WO2008035709A1 - Composition adhésive enlevable de type à solvant et produit adhésif enlevable - Google Patents

Composition adhésive enlevable de type à solvant et produit adhésif enlevable Download PDF

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Publication number
WO2008035709A1
WO2008035709A1 PCT/JP2007/068181 JP2007068181W WO2008035709A1 WO 2008035709 A1 WO2008035709 A1 WO 2008035709A1 JP 2007068181 W JP2007068181 W JP 2007068181W WO 2008035709 A1 WO2008035709 A1 WO 2008035709A1
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Prior art keywords
polymer
pressure
low
sensitive adhesive
parts
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PCT/JP2007/068181
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English (en)
Japanese (ja)
Inventor
Masahiko Saito
Shigeru Oka
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Nippon Shokubai Co., Ltd.
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Priority claimed from JP2006256312A external-priority patent/JP5006608B2/ja
Application filed by Nippon Shokubai Co., Ltd. filed Critical Nippon Shokubai Co., Ltd.
Priority to CN2007800331816A priority Critical patent/CN101511961B/zh
Publication of WO2008035709A1 publication Critical patent/WO2008035709A1/fr

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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C09J131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2431/00—Presence of polyvinyl acetate
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to a re-peeling adhesive product that is re-peeled after being attached to an adherend and then peeled again, and exhibits excellent peelability even at high-speed peeling, and the adhesive product is produced.
  • the present invention relates to a solvent-type pressure-sensitive adhesive composition. More specifically, the present invention relates to a re-peeling adhesive product for protecting the surface of optical members such as optical polarizing plates (TAC), retardation plates, EM 1 (electromagnetic wave) shield films, antiglare films, antireflection films, etc. Is.
  • optical members such as optical polarizing plates (TAC), retardation plates, EM 1 (electromagnetic wave) shield films, antiglare films, antireflection films, etc. Is.
  • optical films having various functions such as optical polarizing plates (TAC), retardation plates, EMI (electromagnetic wave) shield films, antiglare films, antireflection films, etc. Etc. are laminated and used. These optical films have a protective film affixed to the surface in order to prevent damage to the surface during the display manufacturing process and performance inspection stage. Stripped and removed in the panel assembly process.
  • TAC optical polarizing plates
  • EMI electrostatic wave
  • Japanese Patent Application Laid-Open No. 2005-146151 discloses a high Tg (meth) atari which has no adhesiveness at room temperature. By blending a low molecular weight polymer with a low Tg (meth) acrylic polymer with sufficient adhesive strength, there is no lifting or peeling (having a certain level of adhesiveness), and high-speed peelability is good. Further, a pressure sensitive adhesive for a protective film is disclosed.
  • the adhesive product for the protective film as described above is designed to have a considerably lower adhesive strength (slight adhesion) than a general adhesive product on the premise that it is peeled off.
  • Tg of the high ⁇ g polymer is too high, it is inherently at a low level of adhesive strength, so that the adhesiveness at low temperatures is almost lost or the crosslinking progresses over time and sticks to the adherend. It sometimes caused the inconvenience of not sticking.
  • the pressure-sensitive adhesive for the purpose of being applied to the surface protective film of an optical film, the pressure-sensitive adhesive is excellent in high-speed peelability and has low haze and hardly causes troubles such as adherend contamination.
  • a solvent-type re-peeling pressure-sensitive adhesive composition capable of forming a layer was found, and an object was to provide a re-peeling pressure-sensitive adhesive product having good characteristics.
  • the solvent-based re-peeling pressure-sensitive adhesive composition of the present invention has a high Tg polymer (A) having a glass transition temperature (Tg) of o ° c or higher and a Tg lower than this high Tg polymer, A solvent-type re-peeling pressure-sensitive adhesive composition containing a low-Tg polymer (B) exhibiting pressure adhesion and a solvent, wherein a high-Tg polymer (A) and a low Tg are used in the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive product for re-peeling of the present invention is characterized in that a pressure-sensitive adhesive layer obtained from the solvent-based re-peeling pressure-sensitive adhesive composition is formed on at least one side of a support substrate. ing.
  • FIG. 1 is an SEM photograph (sea-island structure) of a coating film of an adhesive polymer solution obtained in Synthesis Example 1.
  • the solvent-based re-peeling pressure-sensitive adhesive composition according to the present invention becomes a pressure-sensitive adhesive product by drying (removing the solvent), and has a 180 ° adhesive strength in low-speed peeling against an acrylic plate measured under the conditions described later. Refers to the case of 10N / 25mm or less.
  • the “polymer” in the present invention includes not only homopolymers but also copolymers and copolymers of three or more.
  • the “monomer” of the present invention is an addition polymerization type monomer.
  • the first essential component in the solvent-based re-peeling pressure-sensitive adhesive composition of the present invention is a high Tg polymer (A) having a glass transition temperature (Tg) of 0 ° C or higher.
  • Tg glass transition temperature
  • the Tg of the polymer can be determined by DSC (Differential Scanning Calorimetry), DTA (Differential Thermal Analysis), and TMA (Thermomechanical Measurement).
  • DSC Denential Scanning Calorimetry
  • DTA Denential Thermal Analysis
  • TMA Thermomechanical Measurement
  • the Tg of homopolymers is described in various literatures (for example, polymer handbooks)
  • the Tg of copolymers is calculated from the following formula using Tg (K) of various homopolymers and mass fraction (W) of monomers. Finding what you want.
  • Tg Tg (K) of homopolymer of each monomer
  • the Tg of the main homopolymer is 105.85 ° C for polyacrylic acid, 9.85 ° C for polymethyl acrylate, 24.15 ° C for polyethyl acrylate, and poly n butyl acrylate. -54.15 ° C, Poly-2-Hethinoreta Talelate (70.00 ° C, Poly-2Hydroxyethylaretalate) 85 ° C, poly 4-hydroxybutyl attalate is 3 ⁇ 00 ° C, polymethylmetatalylate is 104 ° 85 ° C: Polyacetate, Ninole, 30. 00 ° C :, Polybenzenore 6. 00 ° C: 125 ° C for Polynitronitroré and 100 ° C for Polystyrene.
  • the high Tg polymer (A) used in the present invention is not particularly limited as long as Tg is 0 ° C or higher, and may be a homopolymer or a polymer obtained by copolymerizing two or more monomers.
  • Tg is preferably 10 ° C or higher, more preferably 20 ° C or higher, and further preferably 30 ° C or higher.
  • the adhesive strength may be insufficient, so less than 80 ° C is preferred 75 ° C or less
  • the preferred temperature is 70 ° C or less.
  • the high Tg polymer (A) of the present invention is an essential component for improving the high-speed peelability.
  • the preferred composition is different.
  • the high Tg polymer when haze is emphasized is (A-1)
  • the high Tg polymer when emphasis is placed on adherend contamination control is (A-2).
  • the high Tg polymer (A-1) has units derived from butyl acetate! /.
  • the high Tg polymer (A-1) is preferably obtained from a raw material monomer having 70% by mass or more of butyl acetate.
  • the amount of butyl acetate is more preferably 90% by mass or more. Most preferred in terms of haze
  • the high Tg polymer (A-1) is poly (butyl acetate) (bule acetate homopolymer). If polyacetic acid bule is used as a high Tg polymer (A-1), the haze of the resulting adhesive layer can be reduced to 2% or less, and surface protection of optical films that require high transparency is required. It is suitable as a film.
  • the homopolymer has a high Tg.
  • (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, acrylate, styrene Etc. are preferably used in combination with butyl acetate.
  • Monomers that can be used as raw material monomers for the low Tg polymer (B) described below can also be used if the type and amount are selected so that the Tg of the high Tg polymer (A-1) is 0 ° C or higher. .
  • the high Tg polymer (A-2) having a relatively low molecular weight that causes adherend contamination is increased in molecular weight, thereby suppressing adherend contamination.
  • the functional group include a hydroxyl group, a carboxyl group, an amino group, an amide group, and an epoxy group.
  • a functional group-containing monomer may be used as a raw material monomer for the high Tg polymer (A-2).
  • Examples of functional group-containing monomers include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-h
  • Hydroxyl group-containing (meth) acrylates such as mono (meth) acrylate of polyester diol that can also be used with taric acid and propylene glycol; unsaturated carboxylic acids such as (meth) acrylic acid, cinnamate and crotonic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; carboxy group-containing monomers such as monoesters of these unsaturated dicarboxylic acids; amino groups, amide groups, epoxy groups, etc. And meta) atarylates.
  • hydroxyl group-containing (meth) acrylates having a hydroxyl group as a functional group are preferred.
  • the monomers in this group have better cross-linking reactivity and conformability, so if you want to reduce the amount of cross-linking agent or if suitability for adherends is important, 2-hydroxyethyl (meth) atari
  • the hydroxyl group is bonded to an alkyl group having a larger number of carbon atoms than the rate (propyl group or higher)! /
  • (meth) acrylate eg, 4-hydroxy pentanol (meth) acrylate
  • These functional group-containing monomer in the raw material monomer 100 mass 0/0 of the high Tg polymer (A- 2), 0.; is preferably set to 1-10% by mass!. If the amount of the functional group-containing monomer is less than 0.1% by mass, the amount of the functional group in the high Tg polymer (A-2) is decreased, and the effect of suppressing adherend contamination is not sufficiently exhibited. Absent. On the other hand, if it exceeds 10% by mass, the adhesive strength of the adhesive and the wettability to the adherend tend to decrease, which is not preferable.
  • the amount of the functional group-containing monomer is more preferably 0.3 to 8% by mass, and further preferably 0.5 to 6% by mass.
  • the copolymerization partner of the functional group-containing monomer any known radical polymerizable monomer can be used as long as the Tg of the high Tg polymer (A-2) is 0 ° C or higher.
  • the high-Tg polymer (A-1) the use of butyl acetate reduces the haze of the adhesive layer and is suitable as a surface protective film for optical films. Therefore, the high Tg polymer (A-2) is preferably obtained from a raw material monomer that necessarily contains butyl acetate and the functional group-containing monomer.
  • acetic acid vinyl Honoré or 70 to 99.9 mass 0/0 Ca
  • Methyl acrylate may be used as a copolymerization partner for the functional group-containing monomer. Adhesiveness and familiarity are improved. Methyl acrylate is preferably 70-99.9% by weight, more preferably 80-99.9% by weight, and more preferably 90-99.9% by weight.
  • Refractive index control monomer is a monomer used to bring the refractive index of a low Tg polymer close to that of a high Tg polymer.
  • high-Tg polymer (A-2) is synthesized from methyl acrylate and hydroxyl group-containing monomarker, it is added to 2-ethyl hexyl acrylate, butyl acrylate and 2-hydroxyethyl acrylate.
  • the refractive index of the high Tg polymer (A-2) and that of the low Tg polymer (B) can be brought close to each other.
  • the haze can be reduced to 3% or less.
  • high Tg polymer (A-2) For the synthesis of high Tg polymer (A-2), other monomers that can be used in addition to butyl acetate, methyl acrylate, and the above functional group-containing monomers include (meth) acrylic acid having a high homopolymer Tg, Methyl methacrylate, ethyl (meth) acrylate, acrylonitrile, styrene and the like are preferable.
  • a monomer that can be used as a raw material monomer for the low Tg polymer described below can also be used if the type and amount are selected so that the Tg of the high Tg polymer (A-2) is 0 ° C or higher.
  • a preferred embodiment of the high Tg polymer (A-2) is a polymer synthesized from butyl acetate and 2-hydroxyethyl acrylate and / or 4-hydroxybutyl acrylate. The ability to reduce haze to 3% or less while suppressing adherend contamination. Further, as described above, if a monomer for controlling the refractive index is used during the synthesis of the low Tg polymer (B), it is synthesized from methyl acrylate and 2-hydroxyethyl acrylate and / or 4-hydroxy butyl acrylate. High Tg polymer (A-2) can also be preferably used because haze can be reduced to 3% or less while suppressing adherend contamination.
  • polyacrylic acid is 1 ⁇ 5270, polymethyl phthalate 1, 4720, polyurethane tantalate 1, 4685, poly ⁇ -f, chinoleate talate m 4660, polymethylolene methacrylate 1 4900, poly-2-hydroxyhexylene chloride m. 4650, poly-2-hydroxyethylenol talelate (1/4480, poly-2-hydroxyethyl methacrylate) (MA 1.5119, poly 4-hydroxyph, chinolea talylate (MA 1.4520, poly oxalate, Nino acrylate 1. 4665, polybenzeno acrylate 1.5 or 5132.
  • the homopolymer has a high Tg, such as (meth) acrylic acid, methyl methacrylate, ethyl (meth) acrylate, acrylonitrile, styrene, etc. What is necessary is just to comprise a high Tg polymer (A) so that the said Tg range may be satisfied.
  • the molecular weight of the high Tg polymer (A) (hereinafter, simply referred to as high Tg polymer (A) means both high Tg polymer (A-1) and high Tg polymer (A-2)).
  • Mass average molecular weight ( Mw) is preferably from 2000 to about 100,000. More preferably, it is about 40,000 to 90,000.
  • the second essential component contained in the solvent-based re-peeling pressure-sensitive adhesive composition of the present invention is a low Tg polymer (B) exhibiting pressure-sensitive adhesiveness.
  • This low Tg polymer (B) is required to be lower than the Tg (0 ° C or higher) of the above high Tg polymer (A), and Tg force S0 ° Preferably it is less than C. More preferably, it is 1-20 ° C or less, and further preferably 135 ° C or less. However, if the Tg of the low Tg polymer (B) is lower than -80 ° C, the cohesive force tends to decrease, and the adhesive residue tends to occur.
  • the alkyl (meth) acrylate is necessary for ensuring adhesive strength, and the functional group-containing monomer is a monomer for introducing a functional group for reacting with a crosslinking agent described later into the low Tg polymer (B).
  • the functional group-containing monomer any of the monomers exemplified for the high Tg polymer (A-2) can be used.
  • the hydroxyl group-containing monomer (meth) Atallate is preferred.
  • the use amount thereof is preferably from 0.;! To 10% by mass in 100% by mass of the raw material monomer as in the case of the high Tg polymer (A-2).
  • the amount of the functional group-containing monomer is less than 0.1% by mass, the amount of the functional group in the low Tg polymer (B) is decreased, the speed of the crosslinking reaction is decreased, or the high-speed adhesive force is too high. If it exceeds 20% by mass, the adhesive strength of the pressure-sensitive adhesive and the wettability to the adherend tend to decrease, such being undesirable.
  • the use amount of the functional group-containing monomer is more preferably 0.3 to 8% by mass, and further preferably 0.5 to 6% by mass.
  • the alkyl (meth) acrylate which is the main constituent of the low Tg polymer (B) preferably has an alkyl group having a carbon number power of ⁇ 12 from the viewpoint of adhesive properties.
  • This carbon number is preferably 4 to 10; more preferably 4 to 8. If the carbon number is less than 4 (3 or less), or exceeds 12 (13 or more), the adhesive strength may decrease.
  • Atari rate is preferably employed in the range of 50-99. 9 mass 0/0. More preferably «60-99. 7 mass 0/0, even more preferably 70 to 99 ⁇ 5 weight 0/0.
  • Anolequinolate (meth) If the amount of attalylate used is within the above range, the resulting adhesive exhibits sufficient adhesive strength and tackiness, but if it is less than 50% by mass, the adhesive strength and adhesion are reduced. The wettability to the body may be insufficient, and if it exceeds 99.9% by mass, the amount of the functional group-containing monomer that becomes a cross-linking point is too small, and the high-speed adhesive force may become too large.
  • the other monomer is a monomer that can be copolymerized with the alkyl (meth) acrylate and the functional group-containing monomer, and other monomers.
  • the most preferred low Tg polymer (B)! / Embodiments, if the high Tg polymer (A) contains acetic acid Byuruyu knit as the main component (70 mass 0/0 or more), 2- Echiru Hexyl Relay And a polymer obtained from a raw material monomer mixture containing butyl acrylate, 2-hydroxyethyl acrylate and / or 4-hydroxy butyl acrylate.
  • This polymer has good adhesive properties and is close to the refractive index of high Tg polymer (A), the main component of which is a butyl acetate unit, so it can reduce the haze of the resulting adhesive layer.
  • 2-ethyl hexyl acrylate, butinorea acrylate and hydroxy acetyl acrylate is 100% by mass
  • 2-ethyl hexyl acrylate is 20 to 80% by mass
  • butyl acrylate is 20%.
  • the total content of ⁇ 80 mass%, hydroxyethyl acrylate and 4-hydroxybutyl acrylate is preferably 0.5 to 6 mass%.
  • other monomers can be used in combination as described above.
  • the high Tg polymer is a high Tg polymer (A-1)
  • Monomers other than ethyl acrylate and 4-hydroxybutyl acrylate are preferably 10% by mass or less.
  • the most preferred embodiment of the low Tg polymer (B) is 2-ethyl hexyl acrylate and butyrate. This is a copolymer of noreatalylate, 2-hydroxyethyl acrylate and / or 4-hydroxybutyl acrylate and benzyl acrylate.
  • the haze of the pressure-sensitive adhesive layer can be reduced to 3% or less by using benzyl acrylate in combination.
  • the sum of these monomers is 100 mass%, 2 Echiru hexyl Atari rate from 20 to 80 weight 0/0, butyl Atari rate from 20 to 80 weight 0/0, hydroxy E chill Atari rate and 4 over hydroxybutyl Atari rate from 0.5 to 6 weight in total 0/0, benzyl Atari Les chromatography DOO is preferably 5 to 20 wt%.
  • the low Tg polymer (B) preferably has an Mw of 200,000 or more from the viewpoint of improving the adhesive properties.
  • Mw molecular weight of only the low Tg polymer (B) cannot be measured, but a mixture of the high Tg polymer (A) and the low Tg polymer (B) (Draft product).
  • the total Mw is preferably 100,000 to 700,000.
  • a more preferable Mw range is 150,000 to 650,000, and a more preferable Mw range is 200,000 to 600,000.
  • the high Tg polymer (A) and the low Tg polymer (B) are incompatible because of different Tg and different compositions.
  • the high Tg polymer (A) and the low Tg polymer (B) do not form a sea-island structure. I have to.
  • the sea-island structure is in a microphase-separated state, and the larger amount is the sea (continuous phase).
  • the amount of the low Tg polymer (B) is increased to disperse the low Tg polymer (B) as sea (continuous phase) and the high Tg polymer (A) as islands.
  • the content of the high Tg polymer (A) is required to be 1% by mass or more, and if it is less than this, the above effect will be insufficient. More preferably, it is 3% by mass or more, and further preferably 4% by mass or more. However, if the amount is too large, adhesive strength and wettability to the adherend may be insufficient.
  • the pressure-sensitive adhesive layer obtained by applying and drying the pressure-sensitive adhesive composition was measured using an optical microscope, a transmission electron microscope, a scanning electron microscope, a phase difference, and the like.
  • an optical microscope a transmission electron microscope
  • a scanning electron microscope a phase difference
  • the preferred form of the sea-island structure is such that the island-like portions are almost spherical and dispersed in the continuous phase (sea), and the average diameter of each island-like substance is about 0.;! To 10 m.
  • the presence or absence of such a sea-island structure can also be observed using an optical microscope, a phase contrast microscope, and a polarizing microscope.
  • Tg is 2 Check if they are observed.
  • the tan ⁇ of the dynamic viscoelasticity is obtained by, for example, using a rheometer (manufactured by TI-A Instruments Co., Ltd .; “ARES”) and by using the shear mode, paraplate method (8 mm ⁇ ), the angular vibration frequency 6. / s, measuring temperature range 50 ⁇ ;
  • a high-Tg polymer (A) and a low-Tg polymer (B) having an approximate refractive index are used, and a sea-island structure in which both are phase-separated microscopically has a haze of 3% or less. Adhesive products with excellent transparency can be obtained.
  • the haze can be measured, for example, with a turbidimeter.
  • the haze of this invention employ
  • support base material such as a polyethylene terephthalate
  • the method for producing the solvent-type re-peeling pressure-sensitive adhesive composition of the present invention will be described.
  • the blending method is a method in which a high Tg polymer (A) and a low Tg polymer (B) are polymerized separately, and then both are mixed (blended).
  • the polymerization method is not particularly limited, but solution polymerization is simple.
  • the high Tg polymer (A) and the low Tg polymer (B) are polymerized with the same or compatible solvent, they can be blended in solution, eliminating the need for a solvent removal step during blending. Convenient. When blending, it is preferable to stir at high speed with a disperser or the like to form a sea-island structure.
  • the pressure-sensitive adhesive composition of the present invention is prepared by a blending method, when the total amount of non-volatile components of the high Tg polymer (A) and the low T g polymer (B) is 100% by mass, the high Tg polymer (A) The amount is preferably 4 to 20% by mass. In this method, when the high Tg polymer (A) is dispersed in the low Tg polymer, the amount of the high Tg polymer (A) can be reduced because a clear sea-island structure is adopted.
  • the second method is a two-stage polymerization method.
  • this two-stage polymerization method all the monomers for the high Tg polymer (A) (hereinafter referred to as “monomer (A)”) are polymerized by solution polymerization, and then the high Tg polymer (A) solution
  • the monomer for low Tg polymer (B) (hereinafter referred to as “monomer (B)”) is polymerized in the presence.
  • the pressure-sensitive adhesive composition obtained by this two-stage polymerization method is more stable than the pressure-sensitive adhesive composition obtained by the blend method (high Tg polymer (A) and low Tg polymer (B) are difficult to separate). Is excellent.
  • the monomer (B) is polymerized, a part of the polymer is formed such that the low Tg polymer (B) is grafted to the high Tg polymer (A), which has an affinity for both the sea and the islands. It is thought to stabilize the island by exerting its surfactant action.
  • the island diameter is about 0.3 to 10 ⁇ .
  • the two-stage polymerization method it is preferable to start adding the monomer (B) to the reaction vessel after the polymerization rate of the monomer (A) reaches about 70 to 95% by mass. This method causes separation during storage of the composition.
  • the polymerization rate (mass%) is determined by the monomer in the reaction vessel It is the ratio of the mass converted to non-volatile content, and can be easily obtained by measuring the non-volatile content.
  • the low Tg monomer (B) is preferably added dropwise to the reactor together with the polymerization initiator. Increase the molecular weight with the force S.
  • the separately polymerized high Tg polymer (A) may be added after the two-stage polymerization of the high Tg polymer (A) and the low Tg polymer (B) is completed.
  • the composition of the post-added high Tg polymer (A) is preferably the same as the initially polymerized high Tg polymer (A) from the viewpoint of dispersion stability, but the molecular weight may be different. Furthermore, the effect of reducing the adhesive strength of high-speed peeling appears
  • the third method is a combination of the two-stage polymerization method and the post-addition of the high Tg polymer (A).
  • the high Tg polymer (A) to be charged by the two-stage polymerization and the high Tg for post-addition are used.
  • polymer (A) is polymerized together.
  • a part of the obtained high Tg polymer (A) is charged into a reaction vessel for synthesizing the low Tg polymer (B), and then the monomer (B) is polymerized.
  • This is a two-stage polymerization in a broad sense.
  • a graft product in which the low Tg polymer (B) is grafted to the high Tg polymer (A) is formed.
  • This method has the advantage that the high Tg polymer (A) to be charged in the reaction vessel in advance when polymerizing the low Tg polymer (B) and the high Tg polymer (B) to be added later can be polymerized simultaneously.
  • the amount of the high Tg polymer (A) charged during the polymerization of the low Tg polymer (B) is 100% by mass of the total amount of the high Tg polymer (A) and the monomer (B); ! ⁇ 10% by mass is preferable. Storage stability is improved.
  • the high Tg polymer (A) (including the graft content) out of the total non-volatile content of 100% by mass of the high Tg polymer (A) and the low Tg polymer (B) It is preferable to add the high Tg polymer (A) afterwards so that the amount of the polymer becomes 4 to 35% by mass.
  • the post-addition may be performed immediately after the polymerization of the low Tg polymer (B), but may be any time as long as it is actually mixed with a crosslinking agent and applied. The same applies when post-added by the second-stage polymerization method of the second method described above.
  • the solvent used in the solution polymerization include aromatic hydrocarbons such as toluene and xylene; aliphatic esters such as ethyl acetate and butyl acetate; Examples include alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as hexane and pentane, etc., but are not particularly limited as long as the polymerization reaction is not inhibited. Absent. These solvents may be used alone or in combination of two or more. What is necessary is just to determine the usage-amount of a solvent suitably.
  • the solvent-type re-peeling adhesive composition of the present invention contains a solvent as an essential component, but it is preferable to use the same solvent as the polymerization solvent. This is because the power obtained by the completion of the polymerization is directly used as a raw material for the solvent-type re-peeling pressure-sensitive adhesive composition.
  • Reaction conditions such as a polymerization reaction temperature and a reaction time are not particularly limited as long as they are appropriately set according to, for example, the composition and amount of the monomer.
  • the reaction pressure is not particularly limited, and any of normal pressure (atmospheric pressure), reduced pressure and increased pressure may be used.
  • the polymerization reaction is desirably performed in an atmosphere of an inert gas such as nitrogen gas.
  • the polymerization catalyst (polymerization initiator) is not limited, but examples thereof include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydride peroxide, t-butyl.
  • Organics such as peroxyctoate, t-butylperoxybenzoate, lauroyl peroxide, trade name "Nyper B MT-K40J (manufactured by NOF Corporation; m mixture of toluoyl peroxide and benzoyl peroxide)"
  • Known compounds such as peroxides, azobisisobutyronitrile, azo compounds such as “ABN-E” [Nippon Hydrazine Kogyo; 2, 2'-azobis (2-methylbutyronitrile)], etc. Things can be used.
  • known molecular weight regulators represented by mercaptans such as dodecyl mercabtan may be used! /.
  • the pressure-sensitive adhesive composition obtained by the blend method as the first method and the pressure-sensitive adhesive composition obtained by using the second-stage polymerization method as the second or third method are subjected to the following separation degree check.
  • a high-Tg polymer (A), a low-Tg polymer (B), and a solvent are prepared to prepare a solution having a nonvolatile content of 30% by mass, poured into, for example, a test tube and sealed, and then sealed at 25 ° C. What is necessary is just to check the separation state when left for a period of time.
  • the high-Tg polymer (A) and the low-Tg polymer (B) have a sea-island structure that is easy to phase-separate obtained by the blending method, they will separate after standing for 24 hours. If the obtained sea-island structure is difficult to separate, it will not separate at all in 24 hours! /.
  • the solution prepared by the above method may be cloudy as long as the cloudy state is uniform throughout the solution. After standing for 24 hours under the above conditions, two or more phases with transparent parts appearing at the top and bottom of the liquid column or with different turbidity If it is divided, it is determined that it is “separated”.
  • the mass ratio of the high Tg polymer (A) and the low Tg polymer (B) in the solution is within the above-mentioned preferred range.
  • the solvent that can be used for the separation degree check is not particularly limited as long as it is a solvent used at the time of coating, but is not limited to aromatic hydrocarbons such as toluene and xylene; aliphatic esters such as ethyl acetate and butyl acetate. And alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as hexane and pentane, and the like. These may be used alone or in admixture of two or more.
  • the pressure-sensitive adhesive composition of the present invention preferably contains a crosslinking agent.
  • a crosslinking agent a compound having two or more functional groups capable of reacting with a functional group of the high Tg polymer (A) and / or the low Tg polymer (B) is used.
  • the isocyanate compound has a preferred carboxyl group as a crosslinking agent
  • the isocyanate A compound, an epoxy compound, etc. are preferable.
  • the combination of a hydroxyl group and an isocyanate compound is most preferred.
  • Examples of the isocyanate compound include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene, hydrogenated diphenolate.
  • TDI tolylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • hexamethylene diisocyanate xylylene
  • hydrogenated diphenolate hydrogenated diphenolate.
  • Diisocyanate compounds such as methane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; Bullet polyisocyanate compounds: “Desmodur (registered trademark) IL”, “Desmodur (registered trademark) HL” (both manufactured by Bayer AG), “Coronate (registered trademark) EH” (Nippon Polyurethane Industry) Polyisocyanate compound having an isocyanurate ring known as “Sumidur (registered trademark) L” Adduct polyisocyanate compounds such as “Sumitomo Bayer Urethane Co., Ltd.”; Adduct polyisocyanate compounds such as “Coronate (registered trademark) L” (manufactured by Nippon Polyurethane); “Deyuranate (registered trademark) D201” ( It is possible to list polyisocyanate compounds such as Asahi Kasei Corporation.
  • Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexane diglycidyl ether, bisphenol A type epoxy resin, N, N, ⁇ ', N'— Examples thereof include tetraglycidyl 1-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethinole) cyclohexane, N, N-diglycidyl dilin, N, N-diglycidyl toluidine and the like.
  • cross-linking agents should be added so that the total amount of functional groups of the high Tg polymer (A) and the low Tg polymer (B) is 1 equivalent; Is preferred. If the amount of the cross-linking agent is too small, the resulting adhesive may have insufficient cohesive force to cause adhesive residue, but if it is too large, the adhesive force may be insufficient or the wettability to a rough surface may be reduced.
  • the amount of the crosslinking agent is more preferably 0.2 to 4 equivalents, still more preferably 0.3 to 2 equivalents.
  • the non-volatile content of the solvent-based re-peeling pressure-sensitive adhesive composition of the present invention is not particularly limited, but for example, it is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, Preferably it is 25-45 mass%. If the non-volatile content is less than 10% by mass, drying after application takes a long time, which may reduce productivity. On the other hand, if it exceeds 80% by mass, the viscosity of the whole composition becomes high, handling properties and coating properties are lacking, and there is a possibility that the practicality becomes poor.
  • the solvent for the pressure-sensitive adhesive composition any of the above-mentioned polymerization solvents can be used, and as described above, the same solvent as the polymerization solvent is preferred!
  • the compatibilizer is not particularly limited.
  • a block copolymer (graf) copolymer of (meth) acrylate and butyl acetate, a graft copolymer, or the like, or a compatibilizer by an ionic interaction (a compound or polymer having a specific functional group). Etc.) can be used.
  • the addition amount of the compatibilizer is preferably about 0 to 20 parts by mass per 100 parts by mass of the resin component (total amount of the polymer (A) and the polymer (B)) in the solvent-type re-peeling pressure-sensitive adhesive composition. .
  • the pressure-sensitive adhesive composition of the present invention is used for production of a re-peeling pressure-sensitive adhesive product.
  • Base material or An adhesive product adhesive tape or sheet in which an adhesive layer is formed on one side of the substrate by applying the adhesive composition on the release paper and forming a dry coating film on both sides of the substrate It is possible to obtain a pressure-sensitive adhesive product having a pressure-sensitive adhesive layer formed thereon, or a pressure-sensitive adhesive product having only a pressure-sensitive adhesive layer having no base material.
  • a method of applying a pressure sensitive adhesive composition on a release paper to form a pressure sensitive adhesive layer and then transferring it to a paper base material can be employed.
  • it is desirable to heat and dry under conditions where the solvent scatters for example, 50 to; 60 to 120 ° C for 60 to 180 seconds).
  • the base material examples include conventionally known papers such as fine paper, kraft paper, crepe paper, and dalasin paper; plastics such as polyethylene, polypropylene, polyester, polystyrene, polyethylene terephthalate, polychlorinated bure, and cellophane; Textile products such as cloth and non-woven fabric; laminates of these can be used.
  • the substrate is preferably a transparent film such as polyethylene terephthalate!
  • the method of applying the pressure-sensitive adhesive composition to the substrate is not particularly limited, and a known method such as a roll coating method, a spray coating method, or a dating method can be employed. In this case, any of a method of directly applying the pressure-sensitive adhesive composition to the base material, a method of applying the pressure-sensitive adhesive composition to a release paper, and then transferring the coated material onto the base material can be employed. After applying the pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer is formed on the substrate by drying.
  • a release paper may be stuck! /.
  • the surface of the adhesive can be suitably protected and stored.
  • the release paper is peeled off from the surface of the adhesive when the adhesive product is used.
  • a pressure-sensitive adhesive surface is formed on one side of a substrate such as a sheet or tape
  • a known release agent is applied to the back surface of the substrate to form a release agent layer. If the adhesive layer is placed inside and the adhesive sheet (tape) is wound in a roll shape, the adhesive layer comes into contact with the release material layer on the back surface of the substrate. Protection 'Saved.
  • the adhesive product for re-peeling obtained from the pressure-sensitive adhesive composition of the present invention has a 180 ° adhesive strength of 0.05—0.3 N / 25 mm, 30 m / min at a low speed of 0.3 m / min. In high-speed peeling, it is preferably 0.2 to 3 N / 25 mm. If the low-speed peel adhesive strength is in the above range, the optical part This is because if it is sufficient as a surface protective sheet for the material and the high-speed peel adhesive strength is in the above range, it can be peeled smoothly without causing inconveniences such as zipping.
  • a more preferable low-speed peeled rice occupying force is 0.06—0.2 N / 25 mm, and more preferably 0.0 07—0.15 N / 25 mm.
  • the more preferable high-speed peel adhesive strength is 0.3 to 2 N / 25 mm, and more preferably 0.5 to 1.5 N / 25 mm. If the value obtained by dividing the high-speed peel adhesive force by the low-speed peel adhesive force is 15.0 or less, an increase in the adhesive force during high-speed peel can be suppressed.
  • the 180 ° adhesive force was measured at 23 ° C using an adhesive product in which an adhesive layer having a thickness of 20 m was formed on a polyethylene terephthalate film substrate having a thickness of 38 m. The case value is adopted.
  • the part “/ 25 mm” means the width of the pressure-sensitive adhesive sheet that is pressure-bonded to the adherend.
  • the re-peeling pressure-sensitive adhesive product obtained from the pressure-sensitive adhesive composition using the high Tg polymer (A-2) has a low speed of 0.3 m / min when subjected to a 180 ° peel test on an acrylic plate. Adherent contamination does not occur even with peeling! /, (See Examples).
  • VAC butyl acetate
  • a polymer solution of a low Tg polymer was obtained in the same manner as in Synthesis Example 4 except that the monomer yarn was changed to 150 parts BA, 2EHA335 parts, and HEA15 parts.
  • a low Tg polymer solution was obtained in the same manner as in Synthesis Example 4 except that the monomer yarns were changed to 150 parts BA, 2EHA335 parts and HEA15 parts.
  • a low Tg polymer solution was obtained in the same manner as in Synthesis Example 4 except that the monomer yarns were changed to BA335 parts, 2EHA150 parts, and HEA15 parts.
  • a MMA-based high Tg polymer solution was obtained in the same manner as in Synthesis Example 8, except that 250 parts of MMA and 1.0 part of “thiocalcol 20” were used.
  • the 100% non-volatile content of the same low Tg polymer solution as in Synthesis Example 8 is mixed together so that the non-volatile content of this MMA high Tg polymer solution is 20 parts.
  • I got 9. As a result of observing the pressure-sensitive adhesive layer obtained from this pressure-sensitive adhesive polymer solution No. 9 using an optical microscope, it was confirmed that it had a sea-island structure.
  • Table 1 shows the synthesis method for each of the pressure-sensitive adhesive polymer solutions;! To 9, and Table 2 shows the characteristics.
  • the characteristic evaluation method is as follows.
  • GPC measurement apparatus Liquid Chromatography Model 510 (manufactured by Waters) was used under the following conditions.
  • THF Tetrahydrofuran
  • the pressure-sensitive adhesive polymer solution was taken, and the nonvolatile content was adjusted to 34% with ethyl acetate.
  • a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc .; thickness 3 8 111) was used as a supporting substrate, and the pressure-sensitive adhesive composition was applied so that the thickness after drying was 20 m.
  • An adhesive film was prepared by drying at 0 ° C. for 2 minutes. After sticking and protecting the adhesive surface with a PET film that had been subjected to a release treatment, it was cured in an atmosphere of 40 ° C for 3 days. The cured adhesive film was conditioned for 24 hours in an atmosphere of 23 ° C. and 65% relative humidity, and then cut to an appropriate length with a width of 25 mm to prepare a test tape. The release film was peeled off during the test.
  • PET polyethylene terephthalate
  • a 3 mm thick acrylic plate (standard test plate made by Nippon Test Panel Co., Ltd.) was used as the adherend, and the above test tape was placed on the acrylic plate in an atmosphere of 23 ° C and 65% relative humidity. 1 reciprocate and crimp. After standing for 25 minutes after crimping, the peel rate is 0.3 m / min for low speed peel and 30 m / min for high speed peel, and 180 ° peel adhesive strength in accordance with JIS K 6854 under an atmosphere of 23 ° C. It was measured. Table 2 also shows the low-speed peel adhesive strength, the high-speed peel adhesive strength, and the value obtained by dividing the high-speed peel adhesive strength by the low-speed peel adhesive strength (shown as “high speed / low speed”).
  • the haze (%) of the test tape was measured according to JIS K 7105.
  • the pressure-sensitive adhesive compositions of Examples 2 to 3 in which two-stage polymerization was carried out were excellent in storage stability without causing separation.
  • high Tg polymer (A-1) and low Tg polymer (B) are blended in a well-balanced manner. 0 or less. Since Comparative Example 1 consisted of only the low Tg polymer (B), the high-speed peel adhesive strength was too large. Even in Comparative Example 2 in which the high Tg polymer (A) and the low Tg polymer (B) were polymerized in a lump, the high-speed peel adhesive strength was high, and zippering occurred.
  • Example 5 and Reference Example 2 since a MMA-based polymer having a refractive index different from that of 2EHA or BA was used as the high Tg polymer (A), it was not very good for haze! However, in Reference Example 2, it was found that the Tg of the high Tg polymer (A) was too high, so that the peel force at low speed was too small and the adhesive strength might be insufficient.
  • An adhesive polymer solution No. 10 was obtained by adding 20 parts of the high Tg polymer ethyl acetate solution in a nonvolatile content to 100 parts of the nonvolatile content in the obtained graft polymer solution.
  • the pressure-sensitive adhesive layer obtained from this adhesive polymer solution No. 10 was observed using SEM, and as a result, it was confirmed that it had a sea-island structure (Fig. 1).
  • the upper side is polyethylene terephthalate (PET) of the base film, and the lower side is an adhesive layer.
  • a high Tg polymer was synthesized in the same manner as in Synthesis Example 10 except that the monomer composition for the high Tg polymer was changed as shown in Table 3.
  • the ratio of graft polymer to high Tg polymer was 100: 20 in non-volatile content.
  • a coating film was formed on a slide and observed with an optical microscope. As a result, it was confirmed that the structure was a sea-island structure.
  • Synthesis Example 12 and Synthesis Example 13 are examples in which the mixing ratio of the high Tg polymer obtained in Synthesis Example 11 and the graft polymer was changed. As a result of forming a coating film on the preparation using the pressure-sensitive adhesive polymer solutions No. 12 and 13 obtained in each example and observing with an optical microscope, it was confirmed that the structure was a sea-island structure.
  • a high Tg polymer solution and a graft polymer solution were obtained in the same manner as in Synthesis Example 11 except that the amount of DM used to synthesize the graft polymer was reduced to 0.15 part.
  • the ratio of graft polymer to high Tg polymer was 100: 20 in non-volatile content.
  • a high Tg polymer solution and a graft polymer solution were obtained in the same manner as in Synthesis Example 11, except that the amount of the high Tg polymer charged was reduced to 6 parts.
  • the ratio of graft polymer to high-Tg polymer was 100: 20 in terms of nonvolatile content, and both solutions were mixed to obtain adhesive polymer solution No. 15.
  • the structure was a sea-island structure.
  • a high Tg polymer solution was prepared in the same manner as in Synthesis Example 11. Next, a monomer for low Tg polymer was separately polymerized. In a flask equipped with a thermometer, stirrer, inert gas inlet tube, reflux condenser and dropping funnel, 36 parts BA, 2EHA 82.2 parts, HEA 1.8 parts, and ethyl acetate as low Tg polymer monomers 144 parts were charged and mixed well. While the nitrogen gas was circulated under stirring, the internal temperature of the flask was raised to 82 ° C., and 0.15 part of the above-mentioned “Nyper (registered trademark) BMT-K40” was put into the flask to initiate the polymerization.
  • “Nyper (registered trademark) BMT-K40” was put into the flask to initiate the polymerization.
  • the low Tg polymer solution and the high Tg polymer solution were mixed so that the non-volatile content ratio was 100: 20 to obtain an adhesive polymer solution No. 16.
  • the structure was a sea-island structure.
  • a high Tg polymer was synthesized in the same manner as in Synthesis Example 10 except that the monomer composition for the high Tg polymer was changed as shown in Table 3.
  • the monomer for low Tg polymer was polymerized in the presence of high Tg polymer to synthesize the graft polymer.
  • 3 parts as monomers for low Tg polymer 2.7 parts of HEA and 120 parts of ethyl acetate were charged and mixed well. While the nitrogen gas was circulated under stirring, the internal temperature of the flask was raised to 82 ° C., and 0 ⁇ 12 parts of “NIPPER ⁇ — ⁇ 40” were put into the flask to initiate the polymerization.
  • the test tape is reciprocated once with a 2kg rubber roller in an atmosphere of 23 ° C and relative humidity of 65%. And crimp. After crimping, it was left in an oven at 70 ° C. for 72 hours, and then temperature-controlled for 24 hours in an atmosphere at 23 ° C. and 65% relative humidity. The test tape was peeled off at a peeling speed of 0.3 m / min, and the surface state of the acrylic plate after peeling was visually observed. V, no contamination (no glue residue) was rated as 0, and there was a slight amount of glue residue and contamination! /, And X was rated as X.
  • a test piece having a size of 4 cm ⁇ 4 cm is cut out from the test tape.
  • Use the rough surface of a commercially available LCD protective film (antiglare) (manufactured by BUFFALO; BOF-H141 S) as the adherend, and place the antiglare film horizontally on a flat surface so that the rough surface is on top.
  • BA 60 kg, 2EHA 134 kg, HEA 6 kg, and 240 ⁇ m of lutinole acetate as a solvent were added to a flask equipped with a thermometer, a stirrer, an inert gas introduction tube, a reflux condenser, and a dropping funnel. While flowing nitrogen gas under stirring, the internal temperature of the flask was raised to 87 ° C, and 0.25 parts of “Nyper BMT-K40” diluted with 2.3 parts of ethyl acetate as a polymerization initiator was added to the flask. To initiate polymerization.
  • High Tg polymer was synthesized in the same manner as in Synthesis Example 18.
  • the initial monomer composition was changed to BA 60 parts, 2EHA 114 parts, HEA 9 parts, benzyl acrylate (BZA) 20 parts, and the dropped monomer composition was changed to BA 90 parts, 2EHA 171 parts, HE A 9 parts, BZA 30 parts.
  • a low Tg polymer was synthesized in the same manner as in Synthesis Example 18. The non-volatile content of the obtained low Tg polymer solution was 45.5%. The Tg was 58 ° C and the Mw was 64.70,000.
  • the high Tg polymer and the low Tg polymer have a sea-island structure. Adhesive with the advantages of both polymer and low Tg polymer
  • the adhesive products obtained using the above-mentioned adhesive composition are the surfaces of optical members such as optical polarizing plates (TAC), retardation plates, EMI (electromagnetic wave) shield films, antiglare films, antireflection films and the like. It can be used as an adhesive product for re-peeling to protect the film. It can also be used as a protective film for the surface of other plastics and metal plates.
  • optical members such as optical polarizing plates (TAC), retardation plates, EMI (electromagnetic wave) shield films, antiglare films, antireflection films and the like. It can be used as an adhesive product for re-peeling to protect the film. It can also be used as a protective film for the surface of other plastics and metal plates.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne une composition adhésive enlevable de type à solvant qui comporte un polymère de haute Tg (A) ayant une température de transition vitreuse (Tg) de 0˚C ou plus, un polymère de basse Tg (B) ayant une Tg inférieure à celle du polymère de haute Tg et ayant également une propriété d'adhésion sensible à la pression, ainsi qu'un solvant. Dans une couche adhésive obtenue par l'utilisation de la composition adhésive, le polymère de haute Tg (A) et le polymère de basse Tg (B) ne sont pas dissous l'un dans l'autre et forment une structure mer-île, dans laquelle le polymère de haute Tg (A) forme une phase d'île et le polymère de basse Tg (B) forme une phase de mer. La composition permet de former une couche adhésive ayant une excellente propriété d'enlèvement à vitesse élevée lorsqu'elle est utilisée en tant que film de protection de surface pour un film optique.
PCT/JP2007/068181 2006-09-21 2007-09-19 Composition adhésive enlevable de type à solvant et produit adhésif enlevable WO2008035709A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001011396A (ja) * 1999-06-28 2001-01-16 Toagosei Co Ltd シートの施工方法
JP2003277709A (ja) * 2002-03-26 2003-10-02 Nippon Shokubai Co Ltd 粘着剤組成物および粘着製品
JP2005146151A (ja) * 2003-11-17 2005-06-09 Soken Chem & Eng Co Ltd 保護シート用感圧接着剤
JP2006124691A (ja) * 2004-09-30 2006-05-18 Nippon Shokubai Co Ltd エマルション型粘着剤組成物

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JP2002105419A (ja) * 2000-09-29 2002-04-10 Nippon Shokubai Co Ltd 粘着剤用ポリマー混合物、該粘着剤用ポリマー混合物を用いた粘着剤組成物および粘着製品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001011396A (ja) * 1999-06-28 2001-01-16 Toagosei Co Ltd シートの施工方法
JP2003277709A (ja) * 2002-03-26 2003-10-02 Nippon Shokubai Co Ltd 粘着剤組成物および粘着製品
JP2005146151A (ja) * 2003-11-17 2005-06-09 Soken Chem & Eng Co Ltd 保護シート用感圧接着剤
JP2006124691A (ja) * 2004-09-30 2006-05-18 Nippon Shokubai Co Ltd エマルション型粘着剤組成物

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