WO2014208500A1 - 有機質汚れ除去用粘着クリーナー - Google Patents
有機質汚れ除去用粘着クリーナー Download PDFInfo
- Publication number
- WO2014208500A1 WO2014208500A1 PCT/JP2014/066561 JP2014066561W WO2014208500A1 WO 2014208500 A1 WO2014208500 A1 WO 2014208500A1 JP 2014066561 W JP2014066561 W JP 2014066561W WO 2014208500 A1 WO2014208500 A1 WO 2014208500A1
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- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- dirt
- adhesive
- acrylic
- Prior art date
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Classifications
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L25/00—Domestic cleaning devices not provided for in other groups of this subclass
- A47L25/005—Domestic cleaning devices not provided for in other groups of this subclass using adhesive or tacky surfaces to remove dirt, e.g. lint removers
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- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
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- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
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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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Definitions
- the present invention relates to an adhesive cleaner used to remove organic soils. More specifically, the present invention relates to an adhesive cleaner used to remove sebum and other organic contaminants from the surface of a portable device such as a tablet information terminal or a smartphone (for example, the surface of a touch panel display / input unit).
- a portable device such as a tablet information terminal or a smartphone (for example, the surface of a touch panel display / input unit).
- portable devices such as portable PCs such as notebook personal computers (PCs), tablet information terminals such as electronic books, mobile phones such as smartphones, portable game machines, and portable terminals such as various PDAs (personal digital assistants).
- a display unit composed of a liquid crystal panel or an organic EL panel. Since such portable devices are used by carrying them on a daily basis, organic dirt such as dust, dirt, cosmetics and sebum tends to adhere to them.
- touch panel portable devices which have been widely used in recent years, include a display unit / input unit whose display unit also functions as an input unit, and are operated by a user directly touching the surface of the display unit / input unit with a fingertip. Therefore, organic stains such as hand dirt and sebum are more likely to adhere.
- not only those portable devices but also show window glasses, glass tables, showcases and the like are unsightly because the appearance deteriorates when the organic dirt adheres to the surface.
- Patent Document 1 describes an adhesive cleaner for the plate surface, but there is still room for improvement in terms of usability.
- the present invention was created to solve the above-described conventional problems, and an object thereof is to provide an adhesive cleaner that can easily remove sebum and other organic dirt adhering to the surface of an article. That is.
- an adhesive cleaner used for removing sebum and other organic dirt adhering to the surface of an article.
- the adhesive cleaner includes a dirt catching unit that catches the organic dirt by contacting the surface of the article.
- acquisition part is equipped with the adhesive in the part which contacts the surface of the said article
- the pressure-sensitive adhesive contains an acrylic block copolymer having a hard segment (A) and a soft segment (B) in one molecule as a base polymer.
- the organic dirt adhering to the surface is captured by bringing the pressure-sensitive adhesive constituting the dirt capturing portion into contact with the surface of the article (surface to be cleaned). It can be easily removed.
- the monomer unit constituting the soft segment (B) preferably contains an alkyl acrylate having 6 or more carbon atoms in the alkyl group, for example, an alkyl acrylate having 6 or more carbon atoms in the alkyl group as a main component. Is preferred. According to the pressure-sensitive adhesive containing the acrylic block copolymer having the soft segment (B) as a base polymer, a higher-performance pressure-sensitive adhesive cleaner can be realized.
- a preferred example of the alkyl acrylate having 6 or more carbon atoms in the alkyl group is 2-ethylhexyl acrylate (2EHA).
- the pressure-sensitive adhesive further contains a plasticizer.
- a plasticizer By blending a plasticizer with the acrylic block copolymer, the dirt trapping property can be improved. Further, by including a plasticizer, peeling from the surface to be cleaned becomes light, and the dirt removal workability can be improved. In addition, even if the dirt trapping ability is reduced as a result of use, there is an effect that the dirt catching ability is recovered within a relatively short time (for example, several minutes or several hours) (dirt catching ability recovery action). It can be suitably exhibited.
- the pressure-sensitive adhesive containing a plasticizer is also preferable from the viewpoint of reducing the viscosity of the pressure-sensitive adhesive.
- the pressure-sensitive adhesive can further contain a tackifier resin.
- a tackifier resin By containing the tackifier resin, the viscosity (typically melt viscosity) of the pressure-sensitive adhesive is lowered, and the coating property of the pressure-sensitive adhesive can be improved. In particular, the coatability in the hot melt system can be improved. This is advantageous from the viewpoint of improving the productivity of the adhesive cleaner and reducing the environmental load. Inclusion of a tackifying resin in the pressure-sensitive adhesive can also help improve the dirt trapping ability.
- the portion of the dirt catching portion that contacts the surface exhibits an adhesive strength of 1 N / 25 mm or less.
- the dirt catcher is lightly peelable.
- a cleaner having such a light-peelable dirt catching portion is excellent in dirt removal workability because it requires a small force when the dirt removal work is performed on the surface.
- the surface of the article for example, the display surface of a tablet-type information terminal
- the surface of the article covered with the protective film due to the above light peelability
- the cleaning that is, the surface of the protective film
- the protective film is hardly peeled off from the article. And although it is such light peelability, an organic stain
- the organic soil may contain inorganic substances such as sodium, potassium, and salts thereof, as is apparent from the fact that sebum secreted from the skin is contained as described above.
- the said adhesive force refers to the SUS180 degree peeling adhesive force measured based on the 180 degree peeling test mentioned later.
- the adhesive cleaner includes a cylindrical rolling member, and the dirt catching portion is disposed on the outer peripheral surface of the rolling member. According to the cleaner having such a configuration, by rolling the rolling member around the axis of the cylinder, the organic dirt adhering to the article surface is efficiently captured by the dirt catching portion located on the outer peripheral surface thereof, and the It can be removed from the surface.
- the adhesive cleaner disclosed herein may further include a gripping member that supports the rolling member in a rollable manner. By configuring in this way, the user can efficiently remove organic stains on the surface of the article by holding the holding member and rolling the rolling member.
- the dirt capturing portion is configured as a single-sided pressure-sensitive adhesive sheet including a sheet-like support base material and a pressure-sensitive adhesive layer disposed on the support base material.
- the single-sided pressure-sensitive adhesive sheet can be configured as a pressure-sensitive adhesive sheet roll by being wound with the pressure-sensitive adhesive layer outside.
- the surface of the article can be removed using the outer peripheral surface of the adhesive sheet roll.
- the outer periphery An unused pressure-sensitive adhesive layer can be exposed on the surface. That is, the exposure of the unused pressure-sensitive adhesive layer to the outer surface can be easily updated. For this reason, desired dirt removal performance can always be maintained.
- sebum dirt typically sebum dirt derived from animals, such as human sebum dirt
- a preferable embodiment of the adhesive cleaner disclosed herein is an adhesive cleaner used for removing sebum soil as the organic soil.
- the sebum stain refers to a stain containing sebum, and includes a stain due to a mixture of sebum and other organic or inorganic components.
- sebum stains includes, in addition to dirt and fingerprints, for example, a mixture of inorganic components such as pigments contained in the foundation and sebum, a mixture of inorganic components such as sodium chloride contained in sweat and sebum, moisturizing Contamination due to a mixture of organic components such as cream or sunscreen and sebum, etc. may be included.
- the article is a portable device having a display surface (typically a smooth and flat surface) made of glass or synthetic resin. Since the portable device is used by being carried on a daily basis, dust and organic dirt such as hand dirt, cosmetics, and sebum are likely to adhere to the portable device.
- portable devices having a touch panel type display surface are operated by directly touching the display unit / input unit with a finger, and thus organic stains such as dirt, cosmetics, and sebum are more adhered.
- the adhesive cleaner disclosed herein is particularly preferably used for removing dirt from a portable device having the display surface as described above (for example, a touch panel type display surface), because such organic dirt can be easily removed.
- the adhesive type cleaner has been used conventionally (see, for example, Patent Document 3 above)
- the conventional roll-shaped cleaner is used for cleaning floors and carpets. It does not clean the surface (for example, a touch panel surface display / input unit) of the type information terminal or smartphone.
- the adhesive cleaner disclosed herein is different from the conventional adhesive cleaner used for cleaning floors and carpets, and is used to remove organic dirt adhering to the surface of an article such as a portable device. In particular, it is suitable for use in removing organic soil adhering to the smooth surface of an article.
- the article to be used for the adhesive cleaner disclosed herein is not particularly limited. Articles having a smooth surface (typically a smooth and flat surface) are preferred. Examples of such articles include show window glass, glass tables, showcases, mirrors, water tanks, various displays (such as embedded or stationary types, or portable televisions and PC displays), touch panel display / input units (Such as a cash machine (ATM), an operation terminal of a car navigation system, a stationary or portable device such as a guide plate).
- Organic stains adhering to the smooth surfaces they typically have are unsightly and should be removed as soon as they are found. Therefore, it can be a preferred target for use of the adhesive cleaner disclosed herein.
- the portable device refers to a portable device, and is not limited to a specific device.
- Portable devices having a smooth surface typically a smooth and flat surface
- Examples of such portable devices include portable PCs such as notebook PCs, tablet information terminals such as electronic books, smartphones and other mobile phones, portable game machines, PDAs (personal digital assistants) such as electronic notebooks, digital cameras, Examples include digital photo frames and hand mirrors. Since these are carried and used on a daily basis, dust and organic dirt such as hand dirt, cosmetics, and sebum are likely to adhere to them.
- Some of these portable devices have a smooth surface (typically a glass or synthetic resin surface) as a display surface such as a liquid crystal display or an organic EL display. If dirt is attached, it becomes difficult to see the information displayed on the display surface, which is not convenient. In addition, depending on the degree of organic soiling, it may give an unclean impression.
- a portable device having such a display surface can be a preferred target for use of the adhesive cleaner disclosed herein.
- the device having a touch panel type display / input unit is directly touched by a user with a finger, the above-mentioned organic contamination is more likely to adhere. Therefore, it can be a preferred target for use of the adhesive cleaner disclosed herein.
- tablet-type information terminals such as electronic books have a relatively large display surface, and thus are grasped as particularly preferable usage targets of the adhesive cleaner.
- the mobile phone tends to come into contact with the face when making a call with the mobile phone close to the ear or mouth, and organic dirt such as sebum on the face or cosmetics tends to adhere.
- organic dirt such as sebum on the face or cosmetics tends to adhere.
- it since it is a device that can be used in contact with or in close proximity to the face, it is highly significant to remove organic stains on the surface and keep it clean. Therefore, it is grasped as a particularly preferable object of use of the above-mentioned adhesive cleaner.
- an adhesive cleaner (hereinafter also simply referred to as “cleaner”) 10 includes a cylindrical holding member (core) 20, and an adhesive sheet roll 30 held on the outer peripheral surface of the holding member 20. Is provided.
- the holding member 20 and the pressure-sensitive adhesive sheet roll 30 are integrally formed as a cylindrical rolling member.
- the material of the holding member is not particularly limited, and those made of polyolefin or other synthetic resin or paper can be preferably used.
- the cleaner 10 further includes a rod-shaped gripping member 40 that supports the holding member 20 in a rollable manner. Specifically, a central hole (not shown) is formed in the holding member 20 at a position that becomes the central axis of the cylinder, and an end (one end) of the gripping member 40 is inserted into the central hole. Thus, the holding member 20 is attached to the gripping member 40 so as to be rotatable. A handle 42 is attached to the other end of the gripping member 40.
- the material of the grip member and the handle is not particularly limited, and for example, a metal or synthetic resin can be used.
- the pressure-sensitive adhesive sheet roll 30 of the cleaner 10 is formed by winding a pressure-sensitive adhesive sheet 31 serving as a dirt capturing portion.
- the pressure-sensitive adhesive sheet (dirt capturing portion) 31 is arranged on a long sheet-like (band-like) support base material 36 and one surface 36 ⁇ / b> A of the support base material 36.
- a single-sided pressure-sensitive adhesive sheet 31 including the pressure-sensitive adhesive layer 32 is configured.
- the single-sided pressure-sensitive adhesive sheet 31 is formed as a pressure-sensitive adhesive sheet roll 30 by being wound so that the pressure-sensitive adhesive layer 32 is on the outside.
- the cleaner 10 is used to remove organic contaminants attached to the display unit 2 of the portable device 1.
- the display unit 2 of the portable device 1 has a smooth and flat surface.
- the operator places the cleaner 10 on the display unit 2 of the portable device 1, grips the handle 42, and applies a predetermined external force to the cleaner 10. Then, the said external force is transmitted to the holding member 20 from the holding member 40, and the adhesive layer 32 of the adhesive sheet roll 30 arrange
- the pressure-sensitive adhesive layer 32 captures dust and dirt present on the display unit 2 and particularly organic dirt (for example, sebum dirt such as hand dirt and fingerprints containing sebum).
- organic dirt for example, sebum dirt such as hand dirt and fingerprints containing sebum.
- cleaning (dirt removal) of the display unit 2 is easily and reliably performed along the rolling direction of the adhesive sheet roll 30 (more specifically, the adhesive sheet (dirt capturing unit) 31).
- the portable apparatus in this embodiment is a tablet-type information terminal in which the whole display part is comprised with tempered glass, such as aluminosilicate glass, it is as above-mentioned that it is not limited to this.
- the size of the cylindrical pressure-sensitive adhesive sheet roll is not particularly limited, but when the target of use is a portable device such as a tablet-type information terminal, the diameter (which means a diameter (outer diameter) when not in use; the same applies hereinafter) is 4 mm or more. (More preferably, 10 mm or more, for example, 15 mm or more, typically 20 mm or more). Further, from the viewpoint of operability and portability, the diameter is preferably 50 mm or less (for example, 35 mm or less, typically 30 mm or less).
- the pressure-sensitive adhesive sheet constituting the pressure-sensitive adhesive sheet roll is provided with a cut line (not shown) for each length corresponding to substantially one round of the roll.
- This cut is a cutting means for efficiently renewing the pressure-sensitive adhesive layer surface (outer surface of the dirt catching portion) whose cleaning (dirt removal) performance has deteriorated after using the cleaner several times.
- it may be a long hole or corrugated slit arranged, an intermittent slit such as a perforation.
- the cut is preferably provided so as to cross the pressure-sensitive adhesive sheet in the width direction (direction perpendicular to the longitudinal direction).
- the update of the outer surface (outer peripheral surface) of the dirt capturing unit is not limited to the cutting means.
- intermittent slits such as perforations are formed in a spiral shape in a direction that intersects the sheet winding direction of the adhesive sheet roll (typically, a direction that intersects with the width direction at an angle of 30 ° to 60 °). It may be left.
- slits continuous cuts
- the pressure-sensitive adhesive sheet constituting the pressure-sensitive adhesive sheet roll is completely cut at predetermined intervals in the roll winding direction in advance, so that the outer surface of the pressure-sensitive adhesive sheet roll can be easily peeled off at each predetermined interval. The outer surface can be updated.
- the cleaner 10 can be produced by appropriately adopting a conventionally known method.
- the pressure-sensitive adhesive sheet roll 30 of the cleaner 10 can be produced by the same method as that of a conventional roll-shaped cleaner. That is, the pressure-sensitive adhesive layer 32 is formed by applying a pressure-sensitive adhesive composition on the surface 36A of the long sheet-like support base 36 by various conventionally known coating means, and performing a drying treatment or the like as necessary. Form.
- a hot-melt adhesive thermoplastic adhesive
- the adhesive composition is coated with a heat-melted adhesive, and the adhesive is typically allowed to cool to near room temperature. An agent layer can be formed. Therefore, the drying process can be omitted.
- the roll-shaped adhesive sheet roll 30 is formed by winding the adhesive sheet 31 around the holding member 20 so that the adhesive layer 32 may become an outer peripheral surface.
- the cleaner 10 is constructed by attaching the end of the gripping member 40 to the holding member 20 so as to be able to roll.
- the attachment structure of the gripping member 40 to the holding member 20 itself can be the same as that of a conventional roll-shaped cleaner, and does not characterize the present invention, so that detailed description thereof is omitted.
- the adhesive cleaner is not limited to the one in the above embodiment.
- the adhesive cleaner may be composed of, for example, only a dirt catcher.
- a cleaner composed only of a dirt trapping part such as a spherical shape, a columnar shape, a cylindrical shape, a hexahedral shape (for example, a rectangular parallelepiped shape), a sheet shape, and the like can be mentioned.
- the dirt capturing part is composed of the support base material and the pressure-sensitive adhesive layer, but is not limited to this.
- the dirt capturing part may be formed only from an adhesive (baseless adhesive).
- the shape of the support base material is not particularly limited.
- the dirt trapping part may be one in which an adhesive layer is formed on the outer surface of a spherical support substrate.
- the holding member supported the holding member so that rolling was possible, it is not limited to this.
- the gripping member may be directly or indirectly connected (coupled or detachably connected) to the dirt capturing unit.
- an adhesive cleaner for example, a stick-shaped gripping member having a columnar or rectangular parallelepiped-shaped adhesive body fixed to one end thereof can be mentioned.
- the gripping member may have a flat portion, and the dirt catching portion may be fixed to one surface of the flat portion.
- the pressure-sensitive adhesive in the technology disclosed herein has, as a base polymer, a hard segment (A) (hereinafter also referred to as “A block”) and a soft segment (B) (hereinafter also referred to as “B block”) in one molecule. And an acrylic block copolymer.
- the hard segment (A) refers to a relatively hard block in relation to the soft segment (B) in the acrylic copolymer in the structure of the acrylic block copolymer.
- the soft segment (B) refers to a relatively soft block in the relationship with the hard segment (A) in the structure of the acrylic block copolymer.
- the acrylic block copolymer may exhibit the properties of a thermoplastic polymer (typically a thermoplastic elastomer).
- the pressure-sensitive adhesive disclosed herein can be a pressure-sensitive adhesive (hot-melt pressure-sensitive adhesive) suitable for coating in a hot-melt format by including the acrylic block copolymer as a base polymer.
- the hot-melt adhesive includes a general organic solvent-type acrylic adhesive (typically a random copolymer synthesized by solution polymerization from a monomer raw material having an acrylic monomer as a main monomer as a base polymer. Since the amount of the organic solvent used can be reduced as compared with the pressure-sensitive adhesive), it is preferable from the viewpoint of reducing the environmental load.
- the acrylic block copolymer is a monomer having at least one (meth) acryloyl group in one molecule (hereinafter referred to as “acrylic monomer”) as a monomer unit (constituent monomer component) constituting the copolymer.
- acrylic monomer a monomer having at least one (meth) acryloyl group in one molecule
- an acrylic block copolymer in which 50% by mass or more of all monomer units are monomer units derived from an acrylic monomer is preferable.
- Such an acrylic block copolymer can be preferably synthesized from, for example, a monomer raw material containing an alkyl (meth) acrylate having an alkyl group as a main monomer.
- the main monomer refers to a monomer component that occupies 50% by mass or more of the total monomer raw materials.
- (meth) acryloyl means acryloyl and methacryloyl comprehensively.
- (meth) acrylate is a generic term for acrylate and methacrylate.
- the acrylic block copolymer one having at least one acrylate block (hereinafter also referred to as Ac block) and at least one methacrylate block (hereinafter also referred to as MAc block) can be preferably used.
- Ac block acrylate block
- MAc block methacrylate block
- a block copolymer having a structure in which Ac blocks and MAc blocks are alternately arranged is preferable.
- the total number of blocks of Ac blocks and MAc blocks contained in one molecule of polymer can be, for example, about 2.5 to 5 on average (for example, about 2.7 to 3.3, typically about 3).
- the above-mentioned Ac block typically has alkyl acrylate as the main monomer. That is, it is preferable that 50% by mass or more of all monomer units constituting the Ac block are monomer units derived from alkyl acrylate. 75 mass% or more (for example, 90 mass% or more) of the monomer unit may be derived from alkyl acrylate.
- the Ac block contained in the acrylic block copolymer is a polymer substantially composed of one or more (typically one) alkyl acrylate.
- the Ac block may be a copolymer of an alkyl acrylate and another monomer (for example, alkyl methacrylate).
- alkyl acrylate constituting the Ac block examples include alkyl acrylates having an alkyl group having 1 to 20 carbon atoms (preferably 4 to 14, for example, 6 to 12).
- alkyl acrylates having an alkyl group having 1 to 20 carbon atoms preferably 4 to 14, for example, 6 to 12.
- examples thereof include acrylate, 2-ethylhexyl acrylate (2EHA), nonyl acrylate, isononyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate and the
- 50% by mass or more of the monomers constituting the Ac block is an alkyl acrylate having 4 to 14 carbon atoms in the alkyl group.
- the proportion of the alkyl acrylate having 4 to 14 carbon atoms in the alkyl group may be 75% by mass or more, or substantially 100% by mass (for example, more than 99% by mass and 100% by mass or less).
- a constitution in which the monomer unit constituting the Ac block is substantially BA alone, a constitution in which 2EHA is alone, a constitution comprising two types of BA and 2EHA, and the like can be preferably employed.
- the weight ratio of BA to 2EHA is not particularly limited and is, for example, 10/90 to 90/10, preferably 80/20 to 20/80, more preferably 30/70 to 70/30, for example 60/40 to 40 / 60.
- the MAc block typically has alkyl methacrylate as the main monomer. Of all the monomer units constituting the MAc, 75% by mass or more (for example, 90% by mass or more) may be derived from alkyl methacrylate.
- the MAc block contained in the acrylic block copolymer is a polymer consisting essentially of one or more (typically one) alkyl methacrylate.
- the MAc block may be a copolymer of alkyl methacrylate and another monomer (for example, alkyl acrylate).
- alkyl methacrylate constituting the MAc block examples include alkyl methacrylates having 1 to 20 (preferably 1 to 14) carbon atoms in the alkyl group. Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, Examples thereof include n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate and the like. These can be used alone or in combination of two or more.
- 50% by mass or more of the monomers constituting the MAc block is alkyl methacrylate having 1 to 4 (preferably 1 to 3) carbon atoms in the alkyl group.
- the ratio of the alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group may be 75% by mass or more, or substantially 100% by mass (for example, more than 99% by mass and 100% by mass or less).
- preferred alkyl methacrylates include methyl methacrylate (MMA) and ethyl methacrylate (EMA).
- MMA methyl methacrylate
- EMA ethyl methacrylate
- a configuration in which the monomer unit is substantially MMA alone
- a configuration in which the monomer unit is EMA alone a configuration composed of two types of MMA and EMA, and the like can be preferably employed.
- the acrylic block copolymer is composed of an A block (hard segment (A)) made of a polymer having a hard structure excellent in cohesion and elasticity, such as AB type, ABA type, ABAB type, and ABABA type.
- the B block (soft segment (B)) made of a polymer having a soft structure excellent in the structure may be copolymerized so as to be alternately arranged.
- the pressure-sensitive adhesive using the acrylic block copolymer having such a structure as a base polymer can form a pressure-sensitive adhesive layer in which cohesive force, elasticity and viscosity are highly compatible.
- the adhesive of this composition can be preferably used as a hot melt adhesive.
- An acrylic block copolymer (ABA type, ABABA type, etc.) having a structure in which A blocks are arranged at both ends of the molecule can be preferably used.
- An acrylic block copolymer having such a structure is preferable because it tends to have a good balance between cohesiveness and thermoplasticity.
- the acrylic block copolymer has two or more A blocks
- the monomer composition, molecular weight (degree of polymerization), structure, etc. of these A blocks may be the same or different.
- the MAc block as described above can be preferably used.
- the B block the Ac block as described above can be preferably adopted.
- the acrylic block copolymer is a triblock copolymer having a MAc block-Ac block-MAc block (ABA type) structure.
- ABA type MAc block-Ac block-MAc block
- such a triblock copolymer in which two MAc blocks have substantially the same monomer composition can be preferably employed.
- the acrylic block copolymer in the technology disclosed herein preferably has an Ac block containing an alkyl acrylate having an alkyl group having 6 or more carbon atoms (for example, 6 to 12) as the soft segment (B).
- the proportion of the alkyl acrylate having 6 or more carbon atoms in the alkyl group can be, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30%. It is 40% by mass or more, more preferably 40% by mass or more.
- an acrylic block copolymer having, as a soft segment (B), an Ac block containing an alkyl acrylate having an alkyl group having 6 or more carbon atoms (for example, 6 to 12) as a main monomer can be used. That is, it is preferable that 50% by mass or more of the monomer units constituting the Ac block is occupied by one or more alkyl acrylates having 6 or more carbon atoms in the alkyl group.
- the proportion of the alkyl acrylate having 6 or more carbon atoms in the alkyl group can be, for example, 55% by mass or more, and may be 60% by mass or more.
- an acrylic block copolymer having an Ac block whose monomer unit constituting the Ac block is 2EHA alone as the soft segment (B) is preferable.
- the alkyl acrylate having 6 or more carbon atoms in the alkyl group include 2-ethylhexyl acrylate (2EHA), n-octyl acrylate, isononyl acrylate, n-hexyl acrylate and the like.
- An acrylic block copolymer having an Ac block containing an alkyl acrylate having 6 or more carbon atoms in the alkyl group as the soft segment (B) can be excellent in organic soil scavenging. Therefore, for example, a higher sebum soil removal rate can be realized in the evaluation of sebum soil removability described later.
- An acrylic block copolymer having an Ac block containing an alkyl acrylate having an alkyl group with 6 or more carbon atoms as the soft segment (B) can be excellent in compatibility with a plasticizer. This is preferable from the viewpoint of suppressing bleed-out of the plasticizer in the pressure-sensitive adhesive having a composition containing the copolymer and the plasticizer. Moreover, since more plasticizers can be contained appropriately, there are advantages that the degree of freedom in setting the blending amount of the plasticizer is high and the adhesive force can be easily adjusted.
- the mass ratio of the hard segment (A) and the soft segment (B) contained in the acrylic block copolymer is not particularly limited.
- the mass ratio (A / B) of the hard segment (A) / soft segment (B) can be in the range of 4/96 to 90/10, and is usually in the range of 7/93 to 70/30. It is preferable that the range is 10/90 to 50/50 (for example, 15/85 to 40/60).
- the mass ratio of the total mass of the hard segments (A) to the soft segments (B) is preferably in the above range. The same applies to an acrylic block copolymer containing two or more soft segments (B).
- the proportion of the hard segment (A) for example, MAc block
- the adhesive strength tends to decrease, and light peelability tends to be easily obtained.
- the proportion of the soft segment (B) for example, the Ac block
- the organic dirt capturing performance tends to be improved.
- the monomer raw material corresponding to all monomer units constituting the acrylic block copolymer is an alkyl (meth) alkyl group having 1 to 3 carbon atoms.
- the mass ratio (X / Y) of alkyl (meth) acrylate (X) / alkyl (meth) acrylate (Y) can be, for example, 4/96 to 90/10.
- Acrylic block copolymers having a mass ratio of 7/93 to 70/30 are preferred, those having 10/90 to 50/50 are more preferred, and those having 15/85 to 40/60 are more preferred. Those having a ratio of 15/85 to 30/70 (for example, 15/85 to 25/75) are particularly preferable.
- ratios of alkyl (meth) acrylate (X) there exists a tendency for adhesive force to fall and to obtain light peelability easily.
- the ratio of the alkyl (meth) acrylate (Y) is large, the organic dirt capturing performance tends to be improved.
- the alkyl (meth) acrylate (X) is preferably an alkyl methacrylate having an alkyl group having 1 to 3 carbon atoms.
- the alkyl (meth) acrylate (Y) is preferably an alkyl acrylate having an alkyl group with 6 or more carbon atoms (for example, 6 to 12).
- monomer raw materials corresponding to all monomer units constituting the acrylic block copolymer are methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA). And the mass ratio of their contents (MMA / 2EHA) is 4/96 to 90/10.
- Acrylic block copolymers having a mass ratio of 7/93 to 70/30 are preferred, those having 10/90 to 50/50 are more preferred, and those having 15/85 to 40/60 are more preferred. Those having a ratio of 15/85 to 30/70 (for example, 15/85 to 25/75) are particularly preferable.
- the ratio of MMA is large, the adhesive strength is reduced, and light peelability tends to be easily obtained.
- the ratio of 2EHA is large, the organic dirt capturing performance tends to be improved.
- composition of the monomer unit which comprises an acrylic block copolymer can be grasped
- the NMR measurement can be performed under the following conditions using, for example, “AVAVCEIII-600 (with Cryo Probe)” manufactured by Bruker Biospin as an NMR apparatus.
- the mass ratio between 2EHA and MMA contained in the monomer raw material can be calculated based on the peak integrated intensity ratio between 4.0 ppm (2EHA1) and 3.6 ppm (MMA1) in the 1 H NMR spectrum.
- the weight average molecular weight (Mw) of the acrylic block copolymer is not particularly limited, and for example, those having an Mw of about 3 ⁇ 10 4 to 30 ⁇ 10 4 can be preferably used.
- the Mw of the acrylic block copolymer is usually preferably in the range of about 3.5 ⁇ 10 4 to 25 ⁇ 10 4 , for example 4 ⁇ 10 4 to 20 ⁇ 10 4 (for example, 4.5 ⁇ 10 4 to 15 ⁇ 10 4 ).
- the range of 4 ) is more preferable.
- Increasing the Mw of the acrylic block copolymer is advantageous from the viewpoints of improving adhesive properties (for example, cohesiveness) and improving organic dirt capturing properties.
- the Mw of the acrylic block copolymer increases, the amount of the plasticizer that can be appropriately contained tends to increase.
- lowering the Mw of the acrylic block copolymer is advantageous from the viewpoint of reducing the viscosity (for example, melt viscosity) of the pressure-sensitive adhesive. Reducing the melt viscosity of the pressure-sensitive adhesive is particularly significant when the pressure-sensitive adhesive is a hot-melt pressure-sensitive adhesive.
- the Mw of the acrylic block copolymer referred to here is a polystyrene equivalent value obtained by performing gel permeation chromatography (GPC) measurement on a sample prepared by dissolving the copolymer in tetrahydrofuran (THF).
- GPC gel permeation chromatography
- THF tetrahydrofuran
- the GPC measurement can be performed under the following conditions using, for example, “HLC-8120GPC” manufactured by Tosoh Corporation as a GPC measurement apparatus.
- the acrylic block copolymer in the technology disclosed herein may be copolymerized with monomers other than alkyl acrylate and alkyl methacrylate (other monomers).
- the other monomers include vinyl compounds having functional groups such as alkoxy groups, epoxy groups, hydroxyl groups, amino groups, amide groups, cyano groups, carboxyl groups, and acid anhydride groups, vinyl esters such as vinyl acetate, styrene, etc.
- vinyl esters such as vinyl acetate, styrene, etc.
- aromatic vinyl compounds and vinyl group-containing heterocyclic compounds such as N-vinylpyrrolidone.
- alkyl acrylates, fluorinated alkyl acrylates and fluorinated alkyl methacrylates having a structure in which a fluorinated alkyl group is bonded to an acryloyl group can be mentioned.
- the other monomers can be used, for example, for the purpose of adjusting the properties (adhesive properties, moldability, etc.) of the pressure-sensitive adhesive layer, and the content thereof is 20% by mass of the total monomer components constituting the acrylic block copolymer. It is appropriate to set it below (for example, 10 mass% or less, typically 5 mass% or less).
- the acrylic block copolymer contains substantially no other monomer.
- an acrylic block copolymer in which the content of the other monomers is less than 1% by mass (typically 0 to 0.5% by mass) of the total monomer components or below the detection limit is preferable.
- Such an acrylic block copolymer can be easily synthesized by a known method (for example, see JP-A Nos. 2001-234146 and 11-323072), or a commercially available product can be easily obtained. It can be obtained.
- the commercially available products include Kuraray's product name “LA polymer” series (for example, product numbers such as LA2140e and LA2250), Kaneka's product name “NABSTAR”, and the like.
- a method for synthesizing the acrylic block copolymer a method utilizing a living polymerization method can be preferably employed.
- the living polymerization method it is possible to synthesize an acrylic block copolymer excellent in thermoplasticity by maintaining the original weather resistance of the acrylic polymer and by controlling the structure unique to the living polymerization method.
- a pressure-sensitive adhesive and hence a pressure-sensitive adhesive sheet (dirt trapping part)
- excellent in light release property can be realized while suppressing the lack of cohesiveness due to the presence of low molecular weight components.
- the acrylic block copolymer can be used alone or in combination of two or more.
- an acrylic block copolymer (H) having a relatively high Mw and an acrylic block copolymer (L) having a lower Mw than the acrylic block copolymer (H) at an appropriate mass ratio. Can be used.
- the acrylic block copolymer (H) / acrylic block is usually used.
- the copolymer (L) is preferably used in a range where the mass ratio (H / L) is 5/95 to 95/5 (preferably 10/90 to 90/10).
- the individual Mw of the acrylic block copolymer used in combination as described above is preferably in the range of 3 ⁇ 10 4 to 30 ⁇ 10 4 .
- a combination with the acrylic block copolymer (L) in the range of 4 and lower than the Mw of the acrylic block copolymer (H) is preferred.
- an acrylic block copolymer (H) having a Mw in the range of 6 ⁇ 10 4 to 15 ⁇ 10 4 (for example, 7 ⁇ 10 4 to 15 ⁇ 10 4 ) and Mw of 4 ⁇ 10 4 to A combination with the acrylic block copolymer (L) in the range of 6 ⁇ 10 4 and lower than the Mw of the acrylic block copolymer (H) is exemplified.
- the mass ratio (H / L) of these acrylic block copolymers can be, for example, 40/60 to 90/10, and preferably 45/65 to 85/15.
- a plasticizer in the adhesive in the technique disclosed herein.
- Inclusion of a plasticizer improves light peelability.
- coating property improves.
- the organic dirt capturing property on the pressure-sensitive adhesive surface is improved by the inclusion of the plasticizer. By this, for example, a higher sebum dirt removal rate can be realized.
- the above-described dirt trapping ability recovery action will be described with reference to FIG.
- the adhesive layer 32 of the dirt catching portion (adhesive sheet) 31 is brought into contact with the surface 2 of the article 1 such as a portable device, the adhesive layer 32 is attached to the surface 2.
- the dirt 50 is captured.
- the pressure-sensitive adhesive layer 32 has a property of not only capturing the organic dirt 50 but also transferring it into the layer. Therefore, the organic dirt 50 adhering to the surface of the pressure-sensitive adhesive layer 32 moves into the pressure-sensitive adhesive layer 32 over time, and the organic dirt 50 existing on the surface of the pressure-sensitive adhesive layer 32 decreases, and finally the pressure-sensitive adhesive. On the surface of the layer 32, the organic dirt 50 is hardly present.
- the above-mentioned “recovery action” means that when the adhesive traps organic dirt and the dirt trapping ability temporarily decreases, the dirt is removed after a predetermined time (for example, several minutes, preferably several hours). This means that the trapping ability is restored and the adhesive (for example, the adhesive layer) can trap the dirt again, and includes that the time required for recovery of the dirt trapping ability is short.
- plasticizers include: phthalates such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dibutyl phthalate; adipates such as dioctyl adipate and diisononyl adipate; trimellitic acids such as trioctyl trimellitic acid Esters; sebacic acid esters; epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; epoxidized fatty acid alkyl esters such as epoxidized fatty acid octyl ester; sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan And cyclic fatty acid esters and derivatives thereof such as trioleate and their ethylene oxide adducts.
- phthalates such as dioctyl phthalate, diisononyl phthalate, diisode
- Softeners such as process oil are also included in the plasticizer. These can be used alone or in combination of two or more.
- preferable plasticizers include adipic acid esters, epoxidized vegetable oils, and epoxidized fatty acid alkyl esters. Of these, adipic acid esters are preferred.
- Such a plasticizer includes, for example, an acrylic block copolymer having an Ac block containing an alkyl acrylate having an alkyl group having 6 or more carbon atoms (for example, 6 to 12) as a soft segment (B) as a base polymer.
- the blending amount of the plasticizer is not particularly limited, but from the viewpoint of lowering the melt viscosity, imparting light releasability, improving dirt trapping property, etc., with respect to 100 parts by mass of the base polymer (acrylic block copolymer), for example It is appropriate to set it to 1 part by mass or more.
- the blending amount is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more.
- the amount is suitably 150 parts by mass or less, preferably 120 parts by mass or less, more preferably 100 parts by mass or less, The amount is more preferably 80 parts by mass or less, and particularly preferably 60 parts by mass or less.
- an acrylic block copolymer having, as a soft segment (B), an Ac block containing an alkyl acrylate having an alkyl group having 6 or more carbon atoms (for example, 6 to 12) for example, an Ac block having the alkyl acrylate as a main monomer).
- the amount of the plasticizer is, for example, 10 to 80 parts by mass (for example, 20 to 70 parts by mass, typically 25 to 60 parts by mass) with respect to 100 parts by mass of the base polymer. ) Is preferable.
- the pressure-sensitive adhesive in the technology disclosed herein can contain a tackifier as necessary. Incorporating a tackifier can help to improve the thermoplasticity of the adhesive (eg, decrease in melt viscosity).
- a tackifier a well-known tackifier resin etc. in the field of an acrylic adhesive can be used.
- hydrocarbon tackifier resin, terpene tackifier resin, rosin tackifier resin, phenol tackifier resin, epoxy tackifier resin, polyamide tackifier resin, elastomer tackifier resin, ketone tackifier resin Etc can be used alone or in combination of two or more.
- hydrocarbon-based tackifying resins examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins (xylene resins, etc.), aliphatic cyclic hydrocarbon resins, aliphatic / aromatic petroleum resins (styrene-olefins) And other hydrocarbon resins such as aliphatic / alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, coumarone-indene resins, and the like.
- terpene-based tackifier resins include terpene resins such as ⁇ -pinene polymers and ⁇ -pinene polymers; modified terpenes obtained by modifying these terpene resins (phenol modification, aromatic modification, hydrogenation modification, etc.) Resin (for example, terpene phenol resin, styrene-modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, etc.);
- rosin tackifier resins include unmodified rosins such as gum rosin and wood rosin (raw rosin); modified rosins modified with hydrogenation, disproportionation, polymerization, etc.
- phenolic tackifying resins include resol-type or novolac-type alkylphenol resins.
- preferable tackifiers include terpene resins, modified terpene resins, and alkylphenol resins.
- the softening point of the tackifier is not particularly limited, it is preferably 160 ° C. or lower and more preferably 140 ° C. or lower from the viewpoint of reducing the melt viscosity. Moreover, from a viewpoint of avoiding the excessive raise of adhesive force, 60 degreeC or more is preferable and 80 degreeC or more is more preferable.
- the compounding quantity of a tackifier is not specifically limited, From a viewpoint of avoiding the excessive raise of adhesive force, it can be 50 mass parts or less with respect to 100 mass parts of base polymers (acrylic block copolymer), for example, Usually, 40 parts by mass or less is appropriate, and 30 parts by mass or less is preferable. Further, from the viewpoint of better exhibiting the effect (for example, the effect of decreasing the melt viscosity) of the tackifier, it is appropriate to set the blending amount to, for example, 1 part by mass or more with respect to 100 parts by mass of the base polymer. Or the adhesive which does not contain such tackifier substantially may be sufficient.
- the pressure-sensitive adhesive in the technology disclosed herein adjusts the viscosity of the pressure-sensitive adhesive (for example, decreases the melt viscosity) and controls the pressure-sensitive adhesive properties (for example, reduces the pressure-sensitive adhesive force).
- a polymer or oligomer other than the acrylic block copolymer may be contained as an optional component.
- an acrylic random copolymer having an Mw of about 500 to 10,000 (typically about 800 to 5,000) can be used.
- the amount of the optional polymer is, for example, 50 parts by mass or less, preferably 10 parts by mass or less, and preferably 5 parts by mass or less per 100 parts by mass of the acrylic block copolymer. More preferred.
- the pressure-sensitive adhesive layer may contain substantially no polymer other than the acrylic block copolymer.
- a pressure-sensitive adhesive layer in which the content of a polymer other than the acrylic block copolymer is less than 1% by mass (typically 0 to 0.5% by mass) per 100 parts by mass of the acrylic block copolymer is preferable.
- Other adhesives in the technology disclosed herein include surfactants, chain transfer agents, anti-aging agents, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, and colorants (pigments, dyes). Etc.) can be blended with various additive components known in the field of pressure-sensitive adhesives. The types and blending amounts of these additional components that are not essential components may be the same as the normal types and blending amounts of this type of pressure-sensitive adhesive.
- the forming method is not particularly limited.
- a heat-melted pressure-sensitive adhesive thermoplastic pressure-sensitive adhesive
- a conventionally known coating means such as a roll coater, die coater, or gravure coater
- the pressure-sensitive adhesive is brought to about room temperature.
- a method of forming a pressure-sensitive adhesive layer by allowing to cool can be preferably applied.
- the pressure-sensitive adhesive is typically applied to the substrate in the form of a pressure-sensitive adhesive substantially free of an organic solvent (that is, a solventless pressure-sensitive adhesive).
- the pressure-sensitive adhesive may be cross-linked by an appropriate means after being applied to the support substrate, but is usually a non-cross-linked pressure-sensitive adhesive (that is, a thermoplastic pressure-sensitive adhesive without applying special cross-linking means). ) Is preferred because it is simple and convenient.
- the pressure-sensitive adhesive disclosed herein is applied to a support substrate in the form of a pressure-sensitive adhesive composition in which the pressure-sensitive adhesive is dissolved or dispersed in a suitable liquid medium (typically applied at room temperature), It may be formed as an adhesive layer by drying the coated material.
- the pressure-sensitive adhesive composition includes, for example, a composition in which the pressure-sensitive adhesive disclosed herein is dissolved in an organic solvent (solvent-type pressure-sensitive adhesive composition), and a composition in which the pressure-sensitive adhesive is dispersed in water (water dispersion).
- organic solvent general organic solvents such as ethyl acetate, toluene, hexane, ethyl alcohol and the like can be used.
- an organic solvent can be used individually by 1 type or in combination of 2 or more types.
- the pressure-sensitive adhesive composition may contain a solvent (typically an organic solvent) at a ratio of, for example, about 30 to 70% by mass.
- the pressure-sensitive adhesive layer is applied to the surface having a peelable property (peeling surface) and dried to allow the pressure-sensitive adhesive layer to be coated on the peeling surface. You may arrange
- the pressure-sensitive adhesive disclosed herein suitably has a melt viscosity at 180 ° C. of 200 Pa ⁇ s or less, and 100 Pa ⁇ s or less, from the viewpoint of coatability. Preferably, it is 50 Pa ⁇ s or less (typically 20 Pa ⁇ s or less, for example, 10 Pa ⁇ s or less).
- the lower limit of the melt viscosity at 180 ° C. is not particularly limited, but is usually 0.1 Pa ⁇ s or more and 1 Pa ⁇ s or more in consideration of the balance between coatability and adhesive performance. For example, 5 Pa ⁇ s or more is preferable.
- the melt viscosity can be measured by the following melt viscosity measurement method.
- Measuring method of melt viscosity Measuring instrument: Brookfield, USA, programmable viscometer (DV-II + Pro) Measurement conditions: measurement temperature 180 ° C., rotation speed 2.5 rpm, spindle SC4-27 Measurement procedure: About 14 g of adhesive is put in a sample chamber and heated to 180 ° C. to melt. The spindle is submerged and rotated in the melted adhesive, and the melt viscosity 30 minutes after the start of rotation is read.
- the thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the purpose and is not particularly limited.
- the thickness of the pressure-sensitive adhesive layer is about 10 ⁇ m or more (for example, 20 ⁇ m or more, preferably 30 ⁇ m or more, typically 40 ⁇ m or more) from the viewpoint of fully exhibiting the dirt trapping performance and improving the recoverability of the dirt trapping ability. It is preferable that In the case where weight reduction, downsizing, etc. are important, the thickness of the pressure-sensitive adhesive layer is preferably 300 ⁇ m or less (for example, 100 ⁇ m or less, preferably 70 ⁇ m or less, typically 60 ⁇ m or less).
- the pressure-sensitive adhesive layer may be formed over the entire range of one surface of the support substrate, or, for example, the pressure-sensitive adhesive layer is not formed along both ends in the width direction of the support substrate. You may have a non-adhesion part (dry edge).
- the dirt capturing portion disclosed herein includes a support base material as in the above embodiment, for example, a material composed of various synthetic resins, non-woven fabrics, or paper can be used as the support base material.
- the material of the support substrate may be a cloth, a rubber sheet, a foam sheet, a metal foil, a composite thereof, or the like.
- Examples of the synthetic resin include polyolefin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), polyester (polyethylene terephthalate, etc.), vinyl chloride resin, vinyl acetate resin, polyimide resin, polyamide resin, fluororesin and the like.
- a support substrate made of polyethylene terephthalate (PET) can be suitably used.
- Examples of paper include Japanese paper, craft paper, glassine paper, high-quality paper, synthetic paper, topcoat paper, and the like.
- Examples of the fabric include woven fabrics and non-woven fabrics made of various fibrous substances alone or by blending.
- Examples of the fibrous material include cotton, suf, manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, polyolefin fiber and the like.
- Examples of rubber sheets include natural rubber sheets and butyl rubber sheets.
- Examples of the foam sheet include a foamed polyurethane sheet and a foamed polychloroprene rubber sheet.
- Examples of the metal foil include aluminum foil and copper foil.
- fillers inorganic fillers, organic fillers, etc.
- anti-aging agents antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, plasticizers, and coloring, if necessary
- additives such as additives (pigments, dyes, etc.) may be blended.
- a silicone-based release agent is formed on the back surface of the support base material (the pressure-sensitive adhesive layer non-formed surface). It is preferable that a surface treatment (typically, a peeling treatment to prevent the rewinding force from becoming too high) is applied to adjust the rewinding force of the pressure-sensitive adhesive sheet roll to an appropriate range, such as coating. .
- the thickness of the support substrate can be appropriately selected according to the purpose and is not particularly limited. In general, the thickness is preferably about 20 ⁇ m or more (for example, 30 ⁇ m or more, typically 35 ⁇ m or more), 200 ⁇ m or less (more preferably 100 ⁇ m or less, typically 70 ⁇ m or less, for example, 50 ⁇ m or less). It is appropriate to set the degree.
- the dirt catching part (for example, the pressure-sensitive adhesive sheet) is such that the part (for example, the pressure-sensitive adhesive layer side surface) that contacts the surface to be cleaned exhibits an adhesive strength of, for example, 2 N / 25 mm or less (typically 1 N / 25 mm or less). obtain.
- the adhesive strength is preferably less than 1 N / 25 mm.
- a cleaner having such a light-peelable dirt catching portion is excellent in dirt removal workability because it requires a small force when the dirt removal work is performed on the surface. More specifically, the cleaner can be moved more smoothly on the surface (surface to be cleaned) of the article. Further, for example, there is an advantage that the cleaner can be easily separated from the surface after the dirt removal operation.
- the surface of the article for example, the display surface of a tablet-type information terminal
- a peelable protective film for example, a protective film made of a synthetic resin such as silicone or polyester
- the protective film Due to the light releasability, the protective film is difficult to peel off from the article when the surface of the article covered with the protective film (that is, the surface of the protective film) is cleaned using the cleaner. Therefore, there exists an advantage that it is easy to perform cleaning, maintaining the state which the said protective film covered the article
- the surface to be cleaned is the surface of the protective film, but such a surface is also included in the concept of “the surface of the article” here.
- the adhesive force is preferably less than 1 N / 25 mm as described above, more preferably 0.80 N / 25 mm or less, and 0.60 N / 25 mm or less from the viewpoint of workability for removing dirt. Further preferred. From the viewpoint of operability when cleaning the surface of the protective film, the adhesive strength is suitably 0.50 N / 25 mm or less, preferably 0.30 N / 25 mm or less. It is more preferably 20 N / 25 mm or less, and particularly preferably less than 0.10 N / 25 mm. Further, from the viewpoint of dirt trapping property, the above adhesive strength is usually suitably 0.001 N / 25 mm or more (typically 0.005 N / 25 mm or more), and 0.01 N / 25 mm or more. Is preferably 0.02 N / 25 mm or more, and more preferably 0.03 N / 25 mm or more.
- the adhesive strength refers to 180 ° peel adhesive strength measured based on the following 180 ° peel test using a stainless steel (SUS) plate as an adherend.
- SUS stainless steel
- 180 ° peel test (1) As a test plate (adhered body), a SUS304 steel plate polished with water-resistant abrasive paper is used. The dimensions of the test plate are 2 mm or more in thickness, about 50 mm in width, and about 125 mm in length. The test plate is uniformly polished in the length direction over the entire length using # 360 water-resistant abrasive paper. (2) Before measuring the adhesive strength, the test plate polished with the above water-resistant abrasive paper is washed.
- a reagent-use toluene is infiltrated into a waste cloth to wipe the surface of the test plate, and then the dry surface of the test plate is wiped well with a dry waste cloth until the surface is dried. Such a washing operation is repeated three or more times until it is recognized by visual observation that the surface of the test plate is clean.
- the washed test plate (SUS plate) is left for 5 minutes or more in an atmosphere having a temperature of 23 ⁇ 2 ° C. and a relative humidity (RH) of 50 ⁇ 5%, and then used for measuring the adhesive strength.
- RH relative humidity
- the test piece is preferably about 100 to 300 mm in length and preferably about 15 to 30 mm in width.
- the adhesive strength [N / 25 mm] peeled off by 180 ° may be calculated (converted) from the ratio between the actual width and 25 mm.
- the thickness of the test piece is not particularly limited. (5)
- the adhesive surface (for example, the adhesive layer side surface) of the obtained test piece is attached to the test plate (SUS plate) by reciprocating a 2 kg roller.
- the test piece When the test piece is in a form having adhesiveness on both sides, such as a double-sided pressure-sensitive adhesive sheet, it is preferable to attach a polyethylene terephthalate (PET) film having a thickness of about 25 ⁇ m on the surface opposite to the measurement surface for backing. .
- PET polyethylene terephthalate
- a tensile tester in accordance with JIS Z0237, in an environment of 23 ° C. and RH 50%, a peel angle of 180 °, a tensile speed of 300 mm Under the conditions of / min, the 180 ° peel adhesive strength (vs. SUS 180 ° peel adhesive strength) [N / 25 mm] for the SUS plate is measured.
- the tensile tester is not particularly limited, and a conventionally known tensile tester can be used. For example, it can be measured using “Tensilon” manufactured by Shimadzu Corporation.
- acquisition part for example, adhesive sheet
- the part for example, adhesive surface
- the adhesive force is 1 N / 25mm. Or less (more preferably 0.80 N / 25 mm or less, and still more preferably 0.60 N / 25 mm or less).
- a cleaner having such a lightly peelable dirt catching portion is excellent in dirt removal workability.
- the adhesive strength is suitably 0.50 N / 25 mm or less, preferably 0.30 N / 25 mm or less, more preferably 0.20 N / 25 mm or less, and less than 0.10 N / 25 mm.
- the above adhesive strength is usually suitably 0.001 N / 25 mm or more (typically 0.005 N / 25 mm or more), and 0.01 N / 25 mm or more. Is preferably 0.02 N / 25 mm or more, and more preferably 0.03 N / 25 mm or more.
- the 180 ° peel adhesion to the glass plate was measured except that a glass plate (for example, commercially available float plate glass) was used as the adherend. The measurement may be performed in the same manner as described above.
- acquisition part for example, adhesive sheet
- the part for example, adhesive surface
- 180 degree peeling adhesive force with respect to a polyethylene terephthalate (PET) film May be less than 1 N / 25 mm (more preferably 0.80 N / 25 mm or less, and even more preferably 0.60 N / 25 mm or less).
- PET polyethylene terephthalate
- a cleaner having such a lightly peelable dirt catching portion is excellent in dirt removal workability.
- the adhesive strength is suitably 0.50 N / 25 mm or less, preferably 0.30 N / 25 mm or less, and 0.20 N.
- the above adhesive strength is usually suitably 0.001 N / 25 mm or more (typically 0.005 N / 25 mm or more), and 0.01 N / 25 mm or more. Is preferably 0.02 N / 25 mm or more, and more preferably 0.03 N / 25 mm or more.
- the 180 ° peel adhesion to the PET film may be measured in the same manner as the measurement of the SUS 180 ° peel adhesion except that a PET film is used as the adherend. .
- the adhesive sheet roll is preferably configured to suppress the rail pulling phenomenon.
- the rail pulling phenomenon rolls (rotates) in the direction opposite to the direction in which the sheet roll is wound on the surface to be cleaned (typically, the direction in which the wound single-sided adhesive sheet is peeled off).
- the pressure-sensitive adhesive sheet is based on a pressure-sensitive adhesive force (for example, the 180 ° peel test described above) so that occurrence of a rail pulling phenomenon on a surface to be cleaned (for example, a surface made of glass or synthetic resin such as aluminosilicate glass) is suppressed.
- the measured value) and the unwinding force are preferably harmonized.
- the rewinding force refers to the force required to pull out the pressure-sensitive adhesive sheet from the pressure-sensitive adhesive sheet roll (that is, resistance to rewinding).
- the rewinding force can also be grasped as an adhesive force with respect to the back surface of the pressure-sensitive adhesive sheet (typically the back surface of the support base material).
- the unwinding force when the unwinding force is set too low compared to the adhesive force, when the adhesive sheet roll is rolled on the surface to be cleaned, the unwinding force is reduced to the adhesive sheet (typically the adhesive layer) and the surface to be cleaned. There is a risk of causing the rail pulling phenomenon by losing the adhesive force between the two. On the other hand, when the rewinding force is too high, the pressure-sensitive adhesive sheet tends not to be pulled out smoothly.
- Rewind force can be evaluated as follows. That is, the pressure-sensitive adhesive sheet roll is set in a predetermined tensile testing machine, and the outer peripheral side tip of the wound pressure-sensitive adhesive sheet is attached to the chuck of the testing machine in an environment of a temperature of 23 ° C. and RH of 50%. The pressure-sensitive adhesive sheet roll is rewound in the tangential direction by pulling on the sheet, and the unwinding force at this time is obtained by converting the value to a value [N / 150 mm] per width (for example, 150 mm) of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. Can do. For example, a rewinding force of about 0.5 to 2.5 N / 150 mm is preferable.
- acrylic block copolymer In the following examples, the following acrylic polymers A to C synthesized by a known living anionic polymerization method were used as the acrylic block copolymers.
- MMA methyl methacrylate
- BA n-butyl acrylate
- MMA-2EHA / BA- An acryl-based block copolymer having a triblock structure of “MMA” may be used.
- the weight ratio of 2EHA to BA in the poly 2EHA / BA block (that is, the copolymerization ratio based on weight) is 50/50, and the weight of the poly 2EHA / BA block and the weight of the poly MMA block ( Ratio ((2EHA + BA) / MMA) is 82/18, Mw is 10 ⁇ 10 4 , Mn is 8.4 ⁇ 10 4 , and Mw / Mn is 1.21. there were.
- Acrylic polymer B As the acrylic polymer B, an acrylic block copolymer having a triblock structure of MMA-2EHA / BA-MMA was used.
- the weight ratio of 2EHA to BA in the poly 2EHA / BA block is 50/50, and the weight of the poly 2EHA / BA block and the weight of the poly MMA block (the total weight of the two poly MMA blocks)
- the ratio ((2EHA + BA) / MMA) was 81/19, Mw was 5 ⁇ 10 4 , Mn was 4.4 ⁇ 10 4 , and Mw / Mn was 1.13.
- the acrylic polymer C has a triblock structure of poly MMA block-poly (n-butyl acrylate (BA)) block-poly MMA block (hereinafter sometimes referred to as “MMA-BA-MMA”).
- a commercially available acrylic block copolymer trade name “LA polymer LA2140e” (Kuraray Co., Ltd.) was used.
- This copolymer has a ratio (BA / MMA) of poly BA block weight to poly MMA block weight (total weight of two poly MMA blocks) of 78/22, Mw is 8 ⁇ 10 4 , Mn Was 6 ⁇ 10 4 and Mw / Mn was 1.3.
- Example 1 By applying the acrylic polymer A in the molten state to the surface of a PET sheet-like support substrate (width: about 8 cm) having a thickness of 38 ⁇ m, a pressure-sensitive adhesive layer having a thickness (glue thickness) of about 50 ⁇ m is formed on the support base. A single-sided pressure-sensitive adhesive sheet formed on one side of the material was produced. The obtained single-sided pressure-sensitive adhesive sheet was wound around the surface of a synthetic resin cylindrical holding member (diameter 20 mm) to form a pressure-sensitive adhesive sheet roll. Then, a cleaner as schematically shown in FIGS. 1 and 2 was constructed by mounting the holding member on the tip of the gripping member so as to roll (rotate) freely.
- Example 2 A cleaner according to this example was constructed in the same manner as in Example 1 except that the acrylic polymer B was used instead of the acrylic polymer A.
- a hot-melt acrylic pressure-sensitive adhesive was prepared by mixing 100 parts of acrylic polymer A and 30 parts of a plasticizer “Monocizer W-242” (diisononyl adipate) manufactured by DIC. By applying this acrylic pressure-sensitive adhesive in the molten state to the surface of a sheet-like support substrate made of PET having a thickness of 38 ⁇ m (width: about 8 cm), the pressure-sensitive adhesive layer having a thickness of about 50 ⁇ m is formed on the support substrate. A single-sided pressure-sensitive adhesive sheet formed on one side was prepared. A cleaner according to this example was constructed in the same manner as in Example 1 except that this single-sided adhesive sheet was used.
- Example 4 A cleaner according to this example was constructed in the same manner as in Example 3 except that acrylic polymer B was used instead of acrylic polymer A.
- Example 5 In this example, acrylic polymer A and acrylic polymer B were used as the acrylic polymer at a mass ratio of 50:50. 100 parts of the above acrylic polymer (including 50 parts of acrylic polymer A and 50 parts of acrylic polymer B) and 30 parts of the plasticizer “Monocizer W-242” are mixed to prepare a hot-melt acrylic adhesive. did. About the other point, it carried out similarly to Example 3, and constructed
- Example 6 to 8 The cleaners according to Examples 6 to 8 were the same as in Examples 3 to 5, except that “Reodol SP-O30V” (sorbitan trioleate) manufactured by Kao Corporation was used instead of “Monocizer W-242” as a plasticizer. Built.
- Example 9 to 10 A cleaner according to Example 9 and Example 10 was constructed in the same manner as Example 3 and Example 6 except that acrylic polymer C was used instead of acrylic polymer A.
- Acrylic polymer D was synthesized by a solution polymerization method. Specifically, toluene as a polymerization solvent and 2EHA and acrylic acid (AA) as monomers are put into a three-necked flask so that the mass ratio of 2EHA: AA is 95: 5, The mixture was gently stirred for 1 hour or longer. Next, dibenzoyl peroxide (BPO) (“Nipper BW” manufactured by NOF Corporation) is added as a polymerization initiator, the temperature is raised to 60 ° C., the reaction is continued for 2 hours, and the temperature is further raised to 80 ° C. for 1 hour.
- BPO dibenzoyl peroxide
- a toluene solution of acrylic polymer D (random copolymer of the above monomers) having a weight average molecular weight (Mw) of 50 ⁇ 10 4 to 60 ⁇ 10 4 was prepared.
- Mw weight average molecular weight
- 30 parts of a plasticizer “Monocizer W-242”, 0.1 part of an epoxy crosslinking agent (“TETRAD-C” manufactured by Mitsubishi Gas Chemical), 2 parts of an isocyanate-based crosslinking agent (“Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) was mixed to prepare a solvent-type acrylic pressure-sensitive adhesive composition (S1).
- Example 12 Except for the point that the amount of plasticizer “Monocizer W-242” was changed to 60 parts and the amount of the epoxy-based crosslinking agent “TETRAD-C” changed to 0.5 parts, the same as in Example 11, A solvent-type acrylic pressure-sensitive adhesive composition (S2) was prepared. A cleaner according to this example was constructed in the same manner as in Example 11 except that this pressure-sensitive adhesive composition (S2) was used.
- Example 13 A cleaner according to this example was constructed in the same manner as in Example 5 except that the amount of the plasticizer “Monocizer W-242” was changed to 50 parts with respect to 100 parts of the acrylic polymer.
- Example 14 A cleaner according to this example was constructed in the same manner as Example 13 except that 5 parts of a tackifier (terpene phenol resin, “K-125” manufactured by Yasuhara Chemical Co., Ltd.) was further mixed with 100 parts of an acrylic polymer.
- a tackifier Terpene phenol resin, “K-125” manufactured by Yasuhara Chemical Co., Ltd.
- Example 15 to 17 Except that the amount of the tackifier “K-125” was changed to 10 parts (Example 15), 15 parts (Example 16) and 20 parts (Example 17) respectively, Constructed a cleaner.
- Example 18 A cleaner according to this example was constructed in the same manner as in Example 13 except that the plasticizer “Eposizer W-121” (epoxidized fatty acid) manufactured by DIC was used instead of the plasticizer “Monocizer W-242”.
- Example 19 The cleaner according to this example was changed in the same manner as in Example 13 except that the plasticizer “Eposizer W-100-EL” (epoxidized soybean oil) manufactured by DIC was used instead of the plasticizer “Monocizer W-242”. It was constructed.
- the plasticizer “Eposizer W-100-EL” epoxidized soybean oil manufactured by DIC was used instead of the plasticizer “Monocizer W-242”. It was constructed.
- acrylic polymer A and acrylic polymer B were used as the acrylic polymer at a mass ratio of 80:20.
- 100 parts of the above acrylic polymer including 80 parts of acrylic polymer A and 20 parts of acrylic polymer B
- Example 21 100 parts of the same acrylic polymer as in Example 20 (including 80 parts of acrylic polymer A and 20 parts of acrylic polymer B), 50 parts of plasticizer “Monocizer W-242”, and 20 parts of tackifier “UH-115” And 20 parts of an acrylic oligomer (“UP-1000” manufactured by Toagosei Co., Ltd., non-functional group type, Mw about 3000) were mixed to prepare a hot-melt acrylic pressure-sensitive adhesive. About the other point, it carried out similarly to Example 3, and constructed
- Example 22 100 parts of the same acrylic polymer as in Example 20 (including 80 parts of acrylic polymer A and 20 parts of acrylic polymer B), 50 parts of plasticizer “Monocizer W-242”, and 15 parts of tackifier “UH-115” Were mixed to prepare a hot melt type acrylic pressure-sensitive adhesive.
- melt viscosity at 180 ° C. of this acrylic pressure-sensitive adhesive was measured by the above-described melt viscosity measurement method, it was about 10 Pa ⁇ s.
- a cleaner according to this example was constructed in the same manner as in Example 3 except that this acrylic adhesive was used.
- Example 23 100 parts of the same acrylic polymer as in Example 20 (including 80 parts of acrylic polymer A and 20 parts of acrylic polymer B), 30 parts of plasticizer “Monocizer W-242”, and 10 parts of tackifier “UH-115” And 50 parts of an acrylic oligomer “UP-1000” were mixed to prepare a hot-melt acrylic pressure-sensitive adhesive. About the other point, it carried out similarly to Example 3, and constructed
- acrylic polymer A and acrylic polymer B were used as the acrylic polymer at a mass ratio of 65:35.
- 100 parts of the above acrylic polymer including 65 parts of acrylic polymer A and 35 parts of acrylic polymer B
- acrylic A hot-melt acrylic pressure-sensitive adhesive was prepared by mixing 50 parts of the oligomer “UP-1000”. About the other point, it carried out similarly to Example 3, and constructed
- Example 25 100 parts of the same acrylic polymer as Example 24 (including 65 parts of acrylic polymer A and 35 parts of acrylic polymer B), 50 parts of plasticizer “Monocizer W-242” and 10 parts of tackifier “UH-115” Were mixed to prepare a hot melt type acrylic pressure-sensitive adhesive. About the other point, it carried out similarly to Example 3, and constructed
- Example 26 100 parts of the same acrylic polymer as in Example 24 (including 65 parts of acrylic polymer A and 35 parts of acrylic polymer B), 30 parts of plasticizer “Monocizer W-242”, and 30 parts of tackifier “UH-115” And 20 parts of an acrylic oligomer “UP-1000” were mixed to prepare a hot-melt acrylic adhesive. About the other point, it carried out similarly to Example 3, and constructed
- acrylic polymer A and acrylic polymer B were used as the acrylic polymer at a mass ratio of 50:50.
- 100 parts of the above acrylic polymer including 50 parts of acrylic polymer A and 50 parts of acrylic polymer B
- acrylic A hot-melt acrylic pressure-sensitive adhesive was prepared by mixing 20 parts of the oligomer “UP-1000”. About the other point, it carried out similarly to Example 3, and constructed
- Example 28 100 parts of the same acrylic polymer as Example 27 (including 50 parts of acrylic polymer A and 50 parts of acrylic polymer B), 50 parts of plasticizer “Monocizer W-242”, and 30 parts of tackifier “UH-115” And 50 parts of an acrylic oligomer “UP-1000” were mixed to prepare a hot-melt acrylic pressure-sensitive adhesive. About the other point, it carried out similarly to Example 3, and constructed
- Example 29 100 parts of the same acrylic polymer as Example 27 (including 50 parts of acrylic polymer A and 50 parts of acrylic polymer B), 30 parts of plasticizer “Monocizer W-242”, and 20 parts of tackifier “UH-115” Were mixed to prepare a hot melt type acrylic pressure-sensitive adhesive. About the other point, it carried out similarly to Example 3, and constructed
- the glossiness at the measurement angle of 60 ° was approximately the value shown in the table with respect to the blank glossiness G0 (that is, about 70% of G0 in Table 1, 3 was about 80%). And the surface of the said protective film with sebum dirt was cleaned with the cleaner concerning each example.
- the adhesive sheet roll of the cleaner according to each example was rotated once in one direction along the surface of the protective film.
- the rolling speed was about 0.5 m / second, and the pressing force of the operator when rolling was about 700 g.
- the measurement was performed twice and the average value was recorded. The results are shown in Tables 1 and 3.
- a tablet-type information terminal (iPad (trademark): Apple product) was prepared, and the display surface (smooth surface made of aluminosilicate glass) was carefully wiped off with a non-woven cloth.
- the checker IG-331 the glossiness of the display surface (blank glossiness G0) was measured under the condition of a measurement angle of 60 °.
- the sebum component adhering to the tester's face was rubbed onto the finger, and organic soil composed of the sebum component adhering to the finger was rubbed onto the display surface and transferred.
- the amount of organic soil transferred was such that the glossiness at a measurement angle of 60 ° (glossiness at the time of contamination G1) was about 50% of the blank glossiness G0.
- the display surface with the sebum stain was cleaned with the cleaner according to each example. Specifically, the adhesive sheet roll of the cleaner according to each example was rotated once in one direction along the display surface. The rolling speed was about 0.5 m / second, and the pressing force of the operator when rolling was about 700 g.
- the adhesive sheet roll of the cleaner according to each example was rotated three times in one direction along the surface of the protective film.
- the rolling speed was about 0.5 m / second, and the pressing force of the operator when rolling was about 700 g.
- the surface of the protective film after cleaning was visually observed, and the fingerprint removability was evaluated in the following three stages. The results are shown in Tables 1 and 3. 3: The trace of the fingerprint was almost lost. 2: Some fingerprints disappeared. 1: Although the trace of a fingerprint became thin, it did not disappear.
- Example 1 and Example 3 From the comparison between Example 1 and Example 3 and the comparison between Example 2 and Example 4, it can be seen that by containing a plasticizer, the adhesive strength can be reduced and at the same time the sebum dirt removal rate can be improved. Also, comparing Examples 3 to 5 and Examples 6 to 8, the plasticizer is “Monosizer W-242” (diisononyl adipate) rather than “Reodol SP-O30V” (sorbitan trioleate). It turns out that it is excellent in property. Further, it can be seen from the comparison of Examples 3 to 5 that the pressure-sensitive adhesive containing the acrylic polymer A having a higher Mw is superior in the fingerprint removability.
- each of the cleaners of Examples 13 to 19 having an adhesive containing an acrylic block copolymer as a base polymer was sebum while being lightly peeled with an adhesive strength of less than 0.10 N / 25 mm. Excellent organic soil removability with a soil removal rate of 90% or more was exhibited.
- the cleaners of Examples 13 to 19 show the same performance as the cleaner of Example 11 (solvent type) in the removal rate of sebum dirt, and have excellent dirt removal workability because the adhesive strength is significantly lower than that of Example 11. Met. Further, the cleaner (solvent type) of Example 12 in which the amounts of the plasticizer and the crosslinking agent were increased in the pressure-sensitive adhesive composition of Example 11 was similar to the cleaners of Examples 13 to 19 in terms of adhesive strength.
- the cleaners of Examples 20 to 29 each having an adhesive containing an acrylic block copolymer as a base polymer are all sebum while being lightly peeled with an adhesive strength of less than 0.20 N / 25 mm. It was confirmed that the organic soil stain removability was 94% or more.
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Abstract
Description
本出願は、2013年6月25日に出願された日本国特許出願2013-133202に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
好ましい一態様において、アルキル基の炭素原子数が6以上(例えば6~12)のアルキルアクリレートを主モノマーとするAcブロックをソフトセグメント(B)として有するアクリル系ブロック共重合体を用いることができる。すなわち、上記Acブロックを構成するモノマー単位のうち50質量%以上が、アルキル基の炭素原子数が6以上のアルキルアクリレートの1種または2種以上によって占められていることが好ましい。上記Acブロックを構成するモノマー単位のうち、アルキル基の炭素原子数が6以上のアルキルアクリレートの占める割合は、例えば55質量%以上とすることができ、60質量%以上であってもよく、好ましくは70質量%以上、より好ましくは85質量%以上、さらに好ましくは95質量%以上であり、実質的に100質量%であってもよい。例えば、Acブロックを構成するモノマー単位が2EHA単独であるAcブロックをソフトセグメント(B)として有するアクリル系ブロック共重合体が好ましい。
なお、アルキル基の炭素原子数が6以上のアルキルアクリレートの好適例としては、2-エチルへキシルアクリレート(2EHA)、n-オクチルアクリレート、イソノニルアクリレート、n-ヘキシルアクリレート等が例示される。
また、アルキル基の炭素原子数が6以上のアルキルアクリレートを含むAcブロックをソフトセグメント(B)として有するアクリル系ブロック共重合体は、可塑剤との相溶性に優れたものとなり得る。このことは、該共重合体と可塑剤とを含む組成の粘着剤において、可塑剤のブリードアウトを抑制する観点から好ましい。また、より多くの可塑剤を適切に含有させることができるので、可塑剤の配合量の設定自由度が高く、粘着力を調整しやすいという利点がある。
観測周波数:1H;600MHz
フリップ角:30°
測定溶媒:CDCl3
測定温度:300K
化学シフト基準:測定溶媒(CDCl3,1H:7.25ppm)
・カラム:東ソー社製、TSKgel SuperHZM-H/HZ4000/HZ3000/HZ2000
・カラムサイズ:各6.0mmI.D.×150mm
・溶離液:THF
・流量:0.6mL/min
・検出器:示差屈折計(RI)
・カラム温度(測定温度):40℃
・サンプル濃度:約2.0g/L(THF溶液)
・サンプル注入量:20μL
このような可塑剤は、例えば、アルキル基の炭素原子数が6以上(例えば6~12)のアルキルアクリレートを含むAcブロックをソフトセグメント(B)として有するアクリル系ブロック共重合体をベースポリマーとして含む粘着剤に含有されて、該粘着剤の溶融粘度および粘着力を低下させる効果と、有機質汚れの捕捉性を向上させる効果とを高レベルで発揮し得る。
ここで、上記溶融粘度は以下の溶融粘度測定方法により測定することができる。
[溶融粘度測定方法]
測定機:米国ブルックフィールド社製、プログラマブル粘度計(DV-II+Pro)
測定条件:測定温度180℃、回転数2.5rpm、スピンドルSC4-27
測定手順:粘着剤約14gをサンプルチャンバーに入れ、180℃に加熱して溶融させる。その溶融した粘着剤中にスピンドルを沈めて回転させ、回転開始から30分後の溶融粘度を読み取る。
また、上記粘着力は、汚れ捕捉性の観点から、通常は0.001N/25mm以上(典型的には0.005N/25mm以上)とすることが適当であり、0.01N/25mm以上とすることが好ましく、0.02N/25mm以上とすることがより好ましく、0.03N/25mm以上とすることがさらに好ましい。
[180°剥離試験]
(1)試験板(被着体)としては、SUS304鋼板を耐水研磨紙で磨いたものを用いる。試験板の寸法は、厚さ2mm以上、幅約50mm、長さ約125mmとし、♯360の耐水研磨紙を用いて上記試験板を全長にわたって長さ方向に均一に研磨する。
(2)粘着力を測定する前には、上記耐水研磨紙で磨いた試験板を洗浄する。洗浄の手順としては、試薬用のトルエンをウェスに染込ませて試験板の表面を拭いた後、さらに乾いたウェスを用いて上記試験板の表面を乾燥するまでよく拭く。このような洗浄操作を、目視によって試験板の表面が清浄になったと認められるまで3回以上繰り返して行う。
(3)洗浄後の試験板(SUS板)は、温度23±2℃、相対湿度(RH)50±5%の雰囲気中に5分以上放置した後、粘着力の測定に使用する。
(4)汚れ捕捉部(典型的には粘着シート)を長方形シート状にカットした試験片を用意する。試験片は、長さ100~300mm程度とすることが好ましく、幅は15~30mm程度とすることが好ましい。幅が25mmでない場合、実際の幅と25mmとの比から180°引き剥がし粘着力[N/25mm]を算出(換算)すればよい。試験片の厚さは特に限定されない。
(5)得られた試験片の粘着面(例えば粘着剤層側表面)を上記試験板(SUS板)に、2kgのローラーを一往復させて貼り付ける。試験片が両面粘着シート等のように両面に粘着性を有する形態である場合、測定面とは反対側の表面に厚さ25μm程度のポリエチレンテレフタレート(PET)フィルムを貼り付けて裏打ちすることが好ましい。
(6)これを23℃、RH50%の環境下に30分間保持した後、引張試験機を用い、JIS Z0237に準拠して、23℃、RH50%の環境下、剥離角度180°、引張速度300mm/分の条件にて、上記SUS板に対する180°引き剥がし粘着力(対SUS180°引き剥がし粘着力)[N/25mm]を測定する。引張試験機は特に限定されず、従来公知の引張試験機を用いることができる。例えば、島津製作所社製の「テンシロン」を用いて測定することができる。
以下の例では、アクリル系ブロック共重合体として、公知のリビングアニオン重合法により合成された以下のアクリル系ポリマーA~Cを使用した。
(アクリル系ポリマーA)
アクリル系ポリマーAとしては、ポリ(メチルメタクリレート(MMA))ブロック-ポリ(2-エチルヘキシルアクリレート(2EHA)/n-ブチルアクリレート(BA))ブロック-ポリMMAブロック(以下、「MMA-2EHA/BA-MMA」と表記することがある。)のトリブロック構造を有するアクリル系ブロック共重合体を使用した。この共重合体は、ポリ2EHA/BAブロックにおける2EHAとBAとの重量比(すなわち、重量基準の共重合比率)は50/50であり、ポリ2EHA/BAブロックの重量とポリMMAブロックの重量(2つのポリMMAブロックの合計重量)との比((2EHA+BA)/MMA)が82/18であり、Mwは10×104、Mnは8.4×104、Mw/Mnは1.21であった。
(アクリル系ポリマーB)
アクリル系ポリマーBとしては、MMA-2EHA/BA-MMAのトリブロック構造を有するアクリル系ブロック共重合体を使用した。この共重合体は、ポリ2EHA/BAブロックにおける2EHAとBAとの重量比は50/50であり、ポリ2EHA/BAブロックの重量とポリMMAブロックの重量(2つのポリMMAブロックの合計重量)との比((2EHA+BA)/MMA)が81/19であり、Mwは5×104、Mnは4.4×104、Mw/Mnは1.13であった。
(アクリル系ポリマーC)
アクリル系ポリマーCとしては、ポリMMAブロック-ポリ(n-ブチルアクリレート(BA))ブロック-ポリMMAブロック(以下、「MMA-BA-MMA」と表記することがある。)のトリブロック構造を有する市販のアクリル系ブロック共重合体、商品名「LAポリマー LA2140e」(クラレ社製品)を使用した。この共重合体は、ポリBAブロックの重量とポリMMAブロックの重量(2つのポリMMAブロックの合計重量)との比(BA/MMA)が78/22であり、Mwは8×104、Mnは6×104、Mw/Mnは1.3であった。
アクリル系ポリマーAを溶融状態で厚さ38μmのPET製のシート状支持基材(幅:約8cm)の表面に塗付することにより、厚さ(糊厚)約50μmの粘着剤層が支持基材の片面に形成された片面粘着シートを作製した。得られた片面粘着シートを合成樹脂製の円筒状保持部材(直径20mm)の表面に巻回することにより粘着シートロールを形成した。そして、上記保持部材を把持部材の先端に転動(回転)自在に装着することにより、図1,2に模式的に示すようなクリーナーを構築した。
アクリル系ポリマーAに代えてアクリル系ポリマーBを用いた他は例1と同様にして、本例に係るクリーナーを構築した。
アクリル系ポリマーA100部と、DIC社製の可塑剤「モノサイザーW-242」(アジピン酸ジイソノニル)30部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。このアクリル系粘着剤を溶融状態で厚さ38μmのPET製のシート状支持基材(幅:約8cm)の表面に塗付することにより、厚さ約50μmの粘着剤層が上記支持基材の片面に形成された片面粘着シートを作製した。この片面粘着シートを用いた他は例1と同様にして、本例に係るクリーナーを構築した。
アクリル系ポリマーAに代えてアクリル系ポリマーBを用いた他は例3と同様にして、本例に係るクリーナーを構築した。
本例では、アクリル系ポリマーとして、アクリル系ポリマーAとアクリル系ポリマーBとを50:50の質量比で使用した。上記アクリル系ポリマー100部(アクリル系ポリマーA50部、アクリル系ポリマーB50部を含む。)と可塑剤「モノサイザーW-242」30部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
可塑剤として「モノサイザーW-242」に代えて花王社製の「レオドールSP-O30V」(ソルビタントリオレエート)を使用した他は例3~5とそれぞれ同様にして、例6~8に係るクリーナーを構築した。
アクリル系ポリマーAに代えてアクリル系ポリマーCを用いた他は例3および例6とそれぞれ同様にして、例9および例10に係るクリーナーを構築した。
溶液重合法によりアクリル系ポリマーDを合成した。具体的には、重合溶媒としてのトルエンと、モノマーとしての2EHAおよびアクリル酸(AA)とを、2EHA:AAの質量比が95:5となるように3つ口フラスコに投入し、窒素気流下にて1時間以上緩やかに攪拌した。次いで、重合開始剤としてジベンゾイルパーオキサイド(BPO)(日本油脂社製の「ナイパーBW」)を添加し、60℃に昇温させて2時間反応させ、さらに80℃に昇温して1時間反応させることにより、重量平均分子量(Mw)が50×104~60×104のアクリル系ポリマーD(上記モノマーのランダム共重合体)のトルエン溶液を調製した。
このトルエン溶液に含まれるアクリル系ポリマーD100部に対し、可塑剤「モノサイザーW-242」30部と、エポキシ系架橋剤(三菱ガス化学社製の「TETRAD-C」)0.1部と、イソシアネート系架橋剤(日本ポリウレタン工業社製の「コロネートL」)2部とを混合し、溶剤型のアクリル系粘着剤組成物(S1)を調製した。
このアクリル系粘着剤組成物(S1)を厚さ38μmのPET製のシート状支持基材(幅:約8cm)の表面に塗付した後、乾燥処理を行うことにより、厚さ約50μmの粘着剤層が上記支持基材の片面に形成された片面粘着シートを作製した。この片面粘着シートを用いた他は例1と同様にして、本例に係るクリーナーを構築した。
可塑剤「モノサイザーW-242」の使用量を60部に変更した点およびエポキシ系架橋剤「TETRAD-C」の使用量を0.5部に変更した点以外は例11と同様にして、溶剤型のアクリル系粘着剤組成物(S2)を調製した。この粘着剤組成物(S2)を用いた点以外は例11と同様にして、本例に係るクリーナーを構築した。
可塑剤「モノサイザーW-242」の量をアクリル系ポリマー100部に対して50部に変更した他は例5と同様にして、本例に係るクリーナーを構築した。
アクリル系ポリマー100部に対して粘着付与剤(テルペンフェノール樹脂、ヤスハラケミカル社製「K-125」)5部をさらに混合した他は例13と同様にして、本例に係るクリーナーを構築した。
粘着付与剤「K-125」の量を10部(例15)、15部(例16)および20部(例17)にそれぞれ変更した点以外は例14と同様にして、例15~17に係るクリーナーを構築した。
可塑剤「モノサイザーW-242」に代えてDIC社製の可塑剤「エポサイザーW-121」(エポキシ化脂肪酸)を使用した他は例13と同様にして、本例に係るクリーナーを構築した。
可塑剤「モノサイザーW-242」に代えてDIC社製の可塑剤「エポサイザーW-100-EL」(エポキシ化大豆油)を使用した他は例13と同様にして、本例に係るクリーナーを構築した。
本例では、アクリル系ポリマーとして、アクリル系ポリマーAとアクリル系ポリマーBとを80:20の質量比で使用した。上記アクリル系ポリマー100部(アクリル系ポリマーA80部、アクリル系ポリマーB20部を含む。)と、可塑剤「モノサイザーW-242」70部と、粘着付与剤(水素添加テルペンフェノール樹脂、ヤスハラケミカル社製「UH-115」)30部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
例20と同じアクリル系ポリマー100部(アクリル系ポリマーA80部、アクリル系ポリマーB20部を含む。)と、可塑剤「モノサイザーW-242」50部と、粘着付与剤「UH-115」20部と、アクリル系オリゴマー(東亞合成社製「UP-1000」、無官能基タイプ、Mw約3000)20部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
例20と同じアクリル系ポリマー100部(アクリル系ポリマーA80部、アクリル系ポリマーB20部を含む。)と、可塑剤「モノサイザーW-242」50部と、粘着付与剤「UH-115」15部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。このアクリル系粘着剤の180℃における溶融粘度を上述した溶融粘度測定方法により測定したところ、約10Pa・sであった。このアクリル系粘着剤を用いた他は例3と同様にして、本例に係るクリーナーを構築した。
例20と同じアクリル系ポリマー100部(アクリル系ポリマーA80部、アクリル系ポリマーB20部を含む。)と、可塑剤「モノサイザーW-242」30部と、粘着付与剤「UH-115」10部と、アクリル系オリゴマー「UP-1000」50部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
本例では、アクリル系ポリマーとして、アクリル系ポリマーAとアクリル系ポリマーBとを65:35の質量比で使用した。上記アクリル系ポリマー100部(アクリル系ポリマーA65部、アクリル系ポリマーB35部を含む。)と、可塑剤「モノサイザーW-242」70部と、粘着付与剤「UH-115」20部と、アクリル系オリゴマー「UP-1000」50部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
例24と同じアクリル系ポリマー100部(アクリル系ポリマーA65部、アクリル系ポリマーB35部を含む。)と、可塑剤「モノサイザーW-242」50部と、粘着付与剤「UH-115」10部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
例24と同じアクリル系ポリマー100部(アクリル系ポリマーA65部、アクリル系ポリマーB35部を含む。)と、可塑剤「モノサイザーW-242」30部と、粘着付与剤「UH-115」30部と、アクリル系オリゴマー「UP-1000」20部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
本例では、アクリル系ポリマーとして、アクリル系ポリマーAとアクリル系ポリマーBとを50:50の質量比で使用した。上記アクリル系ポリマー100部(アクリル系ポリマーA50部、アクリル系ポリマーB50部を含む。)と、可塑剤「モノサイザーW-242」70部と、粘着付与剤「UH-115」10部と、アクリル系オリゴマー「UP-1000」20部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
例27と同じアクリル系ポリマー100部(アクリル系ポリマーA50部、アクリル系ポリマーB50部を含む。)と、可塑剤「モノサイザーW-242」50部と、粘着付与剤「UH-115」30部と、アクリル系オリゴマー「UP-1000」50部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
例27と同じアクリル系ポリマー100部(アクリル系ポリマーA50部、アクリル系ポリマーB50部を含む。)と、可塑剤「モノサイザーW-242」30部と、粘着付与剤「UH-115」20部とを混合して、ホットメルト型のアクリル系粘着剤を調製した。その他の点については例3と同様にして、本例に係るクリーナーを構築した。
上述した180°剥離試験に基づいて、各例に係る粘着シートの180°引き剥がし粘着力を測定した。より具体的には、各例に係る粘着シートを200mm×25mmの帯状にカットして試験片を用意した。上記試験片の粘着面(粘着剤層の表面)をステンレス鋼(SUS304)板に、2kgのローラーを一往復させて貼り付けた。これを23℃、RH50%の環境下に30分間保持した後、引張試験機を用い、JIS Z0237に準拠して、23℃、RH50%の環境下、剥離角度180°、引張速度300mm/分の条件にて、対SUS180°引き剥がし粘着力[N/25mm]を測定した。測定は、島津製作所社製の「テンシロン」を用いて行った。結果を表1~3に示す。
(保護フィルム表面のクリーニング)
表示面(アルミノケイ酸ガラス製の平滑な表面)に保護フィルムが貼り付けられたスマートフォン(docomo NEXT series「Xperia(商標) Z SO-02E」;Sony Mobile Communications AB社製品)を用意した。保護フィルムとしては、上記スマートフォン用のジャケット(ハードコーティング・グラデーション・シェルジャケット、レイ・アウト社製品)に付属の保護フィルムを使用した。
上記保護フィルムの表面の汚れを不織布製のウェスで念入りに拭き取った後、堀場製作所社製のハンディ光沢計「グロスチェッカIG-331」を用いて、測定角60°の条件で、上記保護フィルム表面の光沢度(ブランク光沢度G0)を測定した。次いで、試験者の顔面(頬)に付着する皮脂成分を手指にこすり付け、当該手指に付いている皮脂成分からなる有機質汚れを、上記表示面に貼り付けられた保護フィルムの表面に擦りつけて転写した。上記有機質汚れの転写量は、測定角60°における光沢度(汚染時光沢度G1)が、ブランク光沢度G0に対して概ね表中に示す値(すなわち、表1ではG0の約70%、表3では約80%)となる量とした。
そして、皮脂汚れが付いた上記保護フィルムの表面を各例に係るクリーナーでクリーニングした。具体的には、各例に係るクリーナーの粘着シートロールを上記保護フィルムの表面に沿う1方向に1回転がした。転がし速度は約0.5m/秒とし、転がす際の作業者の押圧力は約700gとした。そのクリーニング後の保護フィルム表面につき、上記と同様にして測定角60°における光沢度(クリーニング後光沢度G2)を測定した。それらの測定結果から、次式:皮脂汚れ除去率(%)=(G2/G0)×100;に基づき、皮脂汚れ除去率(%)を算出した。測定は2回行い、その平均値を記録した。結果を表1および表3に示す。
タブレット型情報端末(iPad(商標):アップル社製品)を用意し、その表示面(アルミノケイ酸ガラス製の平滑な表面)の汚れを不織布製のウェスで念入りに拭き取った後、上記光沢計「グロスチェッカIG-331」を用いて、測定角60°の条件で、上記表示面の光沢度(ブランク光沢度G0)を測定した。次いで、試験者の顔面(頬)に付着する皮脂成分を手指にこすり付け、当該手指に付いている皮脂成分からなる有機質汚れを上記表示面に擦りつけて転写した。上記有機質汚れの転写量は、測定角60°における光沢度(汚染時光沢度G1)が、ブランク光沢度G0の約50%となる量とした。
そして、皮脂汚れが付いた上記表示面の上を各例に係るクリーナーでクリーニングした。具体的には、各例に係るクリーナーの粘着シートロールを上記表示面に沿う1方向に1回転がした。転がし速度は約0.5m/秒とし、転がす際の作業者の押圧力は約700gとした。そのクリーニング後の表示面につき、上記と同様にして測定角60°における光沢度(クリーニング後光沢度G2)を測定した。それらの測定結果から、次式:皮脂汚れ除去率(%)=(G2/G0)×100;に基づき、皮脂汚れ除去率(%)を算出した。測定は2回行い、その平均値を記録した。結果を表2に示す。
表示面に保護フィルムが貼り付けられたスマートフォンを用意した。スマートフォンおよび保護フィルムとしては、皮脂汚れ除去率の評価に用いたものと同じものを使用した。
上記保護フィルムの表面の汚れを不織布製のウェスで念入りに拭き取った。次いで、試験者の顔面(頬)に付着している皮脂成分を手指(人差し指)にこすり付け、その手指を上記保護フィルムの表面に2秒間じっと押し付けることにより、当該手指に付いている皮脂成分からなる有機質汚れ(指紋)を上記保護フィルムに転写した。
そして、上記指紋が付いた上記保護フィルムの表面を各例に係るクリーナーでクリーニングした。具体的には、各例に係るクリーナーの粘着シートロールを上記保護フィルムの表面に沿う1方向に3回転がした。転がし速度は約0.5m/秒とし、転がす際の作業者の押圧力は約700gとした。クリーニング後の保護フィルム表面を目視で観察し、指紋の除去性を以下の3段階で評価した。結果を表1および表3に示す。
3:指紋の跡が概ね消失した。
2:指紋の跡が一部消失した。
1:指紋の跡が薄くなったが消失はしなかった。
また、可塑剤を用いた例3~10のクリーナーは、粘着力0.80N/25mm以下という軽剥離でありながら、80%以上の皮脂汚れ除去率を示した。特に、アクリル系ポリマーA,Bと可塑剤とを組み合わせた例3~8に係るクリーナーによると、粘着力0.20N/25mm以下の軽剥離でありながら、93%以上の皮脂汚れ除去率が実現された。
2 表面(表示部)
10 粘着クリーナー
20 保持部材
30 粘着シートロール
31 粘着シート(汚れ捕捉部)
32 粘着剤層
36 支持基材
40 把持部材
42 取っ手
50 有機質汚れ
Claims (9)
- 物品の表面に付着している有機質汚れを除去するために使用される粘着クリーナーであって、
前記物品の表面に接触することによって前記有機質汚れを捕捉する汚れ捕捉部を備えており、
前記汚れ捕捉部は、前記物品の表面と接触する部分に粘着剤を備えており、
前記粘着剤は、ベースポリマーとして、1分子中にハードセグメント(A)およびソフトセグメント(B)を有するアクリル系ブロック共重合体を含む、有機質汚れ除去用粘着クリーナー。 - 前記ソフトセグメント(B)を構成するモノマー単位は、アルキル基の炭素原子数が6以上のアルキルアクリレートを主成分とする、請求項1に記載の粘着クリーナー。
- 前記粘着剤は可塑剤をさらに含む、請求項1または2に記載の粘着クリーナー。
- 前記粘着剤は粘着付与樹脂をさらに含む、請求項1から3のいずれか一項に記載の粘着クリーナー。
- 前記汚れ捕捉部の前記表面に接触する部分は1N/25mm以下の粘着力を示す、請求項1から4のいずれか一項に記載の粘着クリーナー。
- 円筒状の転動部材を備えており、前記汚れ捕捉部は該転動部材の外周面に配置されている、請求項1から5のいずれか一項に記載の粘着クリーナー。
- 前記汚れ捕捉部は、シート状の支持基材と該支持基材上に配置された粘着剤層とを備える片面粘着シートとして構成されており、
前記片面粘着シートは、前記粘着剤層を外側にして巻回されることにより粘着シートロールとして構成されている、請求項1から6のいずれか一項に記載の粘着クリーナー。 - 前記有機質汚れとして皮脂汚れを取り除くために使用される、請求項1から7のいずれか一項に記載の粘着クリーナー。
- 前記物品は、ガラス製または合成樹脂製の表示面を有するポータブル機器である、請求項1から8のいずれか一項に記載の粘着クリーナー。
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JP6814527B2 (ja) * | 2014-12-24 | 2021-01-20 | 株式会社ニトムズ | 粘着クリーナー |
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- 2014-06-23 KR KR1020157036719A patent/KR102140999B1/ko active IP Right Grant
- 2014-06-23 CN CN201480035881.9A patent/CN105407779A/zh active Pending
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WO2017014154A1 (ja) * | 2015-07-22 | 2017-01-26 | 株式会社クラレ | (メタ)アクリル系ブロック共重合体 |
CN107849203A (zh) * | 2015-07-22 | 2018-03-27 | 株式会社可乐丽 | (甲基)丙烯酸系嵌段共聚物 |
JPWO2017014154A1 (ja) * | 2015-07-22 | 2018-05-10 | 株式会社クラレ | (メタ)アクリル系ブロック共重合体 |
JP2018111744A (ja) * | 2017-01-06 | 2018-07-19 | リンテック株式会社 | 粘着体 |
JP2017214596A (ja) * | 2017-08-30 | 2017-12-07 | 株式会社クラレ | 粘接着剤組成物 |
JP2018003035A (ja) * | 2017-10-16 | 2018-01-11 | 株式会社クラレ | 粘接着剤組成物 |
Also Published As
Publication number | Publication date |
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JP6704729B2 (ja) | 2020-06-03 |
JPWO2014208500A1 (ja) | 2017-02-23 |
KR102140999B1 (ko) | 2020-08-04 |
EP3015044A4 (en) | 2017-03-15 |
KR20160023722A (ko) | 2016-03-03 |
EP3015044B1 (en) | 2019-08-07 |
CN105407779A (zh) | 2016-03-16 |
US20160213222A1 (en) | 2016-07-28 |
EP3015044A1 (en) | 2016-05-04 |
US10213090B2 (en) | 2019-02-26 |
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