CN113382859B - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
CN113382859B
CN113382859B CN202080012087.8A CN202080012087A CN113382859B CN 113382859 B CN113382859 B CN 113382859B CN 202080012087 A CN202080012087 A CN 202080012087A CN 113382859 B CN113382859 B CN 113382859B
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meth
cation
weight
acrylate
imide
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CN113382859A (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]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a surface protective film which has high adhesion and high light peelability and can suppress the generation of bubbles even when the film is applied to an adherend (preferably an adherend having a surface with a water contact angle of a certain level or more) and then subjected to high-temperature high-pressure treatment by an autoclave or the like and thereafter returned to normal temperature and normal pressure. The surface protective film of the present invention comprises an adhesive layer and a base material layer, wherein when the free induction decay signal of the adhesive layer obtained by pulse NMR measurement is separated into 2 components by a nonlinear least square method, the component with short relaxation time is set as a hard component (S), the component with long relaxation time is set as a soft component (L), and the spin-spin relaxation time T2 (L) of protons of the soft component (L) measured at 30 DEG C 30 Spin-spin relaxation time T2 (L) of proton with soft component (L) measured at 60 DEG C 60 Ratio T2 (L) 60 /T2(L) 30 Is 2.15 to 305, the shear adhesion of the surface protective film was 10N/cm 2 The high-speed peeling force of the surface protection film is 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 the optical member and the electronic member, a surface protective film is usually attached to the exposed surface in order to prevent damage to the surface during processing, assembling, inspection, transportation, and the like. Such a surface protective film is peeled off from the optical member or the electronic member at a time when surface protection is not necessary (patent document 1).
In order to press-bond the surface protective film to the adherend after the application, high-temperature and high-pressure treatment using an autoclave or the like may be performed. After such high-temperature and high-pressure treatment, the temperature needs to be returned to normal temperature and normal pressure.
However, the conventional surface protective film has the following problems: when the pressure-sensitive adhesive is applied to an adherend and then subjected to a high-temperature high-pressure treatment and thereafter returned to normal temperature and normal pressure, bubbles are easily generated. Particularly, a surface protective film designed in such a manner that an adhesive becomes hard in consideration of application in applications requiring light peelability has the following problems: fine bubbles (typically, bubbles having a diameter of about several millimeters) are likely to be generated due to foreign matter, rough processed end portions (burrs), and the like.
Therefore, surface protective films capable of eliminating such problems have been proposed so far (patent documents 2 and 3).
The surface protective film described in patent document 2 has a problem that it is heavy in peeling and cannot be applied to applications requiring light peelability.
The surface protective film for polarizing plate described in patent document 3 is aimed at preventing tunnel-like floating, and is insufficient in light peelability.
In particular, in the case of the application of an adherend in which the surface protective film is attached to the surface with a water contact angle of a certain level or more, the problem of the generation of bubbles is remarkably observed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-17109
Patent document 2: japanese patent laid-open No. 11-961
Patent document 3: japanese patent laid-open No. 2007-304117
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide a surface protective film which has high adhesion and high light peelability and can suppress the generation of bubbles even when the film is applied to an adherend (preferably an adherend having a surface with a water contact angle of a certain level or more) and then subjected to high-temperature high-pressure treatment by an autoclave or the like and thereafter returned to normal temperature and normal pressure.
Solution for solving the problem
The surface protective film of the present invention comprises an adhesive layer and a base material layer,
when the free induction decay signal of the adhesive layer obtained by pulse NMR measurement is separated into 2 components by nonlinear least square method, the component with short relaxation time is set as hard component (S), the component with long relaxation time is set as soft component (L), and spin-spin relaxation time T2 (L) of proton of soft component (L) measured at 30deg.C 30 Spin-spin relaxation time T2 (L) of proton with soft component (L) measured at 60 DEG C 60 Ratio T2 (L) 60 /T2(L) 30 Is 2.15 to 3.05 percent,
The shear adhesion of the surface protection film is 10N/cm 2 The above-mentioned steps are carried out,
the high-speed peeling force of the surface protection film is below 0.8N/25 mm.
In one embodiment, the thickness of the adhesive layer is 1 μm to 500 μm.
In one embodiment, the thickness of the base material 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: (a 1) an alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (a 2) a (meth) acrylate having an OH group.
In one embodiment, the composition (a) contains (meth) acrylic acid.
In one embodiment, the polyfunctional alcohol (C) has a functional group number of 3 to 6.
In one embodiment, the polyfunctional alcohol (C) has a number average molecular weight of 50 to 10000.
In one embodiment, the adhesive composition contains a (meth) acrylic copolymer (B) formed by polymerization of a composition (B) containing an alkyl (meth) acrylate in which the alkyl group of the (B1) alkyl ester moiety is an alicyclic hydrocarbon group.
In one embodiment, the composition (b) contains an alkyl (meth) acrylate having 1 to 3 carbon atoms in the alkyl group of the (b 2) alkyl ester moiety.
In one embodiment, the composition (b) comprises a thiol.
In one embodiment, the (meth) acrylic copolymer (B) has a Tg of 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 protective film of the present invention has a bubble generation number of 10 or less after high-temperature high-pressure treatment.
In one embodiment, the surface protection film of the present invention is used for protecting the 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 protective film having high adhesion and high light peelability, which can suppress the generation of bubbles even if the 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 with a 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 a surface protective film of the present invention.
Fig. 2 is a schematic cross-sectional view showing a method for manufacturing the polarizing plate (a) used for the adherend (a).
Fig. 3 is a schematic cross-sectional view showing a method for manufacturing a polarizing material used for the adherend (C).
Detailed Description
In the present specification, when the expression "weight" is present, the expression "mass" used as SI-based units representing weight may be replaced with "mass" used as usual.
In the present specification, the expression "acrylic acid" means "acrylic acid and/or methacrylic acid", the expression "acrylic acid ester and/or methacrylic acid ester", the expression "allyl (meth) group", the expression "allyl (meth) and/or methallyl", and the expression "acrolein and/or methacrolein".
Surface protective film
The surface protective film of the present invention comprises an adhesive layer and a substrate layer.
The surface protective film of the present invention may have any other suitable member within a range that does not impair the effects of the present invention, as long as the film has an adhesive layer and a base material layer. Typically, the surface protective film of the present invention is formed of a substrate 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, a surface protective film 10 includes a base material layer 1 and an adhesive layer 2. In fig. 1, a base material layer 1 and an adhesive layer 2 are directly laminated.
In fig. 1, the pressure-sensitive adhesive layer 2 may be provided with any suitable release liner (not shown) on the surface opposite to the base layer 1 for protection or the like until use. Examples of the release liner include a release liner in which the surface of a substrate (liner substrate) such as paper or plastic film is subjected to silicone treatment; and release liners in which the surfaces of substrates (liner substrates) such as paper and plastic films are laminated with a polyolefin resin. Examples of the plastic film as the backing material include polyethylene film, polypropylene film, polybutylene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene-vinyl acetate copolymer film. As the plastic film as the backing substrate, a polyethylene film is preferable.
The thickness of the release liner is preferably 1 μm to 500. Mu.m, more preferably 3 μm to 450. Mu.m, still more preferably 5 μm to 400. Mu.m, particularly preferably 10 μm to 300. Mu.m.
The thickness of the surface protective 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, and most preferably 30 μm to 250. Mu.m.
The surface protective film of the present invention was cut into a size of 10mm in width and 100mm in length, and the separator was peeled off to give an adhesive (bonding) area of 1cm in the exposed adhesive layer 2 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) bonded to the surface, and was allowed to stand still in an environment of 23 ℃ x 50% rhAfter 30 minutes, the sheet was peeled off at a peeling speed of 0.06 mm/min in the shearing direction, and the maximum load (N/cm) 2 ) As the shear adhesion, the shear adhesion measured under the above conditions is preferably 10N/cm 2 Above, more preferably 10N/cm 2 ～80N/cm 2 More preferably 10N/cm 2 ～50N/cm 2 Particularly preferably 15N/cm 2 ～45N/cm 2 Most preferably 20N/cm 2 ～40N/cm 2 . 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 was prepared by cutting the surface protective film into dimensions of 25mm in width and 100mm in length, peeling the separator, pressing the separator with a hand press roll against the surface of an adherend having a water contact angle of 60 degrees or more (for example, an unsaponifiable TAC polarizing plate (70 mm in width, 100mm in length, water contact angle=69.9 degrees) obtained in production example 5 described later), laminating the separator under a pressure condition of 0.25MPa and 0.3 m/min, peeling the separator on the polarizing plate side of the sample, pressing the separator with a hand press roll against a carrier glass having a thickness of 1.3mm, 65mm in width and 165mm in length for 30 minutes under an environment of 23 ℃ x 50% rh, peeling one end portion of the surface protective film with a universal tensile tester at a peeling rate of 30 m/min and 180 ° in which the adhesive force measured under the above conditions is preferably 10N/25mm or less, more preferably 0.01N/25mm to 25mm, most preferably 0.01N/25mm and 25mm more preferably 0.25 mm to 25mm. When the high-speed peeling force is within the above range, the surface protective film of the present invention can exhibit high light peelability.
The surface protective film of the present invention was obtained by cutting the surface protective film into a size of 65mm in width and 90mm in length, peeling the separator, pressing the separator with a press roll against the surface of an adherend having a water contact angle of 60 degrees or more (for example, an unsaponifiable TAC polarizing plate (70 mm in width, 100mm in length, water contact angle=69.9 degrees) obtained in production example 5 described later), laminating the resultant sheet under a pressing condition of 0.25MPa and 0.3 m/min, cutting the 4-sided sheet from the surface protective film side with a cutter to obtain a glass carrier having a width of 50mm and a length of 80mm, peeling the separator on the polarizing plate side, pressing the separator with a press roll against a glass carrier having a thickness of 1.3mm, a width of 65mm, and a length of 165mm with a press roll, placing the separator under an environment of 23 ℃ x 50% rh for 30 minutes, then performing autoclave treatment under an environment of 50 ℃ and 5atm, and then recovering the laminate to normal pressure, and counting the bubbles generated at the end of the polarizing plate to obtain a bubble generation number (number of bubble generation after the high temperature high pressure treatment) (number of bubble generation after the high temperature treatment, preferably 10 or less, more preferably 8 or less, and even more preferably 3 or less, and most preferably 0. As described above, the surface protective film of the present invention can suppress the generation of bubbles even when subjected to high-temperature and high-pressure treatment by an autoclave or the like after being attached to an adherend and thereafter returned to normal temperature and normal pressure.
The surface protective film of the present invention may be manufactured by any suitable method. Such a production method may be carried out by any suitable production method such as the following method.
(1) A method of applying a solution of a material for forming an adhesive layer, a hot melt to a substrate layer,
(2) A method of applying a solution or hot melt of a material for forming an adhesive layer to a separator and transferring the formed adhesive layer to a base material layer,
(3) Extruding the material for forming the adhesive layer and forming a coating on the substrate layer,
(4) A method of extruding the base material 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 two layers together with an adhesive layer,
(6) And a method of laminating two or more layers of the adhesive layer and a base layer forming material such as a film or a laminate layer.
As a coating method, 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 the adhesive composition. The pressure-sensitive adhesive layer may be produced by any suitable production method. Examples of such a production method include the following: the adhesive composition is applied onto a substrate layer, and heated and dried as necessary to form an adhesive layer on the substrate 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 brush, spray coating, air knife coating, extrusion coating by a die coater, and the like.
The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 500. Mu.m, more preferably 2 μm to 300. Mu.m, still more preferably 3 μm to 200. Mu.m, particularly preferably 4 μm to 150. Mu.m, and most preferably 5 μm to 100. Mu.m.
The adhesive composition is preferably at least 1 selected from the following adhesive 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 obtained from the above (1) and a urethane adhesive 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 from the adhesive composition. Specifically, from various study results, it is presumed that: the adhesive composition contains the polyfunctional alcohol (C) and the polyfunctional alcohol (C) is combined with the crosslinking agent (D), whereby the (meth) acrylic copolymer (A) obtained from the composition containing the specific kind of monomer component as an essential component is given a characteristic highly crosslinked structure. Thus, it is presumed that the pressure-sensitive adhesive layer has high adhesion and high light peelability, and the surface-protecting film of the present invention having the pressure-sensitive adhesive layer can suppress the generation of bubbles even after being applied to an adherend and subjected to high-temperature high-pressure treatment by an autoclave or the like and thereafter returned to normal temperature and normal pressure.
Further, it is found that when the pressure-sensitive adhesive layer (or the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer) of the surface-protecting film of the present invention is designed so as to have the above-described characteristic highly crosslinked structure, the pressure-sensitive adhesive composition containing the characteristic (meth) acrylic copolymer (B) described later can effectively suppress the increase in the adhesive strength with time and can exhibit more excellent light peelability.
The adhesive layer has a highly crosslinked structure, which can be seen from several angles. Examples of these angles include relaxation times observed by pulse NMR.
The inverse of the spin-spin relaxation time shows a positive linear correlation with the crosslink density of the polymer (the degree of restraint of molecular motion), and the spin-spin relaxation time T2 can be an index of the crosslink density of the polymer components constituting the adhesive layer. Specifically, when pulse NMR of the polymer is measured, 1 component or more (for example, 2 or 3) spin-spin relaxation times T2 can be obtained, and the magnitude of the spin-spin relaxation time T2 corresponds to the level of the crosslink density of the polymer component constituting the adhesive layer. In the method of distinguishing components according to the magnitude of the spin-spin relaxation time, when the analysis residue (offset) is less than 10% by the nonlinear square method, it can be determined that the resolution is adequate. If the component having a high crosslink density when separated into 2 components is referred to as an S component, the component having a low crosslink density is referred to as an L component, and the spin-spin relaxation times of the components are referred to as T2 (S) and T2 (L), the spin-spin relaxation time T2 (S) of the polymer component S having a high crosslink density, in which the molecular motion is restricted, becomes small, and the spin-spin relaxation time T2 (L) of the polymer component L having a low crosslink density becomes large.
When the free induction decay signal of the adhesive layer obtained by pulse NMR measurement is separated into 2 components by nonlinear least square method, the component with short relaxation time is set as hard component (S), the component with long relaxation time is set as soft component (L), and the spin-spin relaxation time of protons of soft component (L) measured at 30 ℃ is set as spin-spin relaxation time of protons of soft component (L)T2(L) 30 Spin-spin relaxation time T2 (L) of proton with soft component (L) measured at 60 DEG C 60 Ratio T2 (L) 60 /T2(L) 30 Preferably 1 or more, more preferably 1 to 5, still more preferably 1.5 to 4, particularly preferably 2 to 3.5, and most preferably 2.15 to 3.
T2 (L) as described above 30 Preferably 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, most preferably 1000 to 2300. Mu.s.
T2 (L) as described above 60 Preferably 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 having a highly crosslinked structure can 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%, and most preferably 95% to 230%.
The swelling degree can be measured, for example, by the following method. Specifically, about 0.1g of the polymer after the crosslinking reaction was wrapped around a porous tetrafluoroethylene sheet (trade name "NTF1122", manufactured by Nito electric Co., ltd.) having an average pore diameter of 0.2 μm, and then the resultant was bound with a kite string, and the weight was measured at that time, and the weight was used as the weight before impregnation (total weight of the polymer and tetrafluoroethylene sheet and kite string), while the total weight of the tetrafluoroethylene sheet and kite string was also measured in advance, and the weight was used as the bag weight. Next, the above polymer was wrapped with a tetrafluoroethylene sheet and bound with kite string, the obtained object (referred to as "sample") was put into a 50ml container filled with ethyl acetate, and left standing at 23 ℃ for 7 days, after which the ethyl acetate-impregnated sample was taken out of the container, ethyl acetate adhering to the sample was sufficiently scraped off with a waste cloth and the weight was measured, the weight was taken as the impregnated weight, and further, the impregnated weight was transferred to an aluminum cup, and drying was performed in a dryer at 130 ℃ for 2 hours to remove ethyl acetate, and then the weight was measured, and the weight was taken as the dried weight, and the swelling degree was calculated according to the following formula.
Swelling degree (%) = (a-b)/(c-b) ×100 (1)
In the formula (1), a is the weight after impregnation, b is the weight of the bag, and c is the weight after drying.
In addition, when the crosslinked polymer is used, the polymer may be used from the adhesive layer of the surface protective film, or may be used by coating the same adhesive layer as that provided on the surface protective film on a silicone separator or the like and drying the same.
Adhesive composition
The adhesive composition comprises a (meth) acrylic copolymer (A). The (meth) acrylic copolymer (a) may be 1 or 2 or more.
The content of the (meth) acrylic copolymer (a) in the 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, from the viewpoint of further exhibiting the effect of the present invention.
The adhesive composition comprises a polyfunctional alcohol (C). The number of the polyfunctional alcohols (C) may be 1 or 2 or more.
The content of the polyfunctional alcohol (C) in the adhesive composition may be any suitable content within a range that does not impair the effect of the present invention. The content of the (meth) acrylic copolymer (a) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, still more 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), in order to further exhibit the effect of the present invention.
The adhesive composition comprises a crosslinking agent (D). The number of the crosslinking agents (D) may be 1 or 2 or more.
The content of the crosslinking agent (D) in the adhesive composition may be any suitable content within a range that does not impair the effect of the present invention. The content is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 30 parts by weight, even more 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) in order to further exhibit the effect 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 components within a range that does not impair the effects of the present invention. Such other components may be 1 or 2 or more.
The adhesive composition may be prepared by compounding its constituent components by any suitable method.
(meth) acrylic copolymer (A) >
The (meth) acrylic copolymer (a) may be any suitable (meth) acrylic copolymer within a range that does not impair the effects of the present invention.
The weight average molecular weight of the (meth) acrylic copolymer (a) is preferably 10 to 500 tens of thousands, more preferably 20 to 400 tens of thousands, still more preferably 25 to 350 tens of thousands, particularly preferably 30 to 300 tens of thousands, from the viewpoint of further exhibiting the effect of the present invention.
The (meth) acrylic copolymer (a) is preferably a (meth) acrylic copolymer formed by polymerization from a composition (a) comprising: (a 1) an alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (a 2) a (meth) acrylate having an OH group.
The number of (a 1) components may be 1 or 2 or more. The number of (a 2) components may be 1 or 2 or more.
Examples of the alkyl (meth) acrylate (component a 1) having 4 to 12 carbon atoms in the alkyl ester moiety 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, dodecyl (meth) acrylate, and the like. Among these, 2-ethylhexyl (meth) acrylate is preferable, and 2-ethylhexyl acrylate (2 EHA) is more 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 of the alkyl (meth) acrylate (a 1) having 4 to 12 carbon atoms in the alkyl group of 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) acrylic acid ester (a 2) having an OH group include (meth) acrylic acid esters having an OH group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4 HBA) are more preferable, and 4-hydroxybutyl acrylate (4 HBA) is particularly preferable.
The content of the (meth) acrylic acid ester (a 2) having an OH group is preferably 0.1 to 50% by weight, more preferably 0.1 to 40% by weight, still more preferably 0.2 to 30% by weight, particularly preferably 0.5 to 20% by weight, and most preferably 1 to 10% by weight, based on the total amount (100% by weight) of the monomer components constituting the (meth) acrylic copolymer (a).
The composition (a) may contain a copolymerizable monomer other than the (a 1) and (a 2) components. The number of copolymerizable monomers may be 1 or 2 or more.
The composition (a) may contain (meth) acrylic acid as a copolymerizable monomer. The (meth) acrylic acid is at least 1 selected from the group consisting of acrylic acid and methacrylic acid, and acrylic acid is preferable in view of further exhibiting the effect of the present invention.
From the viewpoint of further exhibiting the effects of the present invention, the content of (meth) acrylic acid is preferably 0 to 10% by weight, more preferably 0 to 8% by weight, still more preferably 0 to 5% by weight, particularly preferably 0 to 2% by weight, and most preferably 0 to 1% by weight, relative to 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 anhydrides thereof (for example, anhydride group-containing monomers such as maleic anhydride and itaconic anhydride) (excluding (meth) acrylic acid); amide group-containing monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-hydroxymethyl (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-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, and vinyloxazole; sulfonic acid group-containing monomers such as sodium vinylsulfonate; phosphate 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-methacryloxyethyl isocyanate; (meth) acrylic esters having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, and the like; (meth) acrylic esters having an aromatic hydrocarbon group such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and the like; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins such as ethylene, butadiene, isoprene and isobutylene, and dienes; vinyl ethers such as vinyl alkyl ether; vinyl chloride; etc.
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 used within a range that does not impair the effects of the present invention. Examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as vinyl, propenyl, isopropenyl, vinyl ether group (vinyloxy), and allyl ether group (allyloxy). 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. The number of such polyfunctional monomers may be 1 or 2 or more.
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 alkoxyalkyl (meth) acrylate may be 1 or 2 or more.
The composition (a) may contain any appropriate other component within a range that does not impair 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 that does not impair the effects 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 polymerization reaction. The polymerization initiator may be 1 or 2 or more.
The thermal polymerization initiator may be preferably employed in obtaining the acrylic polymer by solution polymerization. Examples of such a thermal polymerization initiator include azo-based polymerization initiators, peroxide-based polymerization initiators (e.g., dibenzoyl peroxide, t-butyl peroxymaleate, etc.), and redox-based polymerization initiators. Among these thermal polymerization initiators, azo-based polymerization initiators disclosed in JP-A2002-69411 are particularly preferable. Such an azo-based polymerization initiator is preferable in that a decomposition product of the polymerization initiator is less likely to remain in the acrylic polymer as a part that causes generation of a heating generation gas (outgas). Examples of the azo-based 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), 4' -azobis-4-cyanovaleric acid, and the like. The amount of the azo-based 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-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α -ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzil-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators.
Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-dimethoxy-1, 2-diphenylethane-1-one, anisole methyl ether, and the like. Examples of the acetophenone photopolymerization initiator include 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl) dichloroacetophenone. Examples of the α -ketol photopolymerization initiator include 2-methyl-2-hydroxyphenylacetone and 1- [4- (2-hydroxyethyl) phenyl ] -2-methylpropan-1-one. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride and the like. Examples of the photo-polymerization initiator include 1-phenyl-1, 1-propanedione-2- (O-ethoxycarbonyl) -oxime. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzil photopolymerization initiator include benzil. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoyl benzoic acid, 3' -dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α -hydroxycyclohexyl phenyl ketone. Examples of the ketal photopolymerization initiator include benzildimethyl ketal. Examples of the thioxanthone 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 a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method, can be suitably employed.
< polyfunctional alcohol (C) >)
As the polyfunctional alcohol (C), any suitable polyfunctional alcohol may be used within a range that does not impair 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, still more preferably 3 to 5, particularly preferably 3 to 4, and most preferably 3, from the viewpoint of further exhibiting the effect 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 functions), a diol obtained by adding bisphenol a to propylene oxide (2 functions), a triol obtained by adding glycerol to propylene oxide (3 functions), a triol obtained by adding trimethylolpropane to propylene oxide (3 functions), a tetrol obtained by adding active hydrogen of ethylenediamine to propylene oxide (4 functions), a polyol obtained by adding sorbitol or sucrose to propylene oxide (multi functions), a triol obtained by adding glycerol to propylene oxide and ethylene oxide and end-capped with ethylene oxide (3 functions), a tetrol obtained by adding active hydrogen of ethylenediamine to propylene oxide and ethylene oxide and end-capped with ethylene oxide (4 functions), a polyethylene glycol obtained by adding polypropylene glycol and ethylene oxide end-capped with ethylene oxide (2 functions), a diol obtained by adding active hydrogen of ethylenediamine to propylene oxide and ethylene oxide and end-capped with ethylene oxide (2 functions), a triol obtained by adding trimethylolpropane to ethylene oxide (3 functions), a triol obtained by adding ethylene oxide and ethylene oxide to random (2 functions), a polyethylene glycol obtained by adding ethylene oxide to ethylene oxide (2 functions), a polyethylene glycol obtained by adding ethylene oxide to random (2 functions), and the like.
Examples of the commercial 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, etc.), polyol (for example, SANNIX GP series, SANNIX PP series, SANNIX TP-400 series, SANNIX SP-750 series, SANNIX PL-2100. PP series, SANESTER series, primepol series, NEWPOL series, MELPOL series, PEG series, MACROCOL series, etc.) of Sanyo chemical industry Co.
The polyether polyol is preferably one which can further exhibit the effects of the present invention: triols obtained by adding propylene oxide to glycerin (3 functions), triols obtained by adding propylene oxide to trimethylolpropane (3 functions), triols obtained by adding propylene oxide and ethylene oxide to glycerin and end-capped with ethylene oxide (3 functions), triols obtained by adding ethylene oxide to trimethylolpropane (3 functions), triols obtained by adding propylene oxide and ethylene oxide to glycerin and randomly adding ethylene oxide and propylene oxide (3 functions), more preferably: triols obtained by adding propylene oxide to glycerin (3 functions), triols obtained by adding propylene oxide and ethylene oxide to glycerin and end-capped with ethylene oxide (3 functions), triols obtained by adding propylene oxide and ethylene oxide to glycerin and randomly adding ethylene oxide and propylene oxide (3 functions), and more preferably triols obtained by adding propylene oxide to glycerin (3 functions).
Examples of the polyester polyol include polyester polyols obtained by reacting an acid component with a glycol 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, butanediol, 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 glycerol, trimethylolpropane, and pentaerythritol. Examples of the polyester polyol (a 1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β -methyl- γ -valerolactone) and polycaprolactone.
Examples of the commercial products of the polyester polyols include ADEKA ADEKA NEWACE (for example, 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.) available from Kyowa.
The number average molecular weight of the polyfunctional alcohol (C) is preferably 50 to 10000, more preferably 60 to 5000, further 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.
< crosslinker (D) >
As the crosslinking agent (D), any suitable crosslinking agent may be used within a range that does not impair the effects of the present invention.
Examples of the crosslinking agent (D) include urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, and amine-based crosslinking agents, in addition to polyfunctional isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, and peroxide-based crosslinking agents. 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-ethylene diisocyanate, 1, 4-butylene diisocyanate, and 1, 6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated xylene diisocyanate; aromatic polyisocyanates such as 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include commercial products such as trimethylolpropane/toluene diisocyanate adduct (Nippon Polyurethane Industry co., ltd., trade name "cornonate L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane Industry co., ltd., trade name "cornonate HL"), trade name "cornonate HX" (Nippon Polyurethane Industry co., ltd.), trimethylolpropane/xylylene diisocyanate adduct (manufactured by three-well chemical company, trade name "TAKENATE 110N"), and trade name "TAKENATE 600" (manufactured by three-well chemical company).
Examples of the epoxy-based crosslinking agent (polyfunctional epoxy compound) include N, N' -tetraglycidyl m-xylylenediamine, diglycidyl aniline, 1, 3-bis (N, N-diglycidyl aminomethyl) 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, sorbitan 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 an epoxy-based resin having 2 or more epoxy groups in the molecule. As the epoxy-based crosslinking agent, commercially available products such as "TETRAD C" (manufactured by Mitsubishi gas chemical Co., ltd.) are also exemplified.
(meth) acrylic copolymer (B)
From the aspect that the effects of the present invention can be further exhibited, the adhesive composition may contain a (meth) acrylic copolymer (B) formed by polymerization from a composition (B) containing an alkyl (meth) acrylate in which the alkyl group of the (B1) alkyl ester moiety is an alicyclic hydrocarbon group. The (meth) acrylic copolymer (B) may be 1 or 2 or more.
The content of the (meth) acrylic copolymer (B) in the adhesive composition may be any suitable content within a range that does not impair the effects of the present invention. The content is preferably 0.01 to 30 parts by weight, more preferably 0.01 to 20 parts by weight, even more 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) in order to further exhibit the effect of the present invention.
The (meth) acrylic copolymer (B) is formed by polymerization from a composition (B) containing an alkyl (meth) acrylate in which the alkyl group of the (B1) alkyl ester moiety is an alicyclic hydrocarbon group.
The number of (b 1) components may be 1 or 2 or more.
The alkyl (meth) acrylate (component b 1) in which the alkyl group of the alkyl ester moiety is an alicyclic hydrocarbon group includes, for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, and the like, and from the viewpoint of further exhibiting the effect of the present invention, dicyclopentadiene (meth) acrylate is preferable, and dicyclopentadiene (meth) acrylate is more preferable.
From the viewpoint of further exhibiting the effects of the present invention, the content of the alkyl (meth) acrylate (B1) in which the alkyl group of the alkyl ester moiety is an alicyclic hydrocarbon group is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more, particularly preferably 30% by weight or more, and most preferably 30% by weight to 99.9% by weight, relative to 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 copolymerizable monomers may be 1 or 2 or more.
From the viewpoint of further exhibiting the effects of the present invention, the composition (b) preferably contains, as the copolymerizable monomer, an alkyl (meth) acrylate having 1 to 3 carbon atoms as the alkyl group of the (b 2) alkyl ester moiety.
The alkyl (meth) acrylate (component b 2) having 1 to 3 carbon atoms in the alkyl group of the alkyl ester moiety includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like. The alkyl (meth) acrylate having 1 to 3 carbon atoms as the alkyl group of the alkyl ester moiety is preferably methyl (meth) acrylate, more preferably methyl methacrylate, from the viewpoint of further exhibiting the effect of the present invention.
From the viewpoint of further exhibiting the effects of the present invention, the content of the alkyl (meth) acrylate (B2) having 1 to 3 carbon atoms in the alkyl group of the alkyl ester moiety 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%, based on 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 b 2) having 1 to 3 carbon atoms in the alkyl ester moiety 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) acrylic esters 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-hydroxymethyl (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-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, and vinyloxazole; sulfonic acid group-containing monomers such as sodium vinylsulfonate; phosphate 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-methacryloxyethyl isocyanate; (meth) acrylic esters having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, and the like; (meth) acrylic esters having an aromatic hydrocarbon group such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and the like; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins such as ethylene, butadiene, isoprene and isobutylene, and dienes; vinyl ethers such as vinyl alkyl ether; vinyl chloride; etc.
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 used within a range that does not impair the effects of the present invention. Examples of such an ethylenically unsaturated group include radically polymerizable functional groups such as vinyl, propenyl, isopropenyl, vinyl ether group (vinyloxy), and allyl ether group (allyloxy). 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. The number of such polyfunctional monomers may be 1 or 2 or more.
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 alkoxyalkyl (meth) acrylate may be 1 or 2 or more.
From the viewpoint of further exhibiting the effects of the present invention, the composition (b) preferably contains a thiol as a chain transfer agent. Examples of the thiol include alkyl thioglycolate, and concretely, methyl thioglycolate, ethyl thioglycolate, and the like.
The chain transfer agent content in the composition (b) may be any suitable content within a range that does not impair the effect of the present invention. As such a content, from the viewpoint of further exhibiting the effects of the present invention, it is preferably 0.01 to 25 parts by weight, more preferably 0.02 to 20 parts by weight, still more preferably 0.05 to 15 parts by weight, and particularly preferably 0.1 to 15 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the (meth) acrylic copolymer (B).
The Tg of the (meth) acrylic copolymer (B) is preferably 50 to 250℃and more preferably 70 to 230℃and even more preferably 80 to 220℃and particularly preferably 90 to 210℃and most preferably 100 to 200℃in view of further exhibiting the effects of the present invention.
The Tg of the (meth) acrylic copolymer (B) is a value obtained by Fox equation based on Tg of a homopolymer of each monomer constituting the (meth) acrylic copolymer (B) and a weight fraction (copolymerization ratio based on weight) of the monomer. The Fox equation is shown below as a relation between Tg of the copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each monomer constituting the copolymer.
1/Tg＝Σ(Wi/Tgi)
In the above Fox formula, tg represents the glass transition temperature (unit: K) of the copolymer, wi represents the weight fraction (copolymerization ratio based on weight) of the monomer i in the copolymer, tgi represents the glass transition temperature (unit: K) of the homopolymer of the monomer i. As the Tg of the homopolymer, the values described in known materials are used.
As Tg of the homopolymer, for example, the following values can be specifically used.
Dicyclopentadiene methacrylate 175 DEG C
Methyl methacrylate 105 DEG C
As Tg's of homopolymers other than those exemplified above, the values described in "Polymer Handbook" (3 rd edition, john Wiley & Sons, inc., 1989) can be used. In the case where a plurality of values are described in the above "Polymer Handbook", conventional values are used. For the monomer not described in the above "Polymer Handbook", a catalog of the monomer manufacturing company was used. The Tg of a homopolymer of a monomer, which is not described in the "Polymer Handbook" and which does not provide a catalog value for a monomer manufacturing company, was obtained by the measurement method described in JP-A2007-51271.
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 effect of the present invention.
The composition (b) may contain any appropriate other component within a range that does not impair 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 that does not impair the effects of the present invention. For their details, the description in item (A) > of the (meth) acrylic copolymer 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 a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method, can be suitably employed.
< Ionic liquid >
The binder composition may comprise an ionic liquid. By including the ionic liquid in the adhesive composition, an adhesive composition having extremely excellent antistatic properties can be provided. The ionic liquid may be 1 or 2 or more.
In the present invention, the ionic liquid means a molten salt (ionic compound) which is in a liquid state at 25 ℃.
The ionic liquid is preferably an ionic liquid containing a fluorine organic 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 extremely excellent in antistatic properties can be provided.
Any suitable onium cation can be used as the onium cation constituting the ionic liquid within a range that does not impair the effect of the present invention. Such onium cations are preferably at least 1 selected from 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 properties can be provided.
The onium cation constituting the ionic liquid is preferably at least 1 selected from cations having structures represented by general formulae (1) to (5).
In the general formula (1), ra represents a hydrocarbon group having 4 to 20 carbon atoms, and may contain a heteroatom, rb and Rc are the same or different, and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and may contain a heteroatom. 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 heteroatom, re, rf and Rg are the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and may contain a heteroatom.
In the general formula (3), rh represents a hydrocarbon group having 2 to 20 carbon atoms, which 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, which 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. Where Z is a sulfur atom, there is no Ro.
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, and a cation having a pyrroline skeleton.
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; pyrrolidinium cations such as 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-propyl-1-butylpyrrolidinium cation, and 1, 1-dibutylpyrrolidinium cation; piperidinium cations such as 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-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 cations; 1-ethylcarbazole cation; etc.
Among these, preferred examples of the pyridinium cations that can further exhibit the effect of the present invention include 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; pyrrolidinium cations such as 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; piperidinium cations such as 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, 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 tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.
Specific examples of the cation represented by the general formula (2) include imidazolium cations such as 1, 3-dimethylimidazolium cation, 1, 3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1, 2-dimethyl-3-propylimidazolium cation, 1-ethyl-2, 3-dimethylimidazolium cation, 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 cations, 1,2, 3-trimethyl-1, 4,5, 6-tetrahydropyrimidinium cations, 1,2,3, 4-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cations, and 1,2,3, 5-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cations; 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; etc.
Among these, from the viewpoint of further exhibiting the effects of the present invention, imidazolium cations such as 1, 3-dimethylimidazolium cation, 1, 3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation and the like are preferable, and 1-ethyl-3-methylimidazolium cation and 1-hexyl-3-methylimidazolium cation are more preferable.
Examples of the cation represented by the general formula (3) include a pyrazolium (pyrazolium) cation and a pyrazolinium (pyrazolium) cation.
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; etc.
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 above alkyl group is substituted with an alkenyl group, an alkoxy group, and further 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, glycidyl trimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and the like.
Among these, preferred examples of the compounds which can further exhibit the effect of the present invention include asymmetric tetraalkylammonium cations such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyl trimethylammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, N-dimethyl-N-ethyl-N-pentylammonium cation, N-dimethyl-N-ethyl-N-hexylammonium cation, N-dimethyl-N-ethyl-N-heptylammonium cation, N, 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, N-dimethyl-N-propyl-N-hexylammonium cation, N-dimethyl-N-propyl-N-heptylammonium cation, N-dimethyl-N-butyl-N-hexylammonium cation, N-diethyl-N-butyl-N-heptylammonium cation, N, 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, N-diethyl-N-methyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N-dipropyl-N-methyl-N-ethylammonium cation, N, 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, N-dibutyl-N-methyl-N-hexylammonium cation, trioctyl methylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, etc., more preferably trimethyl propylammonium cation.
Any suitable fluoroorganic anions may be used as the fluoroorganic anions constituting the ionic liquid within a range that does not impair the effects of the present invention. Such a fluorinated organic anion may be completely fluorinated (perfluorinated) or may be partially fluorinated.
Examples of such a fluorinated organic anion include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyano perfluoroalkanesulfonyl amides, bis (cyano) perfluoroalkanesulfonyl methides, cyano-bis- (perfluoroalkanesulfonyl) methides, tris (perfluoroalkanesulfonyl) methides, trifluoroacetates, perfluoroalkanesulfones, tris (perfluoroalkanesulfonyl) methides, (perfluoroalkanesulfonyl) trifluoroacetamides, and the like.
Of these fluoroorganic anions, perfluoroalkylsulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, more specifically, trifluoromethanesulfonate, pentafluoroethane sulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide are more preferable.
The ionic liquid may be used by appropriately selecting from combinations of the cationic component and the anionic component. 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 heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 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, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-methylpyrrolium bis (trifluoromethanesulfonyl) imide, and 1-methylpyrrolium (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, 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-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium 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-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 5-methyl-1-butylpiperidinium imide, 5-methyl-1-pentylmethyl-1-piperidinium bis (trifluoromethanesulfonyl) imide, 5-ethyl-1-pentylmethyl-piperidinium bis (trifluoromethanesulfonyl) 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, 1-ethyl-1-heptylpyrrolidinium bis (pentafluorosulfonyl) imide, 1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluorosulfonyl) imide, 1-bis (pentafluoroethanesulfonyl) imide, 1-pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-bis (pentafluoroethanesulfonyl) imide, 1, 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 (pentafluorosulfonyl) 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 (pentafluorosulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluorosulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluorosulfonyl) imide, 1-bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluorosulfonyl) imide, 1-ethylpiperidinium bis (pentafluorosulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluorosulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluorosulfonate, 1-ethyl-3-methylimidazolium heptafluoropropane sulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate, 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 bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium triflate, 1-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-methyl) 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) imide, 1-propyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2, 3, 5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-ammonium (trifluoromethanesulfonyl) imide, N-bis (N-methylsulfonyl) imide, 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, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, 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-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, 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-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N, 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 sulfonate, N-difluoromethane-N- (2-methylsulfonyl) trifluoromethanesulfonyl) N-ethylsulfonyl) trifluoromethanemide, N-bis (2-ethylsulfonyl) trifluoromethanesulfonyl) trifluoromethanesulfonate, N-dimethyl-N-ethylsulfonyl) and N-difluoromethyl-N-pentylammonium sulfonate Glycidyl trimethylammonium trifluoromethane sulfonate, glycidyl trimethylammonium bis (trifluoromethane sulfonyl) imide, glycidyl trimethylammonium bis (pentafluoroethane sulfonyl) imide, diallyl dimethylammonium bis (trifluoromethane sulfonyl) imide, diallyl dimethyl bis (pentafluoroethane sulfonyl) imide, lithium bis (trifluoromethane sulfonyl) imide, lithium bis (fluorosulfonyl) imide, and the like.
Of these ionic liquids, more preferred are 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 trifluoromethane sulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 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 trifluoromethane sulfonate, 1-ethyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-methyl-3-methylsulfonyl) imide, 1-methylsulfonyl imide, 1-methyl-3-methylpyridinium bis (fluorosulfonyl) imide, and 1-methylsulfonyl imide 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.
The ionic liquid may be synthesized as described below, or may be a commercially available one. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and 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-the forefront of development and in the future" (CMC Group publication) can be generally used.
In the following, the synthesis method is exemplified by a halide method, a hydroxide method, an acid ester method, a complexing method, and a neutralization method, 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 performed by a reaction represented by the following reaction formulae (1) to (3). First, a tertiary amine is reacted with an alkyl halide to obtain a halide (formula (1), and chlorine, bromine, or iodine can be used as the 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, etc.) having an anion structure (A-) of the target ionic liquid to obtain the target ionic liquid (R) 4 NA)。
(1)R 3 N+RX→R 4 NX (X：Cl，Br，I)
(2)R 4 NX+HA→R 4 NA+HX
(3)R 4 NX+MA→R 4 NA+MX (M：NH 4 Li, na, K, ag, etc
The hydroxide method is a method performed by a reaction represented by the following reaction formulae (4) to (8). First, a halide (R 4 NX) 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) 2 The reaction of O) (equation (6)) to give hydroxide (R) 4 NOH) (as halogen, chlorine, bromine, iodine are used).
The obtained hydroxide was reacted in the same manner as in the halogenation method described above by using the reaction formulae (7) to (8), to thereby obtain the objective ionic liquid (R 4 NA)。
(4)R 4 NX+H 2 O→R 4 NOH+1/2H 2 +1/2X 2 (X：Cl，Br，I)
(5)R 4 NX+P-OH→R 4 NOH+P-X (P-OH: OH type ion)Exchange resin
(6)R 4 NX+1/2Ag 2 O+1/2H 2 O→R 4 NOH+AgX
(7)R 4 NOH+HA→R 4 NA+H 2 O
(8)R 4 NOH+MA→R 4 NA+MOH (M：NH 4 Li, na, K, ag, etc
The acid ester method is a method performed by a reaction represented by the following reaction formulae (9) to (11). First, tertiary amine (R) 3 N) and an acid ester to obtain an acid ester (reaction formula (9), as the acid ester, 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 are used.
The obtained acid ester compound was reacted by using the reaction formulae (10) to (11) in the same manner as in the halogenation method, to obtain the objective ionic liquid (R) 4 NA). In addition, by using methyl trifluoromethane sulfonate, methyl trifluoroacetate or the like as an acid ester, an ionic liquid can be directly obtained.
(9)R 3 N+ROY→R 4 NOY
(10)R 4 NOY+HA→R 4 NA+HOY
(11)R 4 NOY+MA→R 4 NA+MOY (M：NH 4 Li, na, K, ag, etc
The neutralization method is a method performed by a reaction represented by the reaction formula (12). By reacting tertiary amines with CF 3 COOH、CF 3 SO 3 H、(CF 3 SO 2 ) 2 NH、(CF 3 SO 2 ) 3 CH、(C 2 F 5 SO 2 ) 2 Organic acids such as NH.
(12)R 3 N+HZ→R 3 HN + Z - [HZ：CF 3 COOH，CF 3 SO 3 H，(CF 3 SO 2 ) 2 NH，(CF 3 SO 2 ) 3 CH，(C 2 F 5 SO 2 ) 2 Organic acids such as NH]
R in the above-mentioned reaction formulae (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a heteroatom.
The content of the ionic liquid in the adhesive composition may be any suitable content within a range that does not impair the effects of the present invention. From the viewpoint of further exhibiting the effects of the present invention, the content is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more 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). By adjusting the compounding amount of the ionic liquid to the above range, an adhesive composition excellent in antistatic properties can be provided. If the amount of the ionic liquid to be blended is less than 0.01 parts by weight, there is a concern that sufficient antistatic properties cannot be obtained. If the amount of the ionic liquid to be blended exceeds 50 parts by weight, there is a concern that contamination of the adherend increases.
< 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, by using the ionic liquid in combination, the effect of antistatic properties can be more effectively exhibited.
The content of the modified silicone oil in the adhesive composition may be any suitable content within a range that does not impair the effects of the present invention. From the viewpoint of further exhibiting the effects of the present invention, the content is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 40 parts by weight, still more 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). By adjusting the content ratio of the modified silicone oil to the above range, the effect of antistatic properties can be further effectively exhibited.
Any suitable modified silicone oil can be used as the modified silicone oil within a range that does not impair the effects of the present invention. Examples of such modified silicone oils include those available from the company of the shin-Etsu chemical industry.
As the modified silicone oil, polyether modified silicone oil is preferable. By using polyether-modified silicone oil, the effect of antistatic properties can be further effectively exhibited.
Examples of the polyether-modified silicone oil include side chain-type polyether-modified silicone oils and both terminal-type polyether-modified silicone oils. Of these, polyether-modified silicone oils having both ends are preferable from the viewpoint of sufficiently exhibiting the effect of antistatic properties more effectively.
< other ingredients that may be contained in the adhesive composition >
The adhesive composition may contain any appropriate other components within a range that does not impair the effects of the present invention. Examples of such other components include other polymer components, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), antioxidants, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foils, ultraviolet absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, anticorrosive agents, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.
Substrate layer
The substrate layer may be 1 layer or 2 or more layers. The substrate layer may be stretched.
The thickness of the base layer is preferably 1 μm to 500. Mu.m, more preferably 5 μm to 400. Mu.m, still more preferably 10 μm to 300. Mu.m, particularly preferably 15 μm to 200. Mu.m.
For the purpose of forming a wound body or the like that is easily unwound, for example, a surface of the base material layer to which the adhesive layer is not attached may be subjected to a mold release treatment by adding a fatty acid amide, a polyethylenimine, a long-chain alkyl-based additive or the like to the base material layer, or may be provided with a coating layer formed of any suitable release agent such as a silicone-based, long-chain alkyl-based, fluorine-based or the like.
As the material of the base material layer, any appropriate material can be used depending on the application. Examples thereof include plastics, papers, metal films, and nonwoven fabrics. Preferably plastic. That is, the base material layer is preferably a plastic film. The base material layer may be composed of 1 material or 2 or more materials. For example, it may be composed 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 resin include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin resin include homopolypropylene; propylene copolymers such as block copolymers, random copolymers and graft copolymers containing an ethylene component as a copolymerization component; reactor TPO; low density, high density, linear low density, ultra low density, and the like; ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, and other ethylene-based copolymers; etc.
The substrate layer may contain any suitable additives as desired. Examples of the additive that can be contained in the base layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. 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 or the like. From the viewpoint of improving weather resistance, the additives are particularly preferably antioxidants, ultraviolet absorbers, light stabilizers, and fillers.
As the antioxidant, any suitable antioxidant may be used. Examples of such antioxidants include phenol antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat stabilizers, phenol-phosphorus-based antioxidants, and the like. The content of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less, and even more preferably 0.01% by weight to 0.2% by weight, based on the base resin of the base layer (the base resin is the blend when the base layer is a blend).
As the ultraviolet absorber, any suitable ultraviolet absorber can be used. Examples of such ultraviolet absorbers 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 (the blend is the base resin when the base layer is a blend).
As the light stabilizer, any suitable light stabilizer may be used. Examples of such light stabilizers include hindered amine light stabilizers and benzoate light stabilizers. The content ratio 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 (the blend is the base resin when the base layer is a blend).
As the filler, any suitable filler may be used. Examples of such fillers 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 still more preferably 0.01% by weight to 10% by weight, based on the base resin forming the base layer (the blend is the base resin when the base layer is a blend).
Further, for the purpose of imparting antistatic properties, surfactants, inorganic salts, polyols, metal compounds, carbon and other inorganic, low-molecular-weight and high-molecular-weight antistatic agents may be preferably used as the additive. In particular, high molecular weight antistatic agents and carbon are preferable from the viewpoints of contamination and maintenance of adhesion.
Use
The surface protective film of the present invention has high adhesion and high light peelability, and can suppress the generation of bubbles even after being subjected to high-temperature and high-pressure treatment by an autoclave or the like after being attached to an adherend and thereafter being returned to normal temperature and normal pressure. Therefore, the adhesive composition can be suitably used for surface protection of an adherend requiring the above-mentioned properties of a surface protective film.
As such an adherend, an adherend having a surface with a water contact angle of 60 degrees or more is preferable. The water contact angle of the surface of such an adherend is preferably 65 degrees or more, more preferably 70 degrees or more, still more preferably 75 degrees or more, particularly preferably 80 degrees or more. An adherend having a surface water contact angle in the above range is likely to generate bubbles when subjected to high-temperature high-pressure treatment by an autoclave or the like after a conventional surface protective film is attached thereto and thereafter returned to normal temperature and normal pressure. When the surface protective film of the present invention is used, the occurrence of bubbles can be suppressed even if the adherend is subjected to high-temperature high-pressure treatment by an autoclave or the like after the water contact angle applied to the surface falls within the above range, and thereafter, the pressure is returned to normal temperature and normal pressure.
Examples of such an adherend include an unsaponifiable TAC (cellulose triacetate) film, a barrier film usable for devices such as an organic EL display and an OLED.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The test and evaluation methods in examples and the like are as follows. When "part" is described, it means "part by weight" unless otherwise specified, and when "%" is described, it means "% by weight" unless otherwise specified.
< determination of weight average molecular weight >
The weight average molecular weight is determined by Gel Permeation Chromatography (GPC). Specifically, the GPC measurement apparatus was measured under the following conditions using the trade name "HLC-8120GPC" (manufactured by Tosoh Corp.) and calculated from standard polystyrene conversion values.
(conditions for molecular weight measurement)
Sample concentration: 0.2 wt% (tetrahydrofuran solution)
Sample injection amount: 10 mu L
Column: trade name "TSKguardcolumn SuperHZ-H (1 root) +TSKgel SuperHZM-H (2 root)" (manufactured by Tosoh Co., ltd.)
Reference column: trade name "TSKgel SuperH-RC (1 root)" (manufactured by Tosoh Co., ltd.)
Eluent: tetrahydrofuran (THF)
Flow rate: 0.6 mL/min
Detector: differential Refractometer (RI)
Column temperature (measurement temperature): 40 DEG C
< measurement of pulse NMR of adhesive layer >
The measurement of pulse NMR was performed by the CPMG method. Specifically, the pulse NMR measuring apparatus was under the following conditions, using the trade name "TD-NMR theminispecmq20" (manufactured by Brukar Co., ltd.).
(relaxation time measurement conditions)
Measurement method: CPMG method
90 ° pulse width: 2.1 mu s
Repetition time: 1 second
Cumulative number of times: 64 times
Measurement temperature: 30 ℃ and 60 DEG C
Analysis method: nonlinear 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 the separator was peeled off to give an adhesive (bonding) area of 1cm in the exposed adhesive layer 2 The resulting sheet was bonded to an unsaponifiable TAC polarizing plate (width 70mm, length 100mm, water contact angle=69.9 degrees) obtained in production example 5 described later, left standing at 23℃X 50% RH for 30 minutes, and then peeled off in the shearing direction at a peeling rate of 0.06 mm/min, and the maximum load (N/cm) 2 ) As shear adhesion.
< measurement of high-speed Release force >
The surface protective film was cut into dimensions of 25mm in width and 100mm in length, the separator was peeled off, and then the separator was pressed by a hand press roll against the surface of an unsaponifiable TAC polarizing plate (width 70mm, length 100mm, water contact angle=69.9 degrees) obtained in production example 5 described later, and then laminated under pressure conditions of 0.25MPa and 0.3 m/min to prepare an evaluation sample. Then, the separator on the polarizing plate side of the evaluation sample was peeled off, and the film was pressed against a carrier glass having a thickness of 1.3mm, a width of 65mm and a length of 165mm by a press roll, and left to stand in an atmosphere of 23 ℃ x 50% rh for 30 minutes, and then one end of the surface protective film was peeled off by a universal tensile tester at a peeling angle of 30 m/min and 180 ° at a stretching speed, and the adhesive force at this time was measured. For the measurement, the measurement was performed under an atmosphere of 23℃X 50% RH.
< measurement of bubble generation number 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 pressed by a hand press roll against the surface of an adherend (70 mm in width and 100mm in length), and then laminated under a pressure-bonding condition of 0.25MPa and 0.3 m/min, and the 4 sides were cut by a cutter from the surface protective film side to a width of 50mm and a length of 80mm, to obtain an evaluation sample. The separator on the polarizing plate side was peeled off, and the resultant was pressed against a carrier glass having a thickness of 1.3mm, a width of 65mm and a length of 165mm by a press roll, and left under an atmosphere of 23 ℃ x 50% rh for 30 minutes, then subjected to autoclave treatment under an atmosphere of 5atm at 50 ℃ for 40 minutes, and then returned to normal temperature and pressure, and then the number of bubbles generated at the end of the polarizing plate was counted as the number of bubbles generated.
As the adherend, the following one prepared in the production example described below was used.
Adherend (a): unsaponifiable TAC polarizing plate 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 polarizing plate with adhesive layer (water contact angle=53.1 degree)
< measurement of Water contact Angle >
Ion-exchanged water was added dropwise to the mixture in an amount of 2. Mu.L using DM-501 manufactured by Kyowa Kagaku Co., ltd.) by a syringe, and the waiting time until measurement after the addition was 1000 ms. In addition, the contact angle of water was measured at 5 points in the width direction at any of a plurality of positions of the adherend, and the average value was taken as the contact angle of water of the adherend.
< measurement of swelling degree >
The swelling degree was measured by the following method. Specifically, about 0.1g of the polymer after the crosslinking reaction was wrapped around a porous tetrafluoroethylene sheet (trade name "NTF1122", manufactured by Nito electric Co., ltd.) having an average pore diameter of 0.2 μm, and then the resultant was bound with a kite string, and the weight was measured at that time, and the weight was used as the weight before impregnation (total weight of the polymer and tetrafluoroethylene sheet and kite string), while the total weight of the tetrafluoroethylene sheet and kite string was also measured in advance, and the weight was used as the bag weight. Next, the above polymer was wrapped with a tetrafluoroethylene sheet and bound with kite string, the obtained object (referred to as "sample") was put into a 50ml container filled with ethyl acetate, and left standing at 23 ℃ for 7 days, after which the ethyl acetate-impregnated sample was taken out of the container, ethyl acetate adhering to the sample was sufficiently scraped off with a waste cloth and the weight was measured, the weight was taken as the impregnated weight, and further, it was transferred into an aluminum cup, and dried in a dryer at 130 ℃ for 2 hours to remove ethyl acetate, and then the weight was measured, the weight was taken as the dried weight, and the swelling degree was calculated according to the following formula.
Swelling degree (%) = (a-b)/(c-b) ×100 (1)
In the formula (1), a is the weight after impregnation, b is the weight of the bag, and c is the weight after drying.
In addition, when the crosslinked polymer is used, the polymer may be used from the adhesive layer of the surface protective film, or may be used by coating the same adhesive layer as that provided on the surface protective film on a silicone separator or the like and drying the same.
Production example 1: production of acrylic copolymer (1)
Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, 2-ethylhexyl acrylate (2 EHA) (Nippon Shokubai co., ltd.): 100 parts by weight of 4-hydroxybutyl acrylate (4 HBA) (manufactured by Nippon chemical Co., ltd.): 10 parts by weight of Acrylic Acid (AA) (Nippon Shokubai co., ltd.): 0.02 part by weight of 2,2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) as a polymerization initiator: 0.02 parts by weight of ethyl acetate: 180 parts by weight of an acrylic copolymer (1) having a weight-average molecular weight of 54 ten thousand was prepared by conducting polymerization reaction for 6 hours while stirring slowly and introducing nitrogen gas, and maintaining the liquid temperature in the flask at around 65℃and obtaining a solution (solid content: 35% by weight).
Production example 2: production of acrylic copolymer (2)
Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, 2-ethylhexyl acrylate (2 EHA) (Nippon Shokubai co., ltd.): 100 parts by weight of 2-hydroxyethyl acrylate (HEA) (manufactured by Toyama Synthesis Co., ltd.): 4 parts by weight of 2,2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) as a polymerization initiator: 0.02 parts by weight of ethyl acetate: 180 parts by weight of an acrylic copolymer (2) having a weight average molecular weight of 56 g was prepared by conducting polymerization reaction for 6 hours while stirring slowly and maintaining the liquid temperature in the flask at around 65℃with nitrogen introduced thereinto (solid content: 35% by weight).
Production example 3: production of methacrylic copolymer (3)
100 parts by weight of toluene and dicyclopentadiene methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi chemical Co., ltd.) were charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet pipe, and a condenser: 60 parts by weight of Methyl Methacrylate (MMA) (manufactured by Mitsubishi gas chemical Co., ltd.): 40 parts by weight of methyl thioglycolate as a chain transfer agent: 3.5 parts by weight. Then, after stirring at 70℃under a nitrogen atmosphere for 1 hour, 2' -azobisisobutyronitrile (manufactured by Wako pure chemical industries, ltd.) was charged as a polymerization initiator: 0.2 parts by weight, followed by a reaction at 70℃for 2 hours and then at 80℃for 4 hours, and then a reaction at 90℃for 1 hour, to prepare a solution (solid content: 60% by weight) of the methacrylic copolymer (3) having a weight average molecular weight of 4400 and Tg=144 ℃ (calculated according to the Fox formula).
Production example 4: production of acrylic adhesive composition (P1) for forming adhesive for polarizing plate
(production of a solution of acrylic Polymer (A1))
Into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser, a flask containing Butyl Acrylate (BA) was charged: 94.9 parts by weight of Acrylic Acid (AA): 5 parts by weight of hydroxyethyl acrylate (HEA): 0.1 part by weight of a monomer mixture. Further, relative to the monomer mixture: 100 parts by weight of 2,2' -Azobisisobutyronitrile (AIBN) as a polymerization initiator: 0.1 part by weight of the mixture was charged with ethyl acetate, nitrogen was introduced while stirring slowly, and the mixture was replaced with nitrogen, and then the liquid temperature in the flask was kept at about 55℃for 7 hours to carry out polymerization. Thereafter, ethyl acetate was added to the obtained reaction solution to prepare a solution of the acrylic polymer (A1) having a weight average molecular weight of 200 ten thousand, which was 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., manufactured by ltd.): 0.6 part by weight of a silane coupling agent (trade name "KBM-403", manufactured by Xinyue chemical Co., ltd.): 0.1 part by weight of an acrylic adhesive composition (P1) was prepared.
Production example 5: production of adherend (A)
(production of polarizing element)
A polyvinyl alcohol film (KURARAY CO., LTD: VF-PS7500, width 1000 mm) having a thickness of 75 μm was used, and was stretched to a stretching ratio of 2.5 times by immersing it in pure water at 30℃for 60 seconds, was dyed in an aqueous iodine solution (weight ratio: pure water/iodine (I)/potassium iodide (KI) =100/0.01/1) at 30℃for 45 seconds, was stretched to a stretching ratio of 5.8 times in an aqueous 4 wt% boric acid solution, was immersed in pure water for 10 seconds, and was dried at 60℃for 5 minutes while maintaining the film tension, to obtain a polarizing element. The thickness of the polarizer was 25 μm and the water content was 15 wt%.
(production of transparent protective film with adhesive layer)
PVA resin (manufactured by Nippon chemical Co., ltd.: GOHSENOL): 100 parts by weight of a crosslinking agent (WATERSOL, manufactured by Dain ink chemical Co., ltd.): 35 parts by weight of the water was dissolved in pure water: 3760 parts by weight of an adhesive was prepared. The adhesive was applied to one side of a 60 μm thick cellulose Triacetate (TAC) film (TD-60 UL, manufactured by Fujifilm Co., ltd.) 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. Mu.m.
(production of polarizing plate (A))
The polarizing plate (a) was produced by the method shown in fig. 2. The polarizing material was used as the polarizing material, and the non-saponified TAC film with an adhesive layer was used as the 1 st transparent protective film B1. The 2 nd transparent protective film B2 was produced in the same manner as the TAC film with an adhesive layer, except that an acrylic film with an adhesive layer was used and an acrylic film with an adhesive layer was used instead of the TAC film. As shown in fig. 2, the TAC film with adhesive layer (1 st transparent protective film B1) is fed from the 1 st roll R1 side, and the acrylic film with adhesive layer (2 nd transparent protective film B2) is 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-based release agent by a spray coater, and dried in an air-circulating type constant temperature oven at 155℃for 2 minutes to thereby produce a pressure-sensitive adhesive layer having a thickness of 20. Mu.m. Next, the 2 nd transparent protective film surface of the polarizing plate (a) was subjected to corona treatment, and a separator having an adhesive layer formed thereon was bonded to the corona-treated surface to produce an unsaponifiable TAC polarizing plate with an adhesive layer as an adherend (a). The water contact angle of the produced unsaponifiable TAC polarizing plate with an adhesive layer was 69.9 degrees.
Production example 6: production of adherend (B)
(preparation of aqueous adhesive solution)
Polyvinyl alcohol resin containing acetoacetyl group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetyl group modification degree: 5 mol%): 100 parts by weight of methylolmelamine: 50 parts by weight of purified water dissolved at 30℃was prepared to obtain an aqueous solution having a solid content of 3.7% by weight. With respect to the aqueous solution: 100 parts by weight of an aqueous alumina colloid solution (average particle diameter: 15nm, solid content concentration: 10% by weight, positive charge) was added: 18 parts by weight of an aqueous adhesive solution was prepared. The viscosity of the aqueous adhesive solution was 9.6 mPas and the pH was in the range of 4 to 4.5.
(production of polarizing plate with surface treatment)
The composition comprises an ultraviolet curable urethane acrylate monomer: 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 were added: 15 parts by weight of silica particles having an average particle diameter of 1.4. Mu.m: 10 parts by weight of a resin mixture was obtained. To the obtained resin mixture, a viscosity adjusting solvent was further added to a solid content of 50% by weight, and the mixture was mixed with a high-speed mixer. The obtained mixed solution was applied to the 1 st transparent protective film B1 (TAC film) side of the polarizing plate (a) produced in production example 5 by a bar coater, and after the solvent was evaporated, ultraviolet rays were irradiated to perform curing treatment, thereby obtaining an antiglare-treated polarizing plate (B) having a fine uneven surface structure and comprising an ultraviolet-curable resin film having a thickness of 7 μm.
(production of adherend (B))
An antiglare polarizing plate with an adhesive layer as an adherend (B) was obtained in the same manner as in production example 5, except that the antiglare polarizing plate (B) was used instead of the polarizing plate (a). The water contact angle of the prepared antiglare treated polarizing plate with an adhesive layer was 88.4 degrees.
Production example 7: production of adherend (C)
As the green film, a polyvinyl alcohol film (average polymerization degree 2400, KURARAY 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 Process)
The swelling procedure was carried out by means of 2 swelling baths in the manner shown in fig. 3. Pure water was used as the treatment liquid for each swelling bath. As the guide roller 13 provided in the swelling bath of stage 1 in fig. 3, an expanding roller having a radius of curvature of 2000mm was used. The spreader roll was disposed at a position 80% of the length of the polyvinyl alcohol film immersed in the treatment liquid (the length of the broken lines of p1 and p2 in fig. 3). The other guide rollers use a flat pressing roller.
< stage 1 >
The polyvinyl alcohol film was fed to the swelling bath in stage 1, immersed in pure water adjusted to 40 ° for 60 seconds, and uniaxially stretched to a stretching ratio of 1.80 while swelling.
< stage 2 >
Next, the polyvinyl alcohol film subjected to the swelling step of the above stage 1 was transferred to the swelling bath of the stage 2, immersed in pure water adjusted to 30 ℃ for 60 seconds, and uniaxially stretched to a stretching ratio of 1.10 (total stretching ratio of 1.98 times) while swelling.
(dyeing Process)
As a treatment liquid for the dyeing bath, iodine was used: 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, and was dyed while being immersed in the iodine dyeing solution adjusted to 30 ℃ for 60 seconds, and uniaxially stretched to a total stretching ratio of 3 times with respect to the original length.
(crosslinking step)
As the treatment liquid for the crosslinking bath, an aqueous boric acid solution containing 3 wt% boric acid and 3 wt% potassium iodide was used. The polyvinyl alcohol film treated as described above was fed to a crosslinking bath, and was uniaxially stretched to a total elongation magnification of 4 times relative to the original length while immersed in the aqueous boric acid solution adjusted to 30 ℃ for 19 seconds.
(stretching step)
As the treatment liquid for the stretching bath, an aqueous boric acid solution containing 4 wt% boric acid and 5 wt% potassium iodide was used. The polyvinyl alcohol film treated as described above was fed to a stretching bath, and was uniaxially stretched to a total stretching ratio of 6 times relative to the original length while being immersed in an aqueous boric acid solution adjusted to 60 ℃ for 13 seconds.
(cleaning step)
As the treatment liquid for the cleaning bath, an aqueous solution containing 3% by weight of potassium iodide was used. The polyvinyl alcohol film treated as described above was transferred to a washing bath, and immersed in the aqueous solution adjusted to 30℃for 10 seconds.
(drying step)
Then, the polyvinyl alcohol film treated as described above was dried in an oven at 60℃for 4 minutes to obtain a polarizing element.
(production of adherend (C))
A saponified cellulose triacetate film having a thickness of 80 μm was laminated on both sides of the polarizing plate obtained above with an adhesive containing a 5 wt% aqueous solution of completely saponified polyvinyl alcohol, and was brought into close contact with a calender roll, and then dried at 70℃for 4 minutes. Thereafter, a saponified TAC polarizing plate with an adhesive layer as an adherend (C) was obtained 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 prepared saponified TAC polarizing plate with an adhesive layer was 53.1 degrees.
Example 1: adhesive composition (1) and production of surface protective film (1)
To the solution of the acrylic copolymer (1) obtained in production example 1, a solution was added in which an organosiloxane having an oxyalkylene chain (KF-353, manufactured by singe chemical industry co., ltd.) as a silicone component was diluted to 10% by weight with ethyl acetate 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., alkali metal salt (ionic compound) 3 SO 2 ) 2 : liTFSI, tokyo chemical industry co). 0.15 part by weight of an isocyanate-based crosslinking agent (trade name "CORONATE HX", manufactured by Tosoh Co., ltd.): 3.4 parts by weight as crosslinking catalyst0.006 parts of an emilizer OL-1 (Tokyo Fine Chemical co., ltd.): 0.01 part by weight of the solution of the methacrylic copolymer (2) obtained in production example 2 in terms of solid content, and further, a polyoxyalkylene glycol compound (SANNIX GP-250, sanyo chemical Co., ltd.) was added so that the solid content of the whole was 20% by weight based on 100 parts by weight of the solid content of the solution of the acrylic copolymer (1) obtained in production example 1, and the mixture was diluted with toluene and stirred with a disperser to obtain an adhesive composition (1).
The obtained adhesive composition (1) was applied to a substrate "Lumirror S10" (thickness 38 μm, manufactured by Toray Industries, inc.) containing a polyester resin by a spray coater so that the thickness after drying became 10 μm, and cured and dried at a drying temperature of 130 ℃ for 20 seconds. In this way, an adhesive layer is formed on the substrate. Then, a surface protection film (1) was obtained by bonding a surface treated with silicone to a substrate made of a polyester resin, which was treated with silicone to a thickness of 19 μm, to the surface of the adhesive layer.
The results are shown in Table 1.
Example 2: adhesive composition (2) and production of surface protective 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 protective 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 protective film (4)
The amount of CORONATE HX was changed to 1.7 parts by weight in terms of solid content, and GP250 was changed to GP600 (polyoxypropylene glycerol ether, mn=600, manufactured by san yo chemical Co., ltd.): an adhesive composition (4) and a surface protective film (4) were obtained in the same manner as in example 1 except for 1 part by weight.
The results are shown in Table 1.
Example 5: adhesive composition (5) and production of surface protective film (5)
The amount of CORONATE HX was changed to 1.6 parts by weight in terms of solid content, and GP250 was changed to GP1000 (polyoxypropylene glycerol ether, mn=1000, manufactured by san yo chemical Co., ltd.): an adhesive composition (5) and a surface protective film (5) were obtained in the same manner as in example 1 except for 1 part by weight.
The results are shown in Table 1.
Example 6: adhesive composition (6) and production of surface protective film (6)
The amount of CORONATE HX was changed to 3.6 parts by weight in terms of solid contentGP250 was changed to Adeka Polyether EDP to 300 (manufactured by ADEKA, N', -tetrakis (2-hydroxypropyl) ethylenediamine, mn=300): 1 part by weight of a crosslinking catalyst, instead of EMBILIZER OL-1, was changed toAn adhesive composition (6) and a surface protective film (6) were obtained in the same manner as in example 1 except that 0.01 parts by weight of Zinc acetylacetonate monohydrate was used as the substrate.
The results are shown in Table 1.
Example 7: production of adhesive composition (7) and surface protective film (7) as polyol (a), PREMINOL S3011 (manufactured by asahi corporation, mn=10000) was used as polyol having 3 OH groups: 85 parts by weight of sanmix GP-3000 (manufactured by sanyo chemical company, 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 CORONATE HX (Nippon Polyurethane Industry co., ltd.) as a polyfunctional alicyclic isocyanate compound was used as the polyfunctional isocyanate compound (B): 13.5 parts by weight of a catalyst (trade name, manufactured by Japanese chemical industry Co., ltd.): ): 0.04 parts by weight of ethyl acetate as a diluting solvent: 210 parts by weight of a resin was stirred with a disperser to obtain adhesive composition (7).
The obtained adhesive composition (7) was applied to a substrate "Lumirror S10" (thickness 38 μm, manufactured by Toray Industries, inc.) formed of a polyester resin by a spray coater so that the thickness after drying became 10 μm, and cured and dried at a drying temperature of 130 ℃ for 2 minutes. In this way, an adhesive layer is formed on the substrate. Then, a surface protection film (7) was obtained by bonding a surface treated with silicone to a substrate made of a polyester resin, the surface of which was treated with silicone to a thickness of 19 μm, to the surface of the adhesive layer.
The results are shown in Table 1.
Comparative example 1: adhesive composition (C1) and production of 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, an organosiloxane having an oxyalkylene chain as a silicone component (KF-353, manufactured by singe chemical industry co.) was added and diluted 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., alkali metal salt (ionic compound) 3 SO 2 ) 2 : liTFSI, tokyo chemical industry co). 0.15 part by weight of a solution of the methacrylic copolymer (2) obtained in production example 2, which was 0.5 part by weight of an isocyanate-based crosslinking agent (trade name "CORONATE HX", manufactured by eastern co., ltd.) and 0.02 part by weight of an emilizer OL-1 (Tokyo Fine Chemical co., manufactured by ltd.) as a crosslinking catalyst, in terms of solid content, was diluted with toluene so that the solid content of the whole became 20% by weight, and stirred with a disperser to obtain an adhesive composition (C1).
The obtained adhesive composition (C1) was applied to a substrate "Lumiror S10" (thickness: 38 μm, manufactured by Toray Industries, inc.) formed of a polyester resin by a spray coater so that the thickness after drying became 15 μm, and cured and dried at a drying temperature of 130℃for 20 seconds. In this way, an adhesive layer is formed on the substrate. Then, a surface protective film (C1) was obtained by bonding a surface treated with silicone to a substrate made of a polyester resin, the surface of which was treated with silicone to a thickness of 19. Mu.m.
The results are shown in Table 1.
Comparative example 2: production of adhesive composition (C2) and surface protective film (C2)
The solution of the acrylic copolymer (2) obtained in production example 2 was diluted with ethyl acetate to 20% by weight, and to 100 parts by weight of this solution, an organosiloxane (trade name: KF6004, manufactured by singe chemical industry co., ltd.) having a polyoxyalkylene chain in the main chain was added to dilute the solution to 10% by weight: 0.8 part by weight of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo chemical Co., ltd.) was diluted with ethyl acetate to a 10% by weight solution: 0.2 part by weight of an isocyanate-based crosslinking agent (trade name: CORONATE L, manufactured by Tosoh Co., ltd., 75% by weight): 0.8 part by weight of an emillizer OL-1 (Tokyo Fine Chemical co., ltd.): 0.02 parts by weight of the binder composition (C2) was obtained by diluting with toluene so that the total solid content became 20% by weight and stirring with a disperser.
The obtained adhesive composition (C2) was applied to a substrate "Lumirror S10" (thickness 38 μm, manufactured by Toray Industries, inc.) formed of a polyester resin by a spray coater so that the thickness after drying became 10 μm, and cured and dried at a drying temperature of 130 ℃ for 20 seconds. In this way, an adhesive layer is formed on the substrate. Then, a surface protective film (C2) was obtained by bonding a surface treated with silicone to a substrate made of a polyester resin, the surface of which was treated with silicone to a thickness of 19. Mu.m.
The results are shown in Table 1.
TABLE 1
Industrial applicability
The surface protective film of the present invention may 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. Substrate layer
2. Adhesive layer
10. Surface protective film
A polarizing member
B1 1 st transparent protective film
B2 2 nd transparent protective film
R1 st roller
R2 nd roller
M angle changing means

Claims (15)

1. A surface protective film comprising an adhesive layer and a base material layer,
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),
when the free induction decay signal of the adhesive layer obtained by pulse NMR measurement is separated into 2 components by nonlinear least square method, the component with short relaxation time is set as hard component (S), the component with long relaxation time is set as soft component (L), and spin-spin relaxation time T2 (L) of proton of soft component (L) measured at 30deg.C 30 Spin-spin relaxation time T2 (L) of proton with soft component (L) measured at 60 DEG C 60 Ratio T2 (L) 60 /T2(L) 30 Is 2.15 to 3.05 percent,
the shear adhesion of the surface protection film is 10N/cm 2 The above-mentioned steps are carried out,
the high-speed peeling force of the surface protection film is below 0.8N/25 mm.
2. The surface protective film according to claim 1, wherein the thickness of the adhesive layer is 1 μm to 500 μm.
3. The surface protective film according to claim 1 or 2, wherein the thickness of the base material layer is 1 μm to 500 μm.
4. The surface-protecting film according to claim 1 or 2, wherein the (meth) acrylic copolymer (a) is formed by polymerization from a composition (a) comprising: (a 1) an alkyl (meth) acrylate having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (a 2) a (meth) acrylate having an OH group.
5. The surface-protecting film according to claim 4, wherein the composition (a) contains (meth) acrylic acid.
6. The surface-protecting film according to claim 1 or 2, wherein the polyfunctional alcohol (C) has a functional group number of 3 to 6.
7. The surface-protecting film according to claim 1 or 2, wherein the polyfunctional alcohol (C) has a number average molecular weight of 50 to 10000.
8. The surface-protecting film according to claim 1, wherein the adhesive composition comprises a (meth) acrylic copolymer (B) formed by polymerization from a composition (B) comprising an alkyl (meth) acrylate in which the alkyl group of the (B1) alkyl ester moiety is an alicyclic hydrocarbon group.
9. The surface-protecting film according to claim 8, wherein the composition (b) comprises an alkyl (meth) acrylate having 1 to 3 carbon atoms in the alkyl group of the (b 2) alkyl ester moiety.
10. The surface-protecting film according to claim 8 or 9, wherein the composition (b) comprises thiol.
11. The surface-protecting film according to claim 8 or 9, wherein the Tg of the (meth) acrylic copolymer (B) is 50 to 250 ℃.
12. The surface protective film according to claim 8 or 9, wherein the (meth) acrylic copolymer (B) has a weight average molecular weight of 1000 to 30000.
13. The surface protective film according to claim 1 or 2, wherein the adhesive composition comprises an ionic liquid.
14. The surface protective film according to claim 1 or 2, wherein the number of bubbles generated after high-temperature high-pressure treatment is 10 or less.
15. The surface protective film according to claim 1 or 2, 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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