WO2018048243A1 - Composition adhésive pour écran pliable - Google Patents

Composition adhésive pour écran pliable Download PDF

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Publication number
WO2018048243A1
WO2018048243A1 PCT/KR2017/009873 KR2017009873W WO2018048243A1 WO 2018048243 A1 WO2018048243 A1 WO 2018048243A1 KR 2017009873 W KR2017009873 W KR 2017009873W WO 2018048243 A1 WO2018048243 A1 WO 2018048243A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
foldable
adhesive composition
group
Prior art date
Application number
PCT/KR2017/009873
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English (en)
Korean (ko)
Inventor
박현규
노동규
권윤경
박병수
이희제
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170114559A external-priority patent/KR102024252B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP17849127.0A priority Critical patent/EP3511389B1/fr
Priority to CN201780048516.5A priority patent/CN109563395B/zh
Priority to US16/331,767 priority patent/US10920113B2/en
Priority to JP2019500643A priority patent/JP6860128B2/ja
Publication of WO2018048243A1 publication Critical patent/WO2018048243A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/06—Printing inks based on fatty oils
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
    • G06F1/16—Constructional details or arrangements

Definitions

  • the present application relates to a pressure-sensitive adhesive composition for foldable display and its use.
  • the deformable display device may be not only deformed in a predetermined form, but also may be deformed in various forms in response to a user's request or in accordance with the needs of a situation in which the display device is used. Therefore, it is necessary to recognize the modified form of the display and to control the display device in response to the recognized form.
  • the deformable display apparatus since the deformable display apparatus has a problem in that each component of the display apparatus is damaged due to the deformation, the respective components of the display apparatus must satisfy folding reliability and stability.
  • Patent Document 1 Republic of Korea Patent Publication 2015-0011230 A
  • the present application provides a pressure-sensitive adhesive composition for foldable display and its use.
  • the present application provides a pressure-sensitive adhesive composition for foldable display having excellent bending reliability by satisfying a storage modulus within a predetermined range in a wide temperature range, for example, a temperature range of -40 ° C to 90 ° C.
  • the present application also provides a foldable display including a pressure-sensitive adhesive layer having an excellent bending strength and a cohesive force while having a bending reliability suitable for a foldable display, and a method of manufacturing the same.
  • the present application relates to a pressure-sensitive adhesive composition for foldable display and its use.
  • the pressure-sensitive adhesive composition according to the present application has a storage elastic modulus after curing in a wide temperature range, for example, a temperature range of -40 ° C to 90 ° C or less, 5.0 x 10 6 Pa or less, suitable physical properties for use in a foldable display
  • the pressure-sensitive adhesive composition according to the present application includes a predetermined additive, thereby realizing a high cohesive force and adhesive force can overcome the problem of the pressure-sensitive adhesive having a low adhesive force, for example, a low adhesive force.
  • Such an adhesive composition is cured, for example, to form an adhesive layer, which is included in a foldable display, for example, is formed on a base film, and may be present on one or both sides of the polarizing plate.
  • the term “foldable display” is designed to be repeated to be folded and folded like a paper, so that the folded portion may mean a flexible display having a radius of curvature within 5 mm.
  • the adhesive applied to the foldable display must satisfy the bending reliability unlike the conventional adhesive, and in order to have excellent bending reliability, the rheological properties, for example, in the temperature range in which the actual foldable display can be used, can be used.
  • the storage modulus should be kept within an appropriate range.
  • the pressure-sensitive adhesive composition according to the present application is to control the content of the MQ resin to impart the adhesive properties and to design the structure of the silicone gum (gum) appropriately, so that the change in the storage elastic modulus within the commercialization temperature range is minimized and In addition, it contains a predetermined additive.
  • the pressure-sensitive adhesive composition according to the present application may maintain the storage modulus within an appropriate range to ensure the folding reliability required in the foldable display, as well as have excellent adhesion and cohesion.
  • the present application is a first pressure-sensitive adhesive; Second pressure sensitive adhesive; And a borane compound, a borate compound, and a mixture thereof.
  • the present invention relates to a foldable display pressure-sensitive adhesive composition comprising any one additive.
  • the foldable adhesive composition for foldable display has a peel force of 20 gf / in or more against a glass substrate measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees after curing.
  • the first pressure-sensitive adhesive contains a first silicone gum and a first MQ resin, and a peel force on the glass substrate measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees is 10 gf / in or less.
  • the first pressure-sensitive adhesive is a low adhesion component having a relatively low adhesive strength, and includes a first silicone gum.
  • silicone gum refers to a polyorganosiloxane compound commonly included in silicone-based adhesives, and may serve to impart a constant storage modulus and cohesion to the adhesive composition.
  • the first silicon gum may be represented by the following Chemical Formula 1.
  • R 1 and R 6 are each independently a silyl group or silanol group including or without an alkyl group, alkenyl group or aryl group, and R 2 to R 5 are each independently an alkyl group, alkenyl group or aryl group , n and m are each independently integers ranging from 1 to 10,000.
  • alkyl group means an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. Can be.
  • the alkyl group may be linear, branched or cyclic.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group and n- Linear or branched alkyl groups such as hexyl group, n-heptyl group or n-octyl group, or cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group or cycloheptyl group.
  • the alkyl group may be optionally substituted with one or more substituents.
  • alkenyl group means an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. can do.
  • the alkenyl group may be linear, branched or cyclic.
  • the alkenyl group may be exemplified by a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group or 3-butenyl group.
  • the alkenyl group may be optionally substituted with one or more substituents.
  • aryl group in the present application may refer to a monovalent moiety derived from a compound or a derivative thereof including a structure in which a benzene ring or a structure in which two or more benzene rings are condensed or bonded, unless otherwise specified.
  • the range of the aryl group may include a functional group commonly referred to as an aryl group as well as a so-called aralkyl group or an arylalkyl group.
  • the aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.
  • aryl group examples include phenyl group, phenoxy group, phenoxyphenyl group, phenoxybenzyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group or naphthyl group. Can be.
  • the aryl group may be optionally substituted with one or more substituents.
  • silanol group in the present application means a functional group including a Si-OH unit.
  • sil group refers to a generic term for a functional group containing a silicon atom.
  • substituents which may be substituted in a specific functional group for example, the alkyl group, alkenyl group or aryl group in the present application, an alkyl group, an alkoxy group, an alkenyl group, an epoxy group, a cyano group, a thiol group, a carboxyl group, an acryloyl group, Methacryloyl group, acryloyloxy group, methacryloyloxy group or aryl group and the like can be exemplified, but is not limited thereto.
  • the first silicone gum may, for example, have a number average molecular weight in the range of 400,000 to 800,000. Within the range of the number average molecular weight, it is possible to prevent a radical change in storage modulus and to provide an adhesive composition having an appropriate cohesion.
  • the number average molecular weight may be a value measured by a known measuring method using gel phase chromatography (GPC).
  • the silicone gum may have a number average molecular weight in the range of 500,000 to 800,000 or 700,000 to 800,000.
  • the first silicone gum may also have a suitable crosslinkable functional group to have a good degree of crosslinking.
  • the first silicone gum (gum) may be one in which the content of crosslinkable functional groups, for example, vinyl groups, is in the range of 0.5 mol% to 1.5 mol% or 0.5 mol% to 1 mol%. It has an excellent crosslinking degree within the content range of the crosslinkable functional group as described above, and can secure appropriate adhesive force and cohesiveness.
  • crosslinkable functional groups for example, vinyl groups
  • the first pressure-sensitive adhesive may also include an MQ resin.
  • MQ resin silicon having a three-dimensional network of three-dimensional molecular structure containing a monofunctional siloxane unit (hereinafter referred to as "M unit”) and a tetrafunctional siloxane unit (hereinafter referred to as "Q unit”). Means a compound.
  • M unit silicon having a three-dimensional network of three-dimensional molecular structure containing a monofunctional siloxane unit (hereinafter referred to as "M unit”) and a tetrafunctional siloxane unit (hereinafter referred to as "Q unit”).
  • M unit monofunctional siloxane unit
  • Q unit tetrafunctional siloxane unit
  • T units trifunctional siloxane units
  • M represents a unit of units represented by the formula (R 3 SiO 1/2) in the industry
  • unit D means a unit represented in the industry by the formula (R 2 SiO 2/2) and
  • T units It means a unit represented in the industry by the formula (RSiO 3/2)
  • Q unit means a unit of the formula (SiO 4/2).
  • R means a functional group bonded to the silicon atom (Si).
  • the MQ resin serves to impart an adhesive force in the adhesive, and since the first adhesive is a low adhesive having a relatively low peeling force on the glass substrate, the content of the MQ resin may be very low compared to the second adhesive. have.
  • the first pressure-sensitive adhesive may include the first MQ resin in an amount of less than 5 wt%.
  • the adhesive force may be excessively increased, and also may cause a radical change in storage modulus, which is not preferable.
  • the first pressure sensitive adhesive may comprise less than 4 wt%, less than 3 wt%, less than 2 wt% or less than 1 wt% of the first MQ resin.
  • the upper limit of the first MQ resin content may be, for example, 0.0001 wt% or more, 0.001 wt% or more, or 0.01 wt% or more.
  • the first pressure-sensitive adhesive may include 0.0001 to 5 parts by weight of the first MQ resin relative to 100 parts by weight of the first silicone gum.
  • the first MQ resin may include 0.001 to 4.5 parts by weight or 0.01 to 4 parts by weight.
  • the first MQ resin may be, for example represented by Chemical Formula 2, but is not limited thereto.
  • R is hydrogen, a monovalent hydrocarbon group or an alkenyl group.
  • An alkyl group, an aliphatic ring group, an aromatic ring group, etc. can be illustrated as said monovalent hydrocarbon group.
  • the alkyl group may be an alkyl group such as methyl, ethyl, propyl, or pentyl
  • the aliphatic ring group may be exemplified by cyclohexyl
  • the aromatic ring group may be phenyl, tolyl, xylyl, or benzyl. It is not limited to this.
  • alkenyl group may be exemplified by vinyl, allyl, butenyl, hexenyl or cyclohexenyl.
  • the monovalent hydrocarbon group or alkenyl group may be present in radical form.
  • the first MQ resin may further include a D unit or a T unit, and the ratio of the D unit and the T unit further included is preferably less than 5 mol%.
  • the first MQ resin may have a ratio (M: Q) of M units and Q units in a range of 0.6: 1 to 1.7: 1 or 0.7: 1 to 1: 1. If the M unit is less than 0.6 compared to the Q unit may be the initial adhesive strength, if it exceeds 1.7 it is not preferable because the cohesion may be lowered.
  • the first MQ resin may comprise a silanol group, wherein the content of the silanol group may be, for example, in the range of 0.1 mol% to 8 mol% or 0.2 mol% to 5 mol%. If the content of the silanol group is less than 0.1 mol%, the crosslinking density is lowered and the cohesive force is lowered, which is not preferable.
  • the first MQ resin may include a hydrogen atom in a ratio of 1 to 3 mol% based on the total functional groups bonded to the silicon atom.
  • the ratio of hydrogen atoms can be adjusted in the said range, and the fall of an uncured problem, storage stability, etc. can be prevented.
  • the first MQ resin may, for example, have a number average molecular weight in the range of 3,000 to 7,000.
  • MQ resin which has a number average molecular weight in the said range, the outstanding of cohesion force and adhesive force can be achieved.
  • the 1st adhesive mentioned above is a low adhesive which has a low adhesive force, and peeling force with respect to the glass substrate measured at the peeling speed of 0.3 m / min and the peeling angle of 180 degree is 10 gf / in or less.
  • the peel force on the glass substrate may be 9 gf / in or less, 8 gf / in or less, 7 gf / in or less, 6 gf / in or less, 5 gf / in or less, 4 gf / in or less, or 3 It may be less than or equal to gf / in.
  • the lower limit of the peeling force with respect to the glass substrate of the said 1st adhesive agent is not specifically limited, For example, it may be 0.1 gf / in or more.
  • the first pressure-sensitive adhesive may be included in the composition in the range of 5wt% to 50wt% relative to the total solids of the composition. In another example, the first pressure sensitive adhesive may be included in the composition in the range of 8wt% to 45wt% or 10wt% to 30wt% relative to the total solids of the composition.
  • the adhesive composition of this application also contains a 2nd adhesive.
  • the second adhesive has a peel force of 200 gf / in to 400 gf / in with respect to the glass substrate measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees.
  • the second pressure-sensitive adhesive is a high adhesion component having a relatively high adhesive strength compared to the first pressure-sensitive adhesive, and has a high peeling force on the glass substrate.
  • the second pressure sensitive adhesive contains a second silicone gum and a second MQ resin.
  • the second pressure-sensitive adhesive, the storage modulus measured at -40 °C may be 10 7 Pa or less.
  • the second pressure-sensitive adhesive having a storage modulus as described above is mixed with the first pressure-sensitive adhesive, it is possible to provide a pressure-sensitive adhesive composition having a storage modulus of 5.0 x 10 6 Pa or less after curing in a temperature range of -40 ° C to 90 ° C.
  • the second silicon gum may be the same as or different from the aforementioned first silicon gum.
  • the second silicon gum may have a structure different from that of the first silicon gum described above.
  • the second silicon gum may have a low crosslinking degree and a high crosslinking density in order to secure the property of the second adhesive having high adhesive force.
  • the second silicone gum may be a linear polydimethylsiloxane that includes hydroxy groups at both ends.
  • the linear polydimethylsiloxane including a hydroxy group at both ends means a polydimethylsiloxane having a linear structure in which in Formula 1, R 2 to R 5 are all methyl groups, and R 1 and R 6 are Si (CH 3 ) 2 OH. do.
  • the linear polydimethylsiloxane may be, for example, a hydroxyl group in the range of 0.5 mol% to 5 mol% or 1 mol% to 4 mol% relative to the total methyl groups contained in the polydimethylsiloxane.
  • a hydroxyl group in the range of 0.5 mol% to 5 mol% or 1 mol% to 4 mol% relative to the total methyl groups contained in the polydimethylsiloxane.
  • the hydroxyl group is in the above range, it is possible to achieve an appropriate degree of crosslinking to prevent hardening problems such as uncured and to improve long-term physical properties such as shelf life.
  • the second silicone gum may also be one having a number average molecular weight in the range of 500,000 to 1,000,000.
  • the second silicone gum may have a number average molecular weight in the range of 500,000 to 900,000 or 700,000 to 900,000.
  • a silicon gum (gum) having a number average molecular weight within the above range it is possible to provide a pressure-sensitive adhesive composition having a moderate cohesive force to prevent radical changes in storage modulus in a low temperature of 40 °C to a high temperature range of 90 °C.
  • the second silicone gum may have an appropriate viscosity in consideration of adhesion, workability, reactivity with the MQ resin, and the like.
  • the second silicone gum may have a viscosity, for example, in the range of 1,000,000 cP to 100,000,000 cP measured at 25 ° C. temperature and 50% relative humidity conditions.
  • the second silicon gum may have a viscosity measured at 25 ° C. temperature and 50% relative humidity conditions in the range of 1,500,000 cP to 70,000,000 cP. If the viscosity is less than 1,000,000 cP, reactivity or adhesion may be lowered, and if the viscosity exceeds 100,000,000 cP, workability may be significantly reduced.
  • the second MQ resin may be of the same or different type as the above-described first MQ resin.
  • the second MQ resin is an element that provides the adhesive force and the cohesive force of the pressure-sensitive adhesive, and also has a configuration capable of bringing about a change in storage elastic modulus according to its content.
  • the second pressure-sensitive adhesive having a high adhesive property may be more MQ resin content than the first pressure-sensitive adhesive.
  • the second pressure sensitive adhesive may include the second MQ resin within an appropriate range. .
  • the second pressure-sensitive adhesive may include the second MQ resin in an amount of 40 wt% or less.
  • the second pressure sensitive adhesive may include the second MQ resin in a ratio of 38 wt% or less, 36 wt% or less, 34 wt% or less, 32 wt% or less, or 30 wt% or less, preferably 36 wt% or less.
  • the lower limit of the content of the second MQ resin may be, for example, 5 wt% or more, 10 wt% or more, or 15 wt% or more.
  • the second pressure sensitive adhesive may include 60 to 95 parts by weight of the second silicone gum and 5 to 40 parts by weight of the second MQ resin.
  • the second pressure sensitive adhesive is 64 to 90 parts by weight of the second silicone gum and 10 to 36 parts by weight of the second MQ resin or 70 to 85 parts by weight of the second silicone gum and 25 to 25 parts of the second MQ gum. It may include 30 parts by weight.
  • the pressure-sensitive adhesive composition of the present application includes the above-described first pressure sensitive adhesive and second pressure sensitive adhesive in a predetermined ratio.
  • the pressure sensitive adhesive composition comprises the first pressure sensitive adhesive in the range of 5 wt% to 50 wt% relative to the total solids of the composition.
  • the pressure-sensitive adhesive composition may include the first pressure-sensitive adhesive in the range of 8 wt% to 40 wt% or 9 wt% to 35 wt% of the total solids.
  • the second pressure-sensitive adhesive may be changed in accordance with the content of the first pressure-sensitive adhesive in the pressure-sensitive adhesive composition, for example, the second pressure-sensitive adhesive is 50wt% to 95wt%, 55wt% to 94wt% or 70wt% to the total solids of the composition It may be included in the pressure-sensitive adhesive composition in an amount within the range of 90wt%.
  • the pressure-sensitive adhesive composition according to the present application also includes an additive to reinforce the low adhesive strength of the silicone pressure-sensitive adhesive as described above.
  • the pressure-sensitive adhesive composition for foldable display according to the present application includes any one additive selected from the group consisting of borane compounds, borate compounds, and mixtures thereof, together with the silicone pressure sensitive adhesive.
  • a foldable display having excellent adhesion properties after curing, for example, a peel force of 20 gf / in or more on a glass substrate measured at a peel rate of 0.3 m / min and a 180 degree peel angle after curing.
  • a pressure-sensitive adhesive composition can be provided.
  • Borane compounds of the additives may be represented by the formula (3).
  • R4 to R6 are each independently hydrogen, halogen, alkyl or silyl group of 1 to 6 carbon atoms.
  • the borate compound in the additive may be represented by the following formula (4).
  • R 7 to R 9 are each independently hydrogen, halogen, an alkyl group having 1 to 6 carbon atoms, or a silyl group.
  • the borane compound or the borate compound may be exemplified as triethyl borate, ethyl borane or methyl borane, but is not limited thereto, the borane compound or borate that serves to improve the adhesive properties of the silicone pressure-sensitive adhesive Compounds can be used without limitation.
  • the additive may be included in the pressure-sensitive adhesive composition in an amount sufficient to improve the adhesive properties of the silicone pressure-sensitive adhesive and secure the desired adhesive strength of the pressure-sensitive adhesive composition.
  • the additive may be included in the pressure-sensitive adhesive composition in the range of 0.01 to 5wt% relative to the total solids of the pressure-sensitive adhesive composition.
  • the content of the additive exceeds 5wt%, the adhesion may be excessively increased, or agglomeration between the additives may occur, and when the content of the additive is less than 0.01wt%, the purpose of improving the adhesive properties may not be achieved.
  • the additive may be included in the pressure-sensitive adhesive composition in the range of 0.05 to 4 wt% or 0.1 to 3 wt% relative to the total solids of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition for foldable display according to the present application may further include an organic solvent.
  • the organic solvent has solubility in silicon gum and MQ resins, and examples thereof include saturated hydrocarbon-based organic solvents, halogenated hydrocarbon solvents, or aromatic hydrocarbon-based organic solvents.
  • Saturated hydrocarbon-based organic solvents may be exemplified, for example, pentane, isopentane, cyclopentane, hexane, cyclohexane, heptane, isoheptane, cycloheptane, octane, isooctane or cyclooctane, and the halogenated hydrocarbon solvent is trichloro Loethane or chloroform may be exemplified, and the aromatic hydrocarbon-based organic solvent may be exemplified by benzene, xylene or toluene, but is not limited thereto.
  • the pressure-sensitive adhesive composition for a foldable display of the present application may include a first and a second pressure-sensitive adhesive, and thus may have a low storage modulus characteristic in a temperature range of 40 ° C. to 90 ° C., and also have excellent adhesion and cohesion due to additives. Can be secured.
  • the pressure-sensitive adhesive composition of the present application may have a storage modulus (G ′) of 5.0 ⁇ 10 6 Pa or less after curing within a temperature range of ⁇ 40 ° C. to 90 ° C.
  • the storage modulus may be, for example, a value measured according to a manual using an advanced rheological expansion system (Ta Instruments) at a frequency of 0.1 rad / s to 100 rad / s and a strain condition of 10% or less.
  • the storage modulus is derived by measuring the temperature by varying the temperature from -40 °C to 90 °C at a frequency of 6.2rad / s and less than 10% strain conditions using TA G2 series Rheometer Can be.
  • the lower limit of the storage modulus after curing within the temperature range of the pressure-sensitive adhesive composition may be 1.0 x 10 3 Pa, for example.
  • the pressure-sensitive adhesive composition of the present application is 1.0 x 10 3 Pa to 5.0 x 10 6 Pa, 5.0 x 10 3 Pa to 3.0 x 10 6 Pa or 1.0 x 10 4 Pa in the temperature range of -40 °C to 90 °C It may have a storage modulus value in the range from 1.0 x 10 6 Pa. Within the range of the storage elastic modulus change rate, it is possible to ensure the excellent bending reliability suitable for the foldable display.
  • the pressure-sensitive adhesive composition for foldable display has a peel force of 20 gf / in or more on a glass substrate measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees after curing.
  • the pressure-sensitive adhesive composition for foldable displays has a peel force of 25 gf / in or more, 27 gf / in or more, 28 gf to a glass substrate measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees after curing. / in or more, 29gf / in or more, or 30gf / in or more.
  • the present application also relates to a foldable display.
  • the foldable display of the present application may include a pressure-sensitive adhesive layer which is a cured product of the above-described pressure-sensitive adhesive composition, thereby ensuring excellent bending reliability required in the foldable display as well as excellent cohesion and adhesion.
  • the present application relates to a foldable display including a pressure-sensitive adhesive layer that is a cured product of the pressure-sensitive adhesive composition for foldable display attached to an adherend.
  • the pressure-sensitive adhesive composition the first pressure-sensitive adhesive; Second pressure sensitive adhesive; And an additive selected from the group consisting of borane compounds, borate compounds, and mixtures thereof.
  • the said adhesive layer is 20 gf / in or more of peeling force with respect to the glass substrate measured at the peeling speed of 0.3 m / min and the peeling angle of 180 degree
  • the adhesive layer in the foldable display of the present application is attached on the adherend.
  • the adherend may be, for example, a base film.
  • the base film may be, for example, a transparent base film having a haze of 10% or less, or 5% or less, or may be a colored base film having a haze of 30% or more.
  • the base film is, for example, polyolefin such as polyethylene or polypropylene; Polyesters such as polyethylene terephthalate and polyethylene naphthalate; Celluloses such as triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyl cellulose or acetyl cellulose; Polyamides such as 6-nylon or 6,6-nylon; Acrylic polymers such as polymethyl methacrylate; One formed of an organic polymer such as polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, or ethylene vinyl alcohol may be used, but is not limited thereto.
  • the base film may be formed of one or two or more kinds of mixtures or polymers, or may have a structure in which a plurality of layers are laminated.
  • the base film may be, for example, a modified surface.
  • the surface modification may be carried out for the purpose of increasing the adhesive strength with the pressure-sensitive adhesive layer, and specifically adopts a treatment method such as chemical treatment, corona discharge treatment, mechanical treatment, ultraviolet (UV) treatment, active plasma treatment or glow discharge treatment. It may, but is not limited to.
  • the adherend is a base film
  • the base film and the pressure-sensitive adhesive layer is covalently bonded through a silanol group included in the pressure-sensitive adhesive layer by the surface treatment of the base film and the surface treatment process of the pressure-sensitive adhesive layer described later. It may be forming.
  • a functional group such as -OH is induced on the base film, the functional group forms a covalent bond with the silanol group formed by the surface treatment of the pressure-sensitive adhesive layer, and the base film as a whole It may help to maintain a strong bond between the adhesive layer and the adhesive layer.
  • the base film may contain known additives such as antistatic agents, ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants or flame retardants.
  • the pressure-sensitive adhesive layer for example, the surface may be modified.
  • the surface modification can be carried out to maintain a firm adhesion with the adherend, for example the base film.
  • the method of surface modification may be appropriately adopted among the surface modification methods of the base film described above.
  • the pressure-sensitive adhesive layer may form a silanol group, and the silanol group may form a covalent bond with a functional group such as -OH on a base film.
  • the adherend and the pressure-sensitive adhesive layer can secure excellent adhesion.
  • the pressure-sensitive adhesive layer included in the foldable display may have a peel force of 2,000 gf / in with respect to the adherend measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees.
  • the pressure-sensitive adhesive layer may have a peel force of 2,200 gf / in or more than 2,400 gf / in of the adhesive agent measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees.
  • the foldable display according to the present application may further include a polarizing plate, and an adhesive layer may be formed on one or both sides of the polarizing plate.
  • the method for forming the pressure-sensitive adhesive layer for example, a method of coating a composition containing a first pressure-sensitive adhesive, a second pressure-sensitive adhesive, an additive, other solvents, and the like on an arbitrary support, and then curing may be used.
  • the coating and curing methods are not particularly limited.
  • known bar coating, gravure coating, reverse roll coating, reverse gravure coating, slot die coating, comma coating, spray coating, knife coating, die coating and dip coating After the application using a method such as microgravure coating or wire bar coating, it may include curing by applying appropriate heat.
  • the present application can provide a pressure-sensitive adhesive composition and its use having a bending reliability suitable for application to a foldable display, and also excellent in adhesive properties or cohesion.
  • Measuring instrument ARES-RDA with forced convection oven, TA Instruments Inc. (G2 series Rheometer)
  • Thickness about 1 mm
  • test type dynamic strain frequency sweep
  • the pressure-sensitive adhesive layers prepared according to Examples and Comparative Examples were attached to a glass substrate or surface treated PI substrate film as an adherend, and then aged at 50 ° C. and 5 atmospheres for 1 hour or at room temperature for 3 days. After aging, the peel force was measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees at room temperature using a tensile analyzer.
  • a first polysiloxane gum having a vinyl group content of 0.5 mol%, a number average molecular weight of about 600,000, and an MQ resin having a structure of Formula 2 (R is an alkyl group having 1 to 2 carbon atoms).
  • a second pressure sensitive adhesive having a peel force of about 337 gf / in to the glass substrate is mixed with triethyl borate and a solvent, wherein the content of the first pressure sensitive adhesive is adjusted to about 10 wt% of the total composition and the content of triethyl borate relative to the total weight of the composition
  • Pressure-sensitive adhesive composition (A1) was prepared by adjusting to 1wt%.
  • the pressure-sensitive adhesive composition (A1) was coated and cured on the primer-treated PET substrate to form a pressure-sensitive adhesive layer (B1), and surface modification was performed on the pressure-sensitive adhesive layer (B1).
  • a pressure-sensitive adhesive composition (A2) was prepared in the same manner as in Example 1, except that the content of triethyl borate was changed to 2 wt% of the total solids of the composition, and the pressure-sensitive adhesive layer (B2) was formed using the same, and surface modification was performed. Was performed.
  • a pressure-sensitive adhesive composition (A3) was prepared in the same manner as in Example 1, except that the content of the first pressure sensitive adhesive was adjusted to about 30 wt% of the total composition and the content of triethyl borate was adjusted to 1 wt% relative to the total weight of the composition. Using this, an adhesive layer (B3) was formed and surface modification was performed.
  • a pressure-sensitive adhesive composition (A4) was prepared in the same manner as in Example 1 except that triethyl borate was not included, and a pressure-sensitive adhesive layer (B4) was formed using the same, and surface modification was performed.
  • a pressure-sensitive adhesive composition (A5) was prepared in the same manner as in Example 3 except that triethyl borate was not included, and a pressure-sensitive adhesive layer (B5) was formed using the same, and surface modification was performed.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Adhesion to Glass Substrate (gf / in) 32 32 28 10 8 Adhesive force to PI base film (gf / in) 2,737 2,666 2,400 44 22
  • the pressure-sensitive adhesive layer is formed by using the pressure-sensitive adhesive composition according to Examples 1 to 3 in the present application, it has excellent adhesion to the glass substrate or PI substrate film, Comparative Example 1 and In the case of the low pressure-sensitive adhesive layer according to 2, due to the low adhesive strength, it could be confirmed that the adhesive composition for the foldable display is not suitable.
  • Example 1 Example 2
  • Example 3 Storage modulus at -40 °C (Pa) 1.8 x 10 5 Pa 1.8 x 10 5 Pa 1.8 x 10 5 Pa

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • General Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
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  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition adhésive destinée à un écran pliable et son utilisation. Une composition adhésive selon la présente invention présente d'excellentes propriétés de durabilité à la flexion, d'adhérence et de cohésion.
PCT/KR2017/009873 2016-09-09 2017-09-08 Composition adhésive pour écran pliable WO2018048243A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP17849127.0A EP3511389B1 (fr) 2016-09-09 2017-09-08 Composition adhésive pour écran pliable
CN201780048516.5A CN109563395B (zh) 2016-09-09 2017-09-08 用于可折叠显示器的压敏粘合剂组合物
US16/331,767 US10920113B2 (en) 2016-09-09 2017-09-08 Pressure-sensitive adhesive composition for foldable display
JP2019500643A JP6860128B2 (ja) 2016-09-09 2017-09-08 フォルダブルディスプレイ用粘着剤組成物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160116325 2016-09-09
KR10-2016-0116325 2016-09-09
KR10-2017-0114559 2017-09-07
KR1020170114559A KR102024252B1 (ko) 2016-09-09 2017-09-07 폴더블(foldable) 디스플레이용 점착제 조성물

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WO2021000279A1 (fr) * 2019-07-03 2021-01-07 Dow Silicones Corporation Composition de silicone adhésive sensible à la pression et ses procédés de préparation et d'utilisation

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KR20070096278A (ko) * 2006-03-23 2007-10-02 주식회사 엘지화학 유연성 기판 반송용 점착제 조성물
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KR20160083583A (ko) * 2014-12-31 2016-07-12 삼성전자주식회사 점착필름 및 이를 포함하는 광학부재

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021000279A1 (fr) * 2019-07-03 2021-01-07 Dow Silicones Corporation Composition de silicone adhésive sensible à la pression et ses procédés de préparation et d'utilisation
CN114127221A (zh) * 2019-07-03 2022-03-01 美国陶氏有机硅公司 有机硅压敏粘合剂组合物及其制备方法和用途

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