyed in an iodine aqueous solution at 30 ℃ at a weight ratio of pure water/iodine (I)/potassium iodide (KI) of 100/0.01/1 for 45 seconds, stretched in a 4 wt% boric acid aqueous solution at a stretching ratio of 5.8 times, immersed in pure water for 10 seconds, and then dried at 60 ℃ for 5 minutes while maintaining the film tension, to obtain a polarizer. The thickness of the polarizer was 25 μm, and the water content was 15% by weight.
(preparation of transparent protective film with adhesive layer)
A PVA resin (GOHSENOL, manufactured by Nippon synthetic chemical industries Co., Ltd.): 100 parts by weight of a crosslinking agent (WATERSOL, manufactured by Dainippon ink chemical Co., Ltd.): 35 parts by weight of a solvent dissolved in pure water: 3760 parts by weight of a binder. This adhesive was applied to one side of a 60 μm thick cellulose Triacetate (TAC) film (TD-60 UL, manufactured by Fujifilm Co.) using a slit die (slot die), and then dried at 85 ℃ for 1 minute to obtain an adhesive layer-attached TAC film having an adhesive layer with a thickness of 0.1 μm.
(production of polarizing plate (A))
The polarizing plate (a) was produced by the method shown in fig. 2. As the polarizing element, the above-mentioned polarizing element was used, and as the 1 st transparent protective film B1, the above-mentioned unsaponifiable TAC film with an adhesive layer was used. The same procedure as for the adhesive layer-equipped TAC film was carried out except that an adhesive layer-equipped acrylic film was used as the 2 nd transparent protective film B2, and an acrylic film having a thickness of 40 μm was used instead of the TAC film. As shown in fig. 2, the TAC film with an adhesive layer (1 st transparent protective film B1) was fed from the 1 st roll R1 side, and the acrylic film with an adhesive layer (2 nd transparent protective film B2) was fed from the 2 nd roll R2 side. As the 1 st roll R1 and the 2 nd roll R2, iron rolls having a diameter of 200mm were used. The transport speed of each film was 20 m/min. The obtained polarizing plate (a) was dried at 80 ℃ for 2 minutes after lamination.
(production of adherend (A))
The acrylic pressure-sensitive adhesive composition (P1) obtained in production example 4 was uniformly applied to the surface of a 38 μm thick polyethylene terephthalate film (separator) treated with a silicone release agent by a spray column coater, and dried in an air circulation type constant temperature oven at 155 ℃ for 2 minutes to prepare a pressure-sensitive adhesive layer having a thickness of 20 μm. Next, the 2 nd transparent protective film surface of the polarizing plate (a) was subjected to corona treatment, and the separator having the pressure-sensitive adhesive layer formed thereon was bonded to the corona-treated surface to produce an unsaponifiable TAC polarizing plate with a pressure-sensitive adhesive layer as an adherend (a). The water contact angle of the unsaponifiable TAC polarizing plate with the adhesive layer was 69.9 degrees.
[ production example 6 ]: production of adherend (B)
(preparation of aqueous Binder solution)
A polyvinyl alcohol resin containing an acetoacetyl group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetyl group modification degree: 5 mol%): 100 parts by weight of methylol melamine: 50 parts by weight of the aqueous solution was dissolved in pure water at 30 ℃ to prepare an aqueous solution adjusted to have a solid content concentration of 3.7% by weight. Relative to the aqueous solution: 100 parts by weight of an alumina colloidal aqueous solution (average particle diameter: 15nm, solid content concentration: 10% by weight, positive charge): 18 parts by weight of an aqueous binder solution was prepared. The viscosity of the aqueous adhesive solution is 9.6 mPas, and the pH is in the range of 4-4.5.
(production of polarizing plate with surface treatment)
In the case of a composition containing a urethane acrylate monomer of ultraviolet curing type: 100 parts by weight of a benzophenone-based photopolymerization initiator: to 3 parts by weight of the ultraviolet-curable resin composition, silica particles having an average particle diameter of 0.5 μm: 15 parts by weight of silica particles having an average particle diameter of 1.4 μm: 10 parts by weight, a resin mixture was obtained. To the obtained resin mixture, a viscosity adjusting solvent was further added to obtain a solid content concentration of 50% by weight, and then the mixture was mixed with a high-speed mixer. The obtained mixture was applied to the 1 st transparent protective film B1(TAC film) side of the polarizing plate (a) produced in production example 5 using a bar coater, and after the solvent was evaporated, ultraviolet light was irradiated thereto to perform curing treatment, thereby obtaining an antiglare polarizing plate (B) having a fine uneven surface structure and containing an ultraviolet-curable resin film having a thickness of 7 μm.
(production of adherend (B))
An anti-glare polarizing plate with a pressure-sensitive adhesive layer was obtained as an adherend (B) in the same manner as in production example 5, except that the anti-glare polarizing plate (B) was used instead of the polarizing plate (a). The water contact angle of the anti-glare polarizing plate with an adhesive layer was 88.4 degrees.
[ production example 7 ]: production of adherend (C)
As the base film, a polyvinyl alcohol film (average polymerization degree 2400, KURAAY CO., LTD VF-PE-A #6000) having a thickness of 60 μm was used. The polyvinyl alcohol film was subjected to the following steps in the following order.
(swelling step)
The swelling step was carried out by 2 swelling baths in the manner shown in fig. 3. As the treatment liquid for each swelling bath, pure water was used. As the guide roll 13 provided in the swelling bath in stage 1 in FIG. 3, a tenter roll having a curvature radius of 2000mm was used. The spreader roll was disposed at a position where the polyvinyl alcohol film was immersed in 80% of the length of the treatment liquid (the length of the dotted line between p1 and p2 in fig. 3). It should be noted that other guide rolls use flat press rolls.
< stage 1 >
The polyvinyl alcohol film was transferred to the swelling bath in stage 1, and immersed in pure water adjusted to 40 ° for 60 seconds, and uniaxially stretched to a stretch ratio of 1.80 times while swelling.
< stage 2 >
Next, the polyvinyl alcohol film subjected to the swelling step in the 1 st stage was transferred to a swelling bath in the 2 nd stage, and was uniaxially stretched to a stretch ratio of 1.10 (total stretch ratio of 1.98 times) while being swollen by immersing the film in pure water adjusted to 30 ℃ for 60 seconds.
(dyeing step)
As the treatment liquid of the dyeing bath, iodine: iodine staining solution with concentration of 0.3 wt% of potassium iodide (weight ratio ═ 0.5: 8). The polyvinyl alcohol film subjected to the swelling treatment was transferred to a dyeing bath, dipped in the iodine dyeing solution adjusted to 30 ℃ for 60 seconds, stretched in one direction to a total stretching ratio of 3 times the original length, and dyed.
(crosslinking step)
As a treatment liquid of the crosslinking bath, an aqueous boric acid solution containing 3 wt% of boric acid and 3 wt% of potassium iodide was used. The polyvinyl alcohol film thus treated was transferred to a crosslinking bath, and while being immersed in the aqueous boric acid solution adjusted to 30 ℃ for 19 seconds, it was uniaxially stretched to 4 times the total elongation relative to the original length.
(stretching Process)
As a treatment liquid of the stretching bath, an aqueous solution of boric acid containing 4 wt% of boric acid and 5 wt% of potassium iodide was used. The polyvinyl alcohol film thus treated was transferred to a stretching bath, and while being immersed in an aqueous boric acid solution adjusted to 60 ℃ for 13 seconds, it was uniaxially stretched to 6 times the total stretching ratio with respect to the original length.
(cleaning Process)
As a treatment liquid for a cleaning bath, an aqueous solution containing 3 wt% of potassium iodide was used. The polyvinyl alcohol film thus treated was transferred to a cleaning bath, and immersed in the aqueous solution adjusted to 30 ℃ for 10 seconds.
(drying Process)
Subsequently, the polyvinyl alcohol film thus treated was dried in an oven at 60 ℃ for 4 minutes to obtain a polarizing plate.
(production of adherend (C))
A saponification-treated triacetylcellulose film having a thickness of 80 μm was laminated on both sides of the polarizer obtained above with an adhesive containing a 5 wt% completely saponified polyvinyl alcohol aqueous solution, and the laminate was bonded to each other with a calender roll, and then dried at 70 ℃ for 4 minutes. Subsequently, a saponified TAC polarizing plate with a pressure-sensitive adhesive layer was obtained as an adherend (C) in the same manner as in production example 5, except that the saponified TAC polarizing plate (C) was used instead of the polarizing plate (a). The water contact angle of the saponified TAC polarizer with an adhesive layer was 53.1 degrees.
[ example 1 ]: adhesive composition (1) and production of surface-protecting film (1)
To the solution of the acrylic copolymer (1) obtained in production example 1, a solution prepared by diluting an organosiloxane having an oxyalkylene chain (KF-353, manufactured by shin-Etsu chemical Co., Ltd.) as an organosilicon component with ethyl acetate to 10 wt% was added based on 100 parts by weight of the solid content: 2 parts by weight (0.2 parts by weight in terms of solid content) of lithium bis (trifluoromethanesulfonyl) imide (LiN (CF) as an antistatic agent, i.e., an alkali metal salt (ionic compound)3SO2)2: LiTFSI, manufactured by tokyo chemical industries co: 0.15 part by weight of an isocyanate crosslinking agent (trade name "CORONATE HX", manufactured by Tosoh corporation): 3.4 parts by weight of a crosslinking catalyst
Figure BDA0003188433480000501
0.006 part, EMBILIZER OL-1(Tokyo Fine Chemical CO., LTD.): 0.01 part by weight, based on solid content, of a solution of the methacrylic copolymer (2) obtained in production example 2, and further, based on propylene obtained in production example 1The polyoxyalkylene glycol compound (SANNIX GP-250, manufactured by Sanyo chemical Co., Ltd.) was added so that the solid content of the solution of the olefinic acid copolymer (1) became 1 part by weight per 100 parts by weight of the solid content, and the mixture was diluted with toluene so that the solid content of the whole became 20% by weight, and stirred with a dispersing machine to obtain the adhesive composition (1).
The obtained adhesive composition (1) was applied to a polyester resin-containing substrate "lumiror S10" (thickness 38 μm, manufactured by Toray Industries, inc.) by a spray column coater so that the thickness after drying became 10 μm, cured at a drying temperature of 130 ℃ for a drying time of 20 seconds, and dried. In this manner, an adhesive layer is formed on the substrate. Next, the silicone-treated surface of the substrate made of a polyester resin having a thickness of 19 μm, one surface of which was subjected to silicone treatment, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (1).
The results are shown in Table 1.
[ example 2 ]: adhesive composition (2) and production of surface-protecting film (2)
An adhesive composition (2) and a surface protective film (2) were obtained in the same manner as in example 1, except that the amount of CORONATE HX was changed to 8.1 parts by weight in terms of solid content and the amount of GP250 was changed to 3 parts by weight.
The results are shown in Table 1.
[ example 3 ]: adhesive composition (3) and production of surface-protecting film (3)
An adhesive composition (3) and a surface protective film (3) were obtained in the same manner as in example 1, except that the amount of CORONATE HX was changed to 12.8 parts by weight in terms of solid content and the amount of GP250 was changed to 5 parts by weight.
The results are shown in Table 1.
[ example 4 ]: adhesive composition (4) and production of surface-protecting film (4)
The amount of CORONATE HX was changed to 1.7 parts by weight in terms of solid content, GP250 was changed to GP600 (manufactured by sanyo chemical industries, polyoxypropylene glycerol ether, Mn: 600): an adhesive composition (4) and a surface protection film (4) were obtained in the same manner as in example 1, except that the amount of the adhesive composition was changed to 1 part by weight.
The results are shown in Table 1.
[ example 5 ]: adhesive composition (5) and production of surface-protecting film (5)
The amount of CORONATE HX was changed to 1.6 parts by weight in terms of solid content, GP250 was changed to GP1000 (manufactured by sanyo chemical industries, polyoxypropylene glycerol ether, Mn: 1000): an adhesive composition (5) and a surface protection film (5) were obtained in the same manner as in example 1 except that the amount of the adhesive composition was changed to 1 part by weight.
The results are shown in Table 1.
[ example 6 ]: adhesive composition (6) and production of surface-protecting film (6)
Changing the amount of CORONATE HX to 3.6 parts by weight in terms of solid content, changing GP250 to Adeka polyester EDP-300 (N, N', -tetrakis (2-hydroxypropyl) ethylenediamine, Mn 300): 1 part by weight of a crosslinking catalyst in place of EMBILIZER OL-1
Figure BDA0003188433480000522
An adhesive composition (6) and a surface-protecting film (6) were obtained in the same manner as in example 1, except that 0.01 part by weight of Zinc acetylacetonate monohydrate (manufactured by japan chemical industry co., ltd.) was used.
The results are shown in Table 1.
[ example 7 ]: production of pressure-sensitive adhesive composition (7) and surface-protecting film (7) As polyol (A), PREMINOL S3011 (manufactured by Asahi glass Co., Ltd., Mn: 10000) which is a polyol having 3 OH groups was used: 85 parts by weight of SANNIX GP-3000 (manufactured by Sanyo chemical Co., Ltd., Mn 3000) as a polyol having 3 OH groups: 13 parts by weight of SANNIX GP-1000 (manufactured by sanyo chemical co., ltd., Mn 1000) as a polyol having 3 OH groups: 2 parts by weight of a polyfunctional isocyanate compound (B) used was CORONATE HX (Nippon Polyurethane Industry co., Ltd.): 13.5 parts by weight of a catalyst (Japanese chemical Co., Ltd.)Trade name manufactured by industrial co:
Figure BDA0003188433480000521
): 0.04 parts by weight of ethyl acetate as a diluting solvent: 210 parts by weight, was stirred with a disperser to obtain adhesive composition (7).
The obtained adhesive composition (7) was applied to a polyester resin substrate "lumiror S10" (thickness 38 μm, manufactured by Toray Industries, inc.) by a spray column coater so that the thickness after drying became 10 μm, and cured and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 2 minutes. In this manner, an adhesive layer is formed on the substrate. Then, the silicone-treated surface of the substrate made of a polyester resin having a thickness of 19 μm, one surface of which was subjected to silicone treatment, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (7).
The results are shown in Table 1.
[ comparative example 1 ]: production of adhesive composition (C1) and surface protective film (C1)
The solution of the acrylic copolymer (1) obtained in production example 1 was diluted with ethyl acetate to 20% by weight, and to 500 parts by weight (100 parts by weight in terms of solid content) of the solution was added a solution prepared by diluting an organosiloxane (KF-353, manufactured by shin-Etsu chemical Co., Ltd.) having an oxyalkylene chain as an organosilicon component with ethyl acetate to 10% by weight: 2 parts by weight (0.2 parts by weight in terms of solid content) of lithium bis (trifluoromethanesulfonyl) imide (LiN (CF) as an antistatic agent, i.e., an alkali metal salt (ionic compound)3SO2)2: LiTFSI, manufactured by tokyo chemical industries co: 0.15 parts by weight, 3.5 parts by weight of an isocyanate crosslinking agent (trade name "CORONATE HX", manufactured by Tokyo co., ltd.), 0.02 parts by weight of EMBILIZER OL-1(Tokyo Fine Chemical co., ltd.) as a crosslinking catalyst, and 0.5 parts by weight of a solution of the methacrylic copolymer (2) obtained in production example 2 as a solid content were diluted with toluene so that the solid content of the whole became 20% by weight, and the mixture was stirred with a disperser to obtain an adhesive composition (C1).
The obtained adhesive composition (C1) was applied to a polyester resin-made substrate "lumiror S10" (thickness 38 μm, manufactured by Toray Industries, inc.) by a spray column coater so that the dried thickness became 15 μm, and cured and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 20 seconds. In this manner, an adhesive layer is formed on the substrate. Next, the silicone-treated surface of the substrate made of a polyester resin having a thickness of 19 μm, one surface of which was subjected to silicone treatment, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (C1).
The results are shown in Table 1.
[ comparative example 2 ]: production of adhesive composition (C2) and surface protective film (C2)
A solution of the acrylic copolymer (2) obtained in production example 2 was diluted with ethyl acetate to 20% by weight, and 100 parts by weight of the solution was added with a 10% by weight solution of an organosiloxane (trade name: KF6004, manufactured by shin-Etsu chemical Co., Ltd.) having a polyoxyalkylene chain in its main chain, diluted with ethyl acetate: 0.8 part by weight of a 10% by weight solution of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo chemical Co., Ltd.) diluted with ethyl acetate: 0.2 part by weight, isocyanate crosslinking agent (trade name: CORONATE L, manufactured by Tosoh corporation, 75% by weight): 0.8 part by weight of EMBILIZER OL-1(Tokyo Fine Chemical CO., LTD.): 0.02 part by weight, was diluted with toluene so that the total solid content became 20% by weight, and stirred with a disperser, to obtain a pressure-sensitive adhesive composition (C2).
The obtained adhesive composition (C2) was applied to a polyester resin-made substrate "lumiror S10" (thickness 38 μm, manufactured by Toray Industries, inc.) by a spray column coater so that the dried thickness became 10 μm, and cured and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 20 seconds. In this manner, an adhesive layer is formed on the substrate. Next, the silicone-treated surface of the substrate made of a polyester resin having a thickness of 19 μm, one surface of which was subjected to silicone treatment, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface-protecting film (C2).
The results are shown in Table 1.
[ Table 1]
Figure BDA0003188433480000551
Industrial applicability
The surface protective film of the present invention can be used for any suitable purpose. The surface protective film of the present invention is preferably used in the fields of optical members and electronic members.
Description of the reference numerals
1 base material layer
2 adhesive layer
10 surface protective film
A polarizing piece
B1 transparent 1. sup. st protective film
B2 transparent 2 th protective film
R1 roll No. 1
R2 roll No. 2
M-angle changing means

Claims (16)

1. A surface protective film comprising an adhesive layer and a substrate layer,
when the free induction decay signal obtained by pulse NMR measurement of the pressure-sensitive adhesive layer is separated into 2 components by the nonlinear least squares method, the component with a short relaxation time is a hard component (S), the component with a long relaxation time is a soft component (L), and the spin-spin relaxation time T2(L) of the proton of the soft component (L) measured at 30 ℃ is determined30With the spin-spin relaxation time T2(L) of the protons of the soft component (L) measured at 60 DEG C60Ratio of (A) T2(L)60/T2(L)30Is 2.15 to 3.05,
the surface protective film had a shear adhesion of 10N/cm2In the above-mentioned manner,
the surface protective film has a high-speed peeling force of 0.8N/25mm or less.
2. The surface protection film according to claim 1, wherein the adhesive layer has a thickness of 1 μm to 500 μm.
3. The surface protection film according to claim 1 or 2, wherein the thickness of the base material layer is 1 μm to 500 μm.
4. The surface protection film according to any one of claims 1 to 3, wherein the adhesive layer is constituted by an adhesive formed by an adhesive composition comprising: a (meth) acrylic copolymer (A), a polyfunctional alcohol (C), and a crosslinking agent (D).
5. The surface protection film according to claim 4, wherein the (meth) acrylic copolymer (A) is formed by polymerization from a composition (a) comprising: alkyl (meth) acrylate in which the alkyl group of the alkyl ester part (component a1) has 4 to 12 carbon atoms, and (meth) acrylate having an OH group (component a 2).
6. The surface protection film according to claim 5, wherein the composition (a) comprises (meth) acrylic acid.
7. The surface-protective film according to any one of claims 4 to 6, wherein the number of functional groups of the polyfunctional alcohol (C) is 3 to 6.
8. The surface-protective film according to any one of claims 4 to 7, wherein the polyfunctional alcohol (C) has a number average molecular weight of 50 to 10000.
9. The surface protection film according to any one of claims 4 to 8, wherein the adhesive composition comprises a (meth) acrylic copolymer (B) formed by polymerization from a composition (B) comprising (B1 component) an alkyl (meth) acrylate in which an alkyl group of an alkyl ester moiety is an alicyclic hydrocarbon group.
10. The surface protection film according to claim 9, wherein the composition (b) comprises (b2 component) an alkyl (meth) acrylate in which an alkyl group of the alkyl ester moiety has 1 to 3 carbon atoms.
11. The surface protective film according to claim 9 or 10, wherein the composition (b) comprises thiol.
12. The surface protection film according to any one of claims 9 to 11, wherein the Tg of the (meth) acrylic copolymer (B) is 50 to 250 ℃.
13. The surface protection film according to any one of claims 9 to 12, wherein the (meth) acrylic copolymer (B) has a weight average molecular weight of 1000 to 30000.
14. The surface protection film according to any one of claims 4 to 13, wherein the adhesive composition comprises an ionic liquid.
15. The surface protection film according to any one of claims 1 to 14, wherein the number of bubbles generated after the high-temperature high-pressure treatment is 10 or less.
16. The surface protection film according to claim 15, which is used for protecting a surface of an adherend, the surface having a water contact angle of 60 degrees or more.
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