WO2018048245A1 - Adhesive composition for foldable display - Google Patents

Adhesive composition for foldable display Download PDF

Info

Publication number
WO2018048245A1
WO2018048245A1 PCT/KR2017/009876 KR2017009876W WO2018048245A1 WO 2018048245 A1 WO2018048245 A1 WO 2018048245A1 KR 2017009876 W KR2017009876 W KR 2017009876W WO 2018048245 A1 WO2018048245 A1 WO 2018048245A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
group
adhesive composition
foldable
Prior art date
Application number
PCT/KR2017/009876
Other languages
French (fr)
Korean (ko)
Inventor
박현규
노동규
권윤경
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 KR1020170114558A external-priority patent/KR102024251B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780048568.2A priority Critical patent/CN109563396B/en
Priority to JP2019500648A priority patent/JP2019527745A/en
Priority to EP17849129.6A priority patent/EP3511390B1/en
Priority to US16/331,743 priority patent/US10920112B2/en
Publication of WO2018048245A1 publication Critical patent/WO2018048245A1/en

Links

Classifications

    • 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
    • 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

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 No. 2015-0011230 A
  • the present application provides a pressure-sensitive adhesive composition for foldable display and its use.
  • the present application satisfies the storage elastic modulus within a predetermined range in a wide temperature range, for example, a temperature range of -40 ° C to 90 ° C to form a pressure-sensitive adhesive layer having excellent bending reliability and improved release peeling force on a fluorine-based release film. It provides an adhesive composition for a foldable display.
  • 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 can provide a pressure-sensitive adhesive composition for foldable (foldable) display having a proper adhesiveness and cohesion and further secure the above-described storage modulus range.
  • the pressure-sensitive adhesive composition according to the present application can form a pressure-sensitive adhesive layer having a suitable release peel force for the fluorine-based release film, it is possible to improve the unpeeled problem due to the adhesive properties from the release film.
  • 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.
  • this pressure-sensitive adhesive composition may have a low storage modulus.
  • the present applicant when preparing a pressure-sensitive adhesive composition by mixing a high adhesive and a low adhesive component having a low storage elastic modulus having an appropriate storage elastic modulus in a predetermined content, having an appropriate adhesive force and folding reliability due to the rapid rise in rheological properties
  • the present invention has been realized by preventing the drop of, minimizing the variation in storage modulus within the commercialization temperature range, and at the same time maintaining the fluorine-based release film and appropriate release force.
  • the present application includes a first pressure sensitive adhesive and a second pressure sensitive adhesive.
  • the pressure-sensitive adhesive composition includes the first pressure-sensitive adhesive in a ratio of 5wt% to 50wt% relative to the total solids of the composition, and also satisfies the following Equation 1.
  • A means the peeling force with respect to the fluorine-type release film measured at the peeling speed of 0.3 m / min and the peeling angle of 180 degrees of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition according to the present application by mixing a high adhesive component and a low adhesive component having a low storage elastic modulus in a predetermined ratio, it may have a low peel force for the fluorine-based release film.
  • the peeling force for the fluorine-based release film measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition according to the present application is 15 gf / in or less, 14 gf / in or less, 13 gf / in or less, 12 gf / in or less, 11 gf / in or less, or 10 gf / in or less.
  • 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 low adhesive force 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 plays a role of imparting adhesive force in the pressure-sensitive adhesive, and since the first pressure-sensitive adhesive has a low peel strength with respect to the glass substrate relative to the second pressure-sensitive adhesive, the content of the MQ resin may be very low. 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 the range of 0.6: 1 to 1.7: 1 or 0.7: 1 to 1.0: 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 improve the release peel force problem for the desired fluorine-based release film, and also to store after curing in the temperature range of -40 °C to 90 °C
  • An adhesive composition having an elastic modulus of 5.0 ⁇ 10 6 Pa or less can be provided.
  • 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 silicone gum may have a structure having a low crosslinking degree and a high crosslinking density in order to secure a property having a high adhesive force despite the low MQ resin content of the second adhesive.
  • 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 at a low temperature of 40 °C and a high temperature zone 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 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 foldable display according to the present application may further include a known additive such as an oxidation inhibitor or a curing catalyst, and the type and content thereof may be a curing type of the first and second pressure-sensitive adhesives, Given the purpose of the present application, those skilled in the art can easily make design changes.
  • the pressure-sensitive adhesive composition for foldable display according to the present application has an advantage of achieving a desired storage elastic modulus range at a low temperature due to the addition of a low pressure-sensitive adhesive, such as the first pressure-sensitive adhesive, but the adhesive force may be lowered. There is. Therefore, the pressure-sensitive adhesive composition may overcome the above problems by including any one additive selected from the group consisting of borane compounds, borate compounds, and mixtures thereof.
  • the pressure-sensitive adhesive composition for foldable display of the present application includes the above-described first and second pressure-sensitive adhesives, and thus 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 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.
  • 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 said adhesive composition contains a 1st adhesive and a 2nd adhesive, and satisfy
  • A means the peeling force with respect to the fluorine-type release film measured at the peeling speed of 0.3 m / min and the peeling angle of 180 degrees of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition.
  • 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 adhesive force between the base film and the pressure-sensitive adhesive layer may be increased by the surface treatment of the base film and the surface treatment process of the pressure-sensitive adhesive layer described later.
  • 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.
  • a functional group such as -OH is formed on the adherend.
  • silanol groups are formed on the pressure sensitive adhesive layer, and when the two layers are laminated, the base film and the pressure sensitive adhesive layer form covalent bonds through the silanol groups. can do.
  • 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 may be a layer formed by curing a pressure-sensitive adhesive composition for a foldable display including a first pressure-sensitive adhesive and a second pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer may be, for example, the surface will 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 or more with respect to the adherend measured at a peel angle of 180 ° and a peel rate of 0.3 mm / min.
  • the pressure-sensitive adhesive layer may have a peel force of 2,200 gf / in or more than 2,400 gf / in of the adherend measured at a peel angle of 180 ° and a peel rate of 0.3 mm / min.
  • 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.
  • the delaminated film of the heavy peeling type and light peeling type of the pressure-sensitive adhesive layer was measured.
  • the measurement was measured under constant temperature and humidity conditions, the peel force was measured using a texture analyzer, based on ASTM3330.
  • a first polysiloxane gum having a vinyl group content of 0.5 mol% and 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).
  • 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).
  • the pressure-sensitive adhesive composition (A2) 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%, and the pressure-sensitive adhesive layer (B2) was formed using the same, and surface modification was performed.
  • the pressure-sensitive adhesive composition (A3) consisting of only the first pressure-sensitive adhesive and the solvent according to Example 1 was prepared, and the pressure-sensitive adhesive layer (B3) was formed in the same manner as in Example 1, and surface modification was performed.
  • a pressure-sensitive adhesive composition (A4) consisting of only the second pressure-sensitive adhesive and the solvent according to Example 1 was prepared, and the pressure-sensitive adhesive layer (B4) was formed in the same manner as in Example 1, and surface modification was performed.
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2 Adhesion to Glass Substrate (gf / in) 32 28 2 337 Adhesive force to PI base film (gf / in) 2,200 2,700 - 1200
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2 Storage modulus at -40 °C (Pa) 1.8 x 10 5 Pa 1.8 x 10 5 Pa 8 x 10 5 Pa 3 x 10 5 Pa Storage modulus at 90 ° C (Pa) 1.1 x 10 5 Pa 1.7 x 10 5 Pa 7 x 10 5 Pa 3 x 10 4 Pa
  • the pressure-sensitive adhesive layer according to Examples 1 and 2 and Comparative Examples 1 and 2 was 1 inch in width for 1 week at 25 ° C. and 50% relative humidity, and then the pressure-sensitive adhesive layer was fluorine-based and light-peeled, respectively. After attaching with the release film, at a peel rate of 0.3 m / min and a peel angle of 180 degrees, using a texture analyzer, measured based on ASTM3330, the results are shown in Table 3 below.

Landscapes

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

Abstract

The present application relates to an adhesive composition for a foldable display and the use of same. An adhesive composition according to the present application has appropriate adhesion and cohesion as well as excellent bending durability, and can be utilized for forming an adhesive layer, for a foldable display, having enhanced release strength.

Description

폴더블 디스플레이용 점착제 조성물 Adhesive composition for foldable display
관련 출원과의 상호 인용Cross Citation with Related Applications
본 출원은 2016년 09월 09일 자 한국 특허 출원 “제10-2016-0116324호” 및 2017년 09월 07일 자 한국 특허 출원 “제10-2017-0114558호” 에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0116324 dated 09/09/2016 and Korean Patent Application No. 10-2017-0114558 dated September 07, 2017. All contents disclosed in the literature of the said Korean patent application are included as a part of this specification.
기술분야Field of technology
본 출원은 폴더블(foldable) 디스플레이용 점착제 조성물 및 이의 용도에 대한 것이다.The present application relates to a pressure-sensitive adhesive composition for foldable display and its use.
최근 디스플레이 관련 기술의 발달과 함께, 접거나, 롤(Roll) 형상으로 말거나, 고무줄처럼 늘리는 등, 사용 단계에서 변형 가능한 디스플레이 장치들이 연구 및 개발되고 있다. 이들 디스플레이는 다양한 형태로 변형 가능하기 때문에, 사용 단계에서의 디스플레이의 대형화 요구와 휴대를 위한 디스플레이의 소형화의 요구를 모두 만족시킬 수 있다. Recently, with the development of display technology, display devices that can be deformed at the use stage, such as folding, rolling in a roll shape, or stretching like a rubber band, have been researched and developed. Since these displays can be modified in various forms, it is possible to satisfy both the demand for larger display in the use stage and the need for smaller display for portable use.
변형 가능한 디스플레이 장치는 미리 설정된 형태로 변형될 수 있을 뿐 아니라, 사용자의 요구에 상응하여 또는 디스플레이 장치가 사용되는 상황의 필요에 맞추어 다양한 형태로 변형될 수 있다. 따라서, 디스플레이의 변형된 형태를 인식하고, 인식한 형태에 대응하여 디스플레이 장치를 제어할 필요가 있다.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.
한편, 변형 가능한 디스플레이 장치는 변형에 따라 디스플레이 장치의 각 구성이 손상될 문제가 있기 때문에, 이러한 디스플레이 장치의 각 구성들은 폴딩(Folding) 신뢰성 및 안정성을 만족해야 한다. On the other hand, 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.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
특허문헌 1 : 대한민국 공개 특허공보 2015-0011230 APatent Document 1: Republic of Korea Patent Publication No. 2015-0011230 A
본 출원은 폴더블(foldable) 디스플레이용 점착제 조성물 및 이의 용도를 제공한다.The present application provides a pressure-sensitive adhesive composition for foldable display and its use.
본 출원은 넓은 온도 구간, 예를 들면 -40℃ 내지 90℃의 온도 구간에서 소정 범위 내의 저장 탄성률을 만족하여 굽힘 신뢰성이 우수하고, 또한 불소계 이형 필름에 대한 이형 박리력이 개선된 점착제층을 형성할 수 있는 폴더블(foldable) 디스플레이용 점착제 조성물을 제공한다. The present application satisfies the storage elastic modulus within a predetermined range in a wide temperature range, for example, a temperature range of -40 ° C to 90 ° C to form a pressure-sensitive adhesive layer having excellent bending reliability and improved release peeling force on a fluorine-based release film. It provides an adhesive composition for a foldable display.
본 출원은 또한, 폴더블(foldable) 디스플레이에 적합한 굽힘 신뢰성을 가짐과 동시에, 우수한 점착력 및 응집력을 가지는 점착제층을 포함하는 폴더블(foldable) 디스플레이 및 이의 제조방법을 제공한다. 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.
본 출원은 폴더블(foldable) 디스플레이용 점착제 조성물 및 이의 용도에 대한 것이다.The present application relates to a pressure-sensitive adhesive composition for foldable display and its use.
본 출원에 따른 점착제 조성물은 넓은 온도 구간, 예를 들면 -40℃ 내지 90℃의 온도 구간에서 경화 후 저장 탄성률이 5.0 x 106 Pa 이하이므로, 폴더블(foldable) 디스플레이에 이용하기에 적합한 물성을 가진다.Since 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 Have
또한, 본 출원에 따른 점착제 조성물은 적절한 접착성과 응집력을 가지고 나아가 전술한 저장 탄성률 범위를 확보할 수 있는 폴더블(foldable) 디스플레이용 점착제 조성물을 제공할 수 있다. In addition, the pressure-sensitive adhesive composition according to the present application can provide a pressure-sensitive adhesive composition for foldable (foldable) display having a proper adhesiveness and cohesion and further secure the above-described storage modulus range.
더욱이, 본 출원에 따른 점착제 조성물은 불소계 이형 필름에 대한 적절한 이형 박리력을 가지는 점착제층을 형성할 수 있어, 이형 필름으로부터의 접착 특성에 따른 미박리 문제를 개선할 수 있다.Moreover, the pressure-sensitive adhesive composition according to the present application can form a pressure-sensitive adhesive layer having a suitable release peel force for the fluorine-based release film, it is possible to improve the unpeeled problem due to the adhesive properties from the release film.
이러한 점착제 조성물은, 예를 들면 경화되어 점착제층을 형성하고, 상기 점착제층은 폴더블(foldable) 디스플레이에 포함되어, 예를 들면 기재 필름 상에 형성되며, 편광판의 일면 또는 양면에 존재할 수 있다. 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.
본 출원에서 용어 「폴더블(foldable) 디스플레이」는 종이처럼 접혔다 폈다는 반복할 수 있도록 설계되어, 접힘 부분이 곡률 반경이 5mm 이내인 플렉시블 디스플레이를 의미할 수 있다.In the present application, 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.
폴더블(foldable) 디스플레이에 적용되는 점착제는 기존 점착제와 달리 굽힌 신뢰성을 만족해야 하는데, 이러한 굽힘 신뢰성이 우수하기 위해서는 실제 폴더블(foldable) 디스플레이가 사용될 수 있는 온도 범위에서, 레올로지 물성, 예를 들면 저장 탄성률이 적정 범위 이내로 유지되어야 한다.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. For example, the storage modulus should be kept within an appropriate range.
한편, 목적하는 레올로지 물성을 만족하기 위하여, 점착제 조성물에 포함되는 MQ 수지의 함량이나 실리콘 검(gum)의 구조를 변경할 수 있는데, 이러한 점착제 조성물은 낮은 저장 탄성률을 가질 수 있다.On the other hand, in order to satisfy the desired rheological properties, the content of the MQ resin contained in the pressure-sensitive adhesive composition or the structure of the silicone gum (gum) can be changed, this pressure-sensitive adhesive composition may have a low storage modulus.
그러나, 점착제 조성물의 저장 탄성률이 낮아지게 되는 경우, 점착제 조성물의 경화에 의해 형성된 점착제층의 일면 또는 양면에 부착되는 이형 박리 라이너, 예를 들면 불소계 이형 필름과의 접착력이 지나치게 증대되어, 이형력이 사라질 수 있는 문제점이 존재한다.However, when the storage elastic modulus of the pressure-sensitive adhesive composition becomes low, the adhesive force with a release release liner attached to one or both sides of the pressure-sensitive adhesive layer formed by curing of the pressure-sensitive adhesive composition, for example, a fluorine-based release film, is excessively increased, and the release force is increased. There is a problem that can disappear.
이에, 본 출원인은 적절한 저장 탄성률을 가지는 낮은 저장 탄성률을 가지는 고점착제와 저점착 성분을 소정 함량으로 혼합하여 점착제 조성물을 제조하는 경우, 적절한 접착력을 가짐과 동시에 레올로지 물성의 급격한 상승에 따른 폴딩 신뢰성의 하락을 방지하고, 상용화 온도 범위 내에서 저장 탄성률의 변화 폭을 최소화할 수 있음과 동시에 불소계 이형 필름과 적절한 이형력이 유지될 수 있음을 착안하여 본 발명에 이르렀다.Accordingly, the present applicant, when preparing a pressure-sensitive adhesive composition by mixing a high adhesive and a low adhesive component having a low storage elastic modulus having an appropriate storage elastic modulus in a predetermined content, having an appropriate adhesive force and folding reliability due to the rapid rise in rheological properties The present invention has been realized by preventing the drop of, minimizing the variation in storage modulus within the commercialization temperature range, and at the same time maintaining the fluorine-based release film and appropriate release force.
즉, 본 출원은 제 1 점착제 및 제 2 점착제를 포함한다. 상기 점착제 조성물은 제 1 점착제를 조성물의 총 고형분 대비 5wt% 내지 50wt%의 비율로 포함하고 또한, 하기 수식 1을 만족한다. That is, the present application includes a first pressure sensitive adhesive and a second pressure sensitive adhesive. The pressure-sensitive adhesive composition includes the first pressure-sensitive adhesive in a ratio of 5wt% to 50wt% relative to the total solids of the composition, and also satisfies the following Equation 1.
[수식 1][Equation 1]
A<20gf/inA <20gf / in
수식 1에서, A는 점착제 조성물이 경화되어 형성된 점착제층의 0.3 m/min의 박리 속도 및 180도의 박리 각도에서 측정한 불소계 이형필름에 대한 박리력을 의미한다.In Formula 1, A means the peeling force with respect to the fluorine-type release film measured at the peeling speed of 0.3 m / min and the peeling angle of 180 degrees of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition.
즉, 본 출원에 따른 점착제 조성물은, 낮은 저장 탄성률을 가지는 고점착제 성분과 저점착 성분을 소정 비율로 혼합하여, 불소계 이형 필름에 대한 낮은 박리력을 가질 수 있다.That is, the pressure-sensitive adhesive composition according to the present application, by mixing a high adhesive component and a low adhesive component having a low storage elastic modulus in a predetermined ratio, it may have a low peel force for the fluorine-based release film.
다른 예시에서, 본 출원에 따른 점착제 조성물이 경화되어 형성된 점착제층의 0.3 m/min의 박리 속도 및 180도의 박리 각도에서 측정한 불소계 이형필름에 대한 박리력은 15gf/in 이하, 14gf/in 이하, 13gf/in이하, 12gf/in이하, 11gf/in이하 또는 10 gf/in 이하 일 수 있다.In another example, the peeling force for the fluorine-based release film measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition according to the present application is 15 gf / in or less, 14 gf / in or less, 13 gf / in or less, 12 gf / in or less, 11 gf / in or less, or 10 gf / in or less.
상기 제 1 점착제는 제 1 실리콘 검(gum) 및 제 1 MQ 수지를 포함하고, 0.3 m/min의 박리 속도 및 180도의 박리 각도에서 측정한 유리 기판에 대한 박리력이 10 gf/in 이하이다. 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.
상기 제 1 점착제는 낮은 점착력을 가지는 저점착 성분으로써, 제 1 실리콘 검(gum)을 포함한다.The first pressure-sensitive adhesive is a low adhesion component having a low adhesive force and includes a first silicone gum.
상기에서 용어 「실리콘 검(gum)」은 실리콘계 점착제에 통상적으로 포함되는 폴리오가노실록산 화합물을 통칭하는 것으로써, 점착제 조성물에 일정한 저장 탄성률 및 응집력을 부여하는 역할을 수행할 수 있다.As used herein, the term "silicone gum (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.
하나의 예시에서, 제 1 실리콘 검(gum)은 하기 화학식 1로 표현될 수 있다.In one example, the first silicon gum may be represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
Figure PCTKR2017009876-appb-I000001
Figure PCTKR2017009876-appb-I000001
상기 화학식 1에서, R1 및 R6는 각각 독립적으로 알킬기, 알케닐기 또는 아릴기를 포함하거나 포함하지 않는 실릴기 또는 실라놀기이고, R2 내지 R5는 각각 독립적으로 알킬기, 알케닐기 또는 아릴기이며, n 및 m은 각각 독립적으로 1 내지 10,000의 범위 내에 있는 정수이다.In 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.
본 출원에서 용어 「알킬기」는, 특별히 달리 규정하지 않는 한, 탄소수 1 내지 20, 탄소수 1 내지 16, 탄소수 1 내지 12, 탄소수 1 내지 8, 탄소수 1 내지 6 또는 탄소수 1 내지 4의 알킬기를 의미할 수 있다. 상기 알킬기는 직쇄형, 분지쇄형 또는 고리형일 수 있다. 알킬기로는 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기,sec-부틸기, t-부틸기, n-펜틸기, 이소펜틸기, 네오펜틸기, n-헥실기,n- 헵틸기 또는 n-옥틸기 등의 직쇄형 또는 분지쇄형 알킬기이거나, 시클로부틸기, 시클로펜틸기, 시클로헥실기 또는 시클로헵틸기 등의 시클로 알킬기 등이 예시될 수 있다. 또한, 상기 알킬기는 임의적으로 하나 이상의 치환기로 치환되어 있을 수 있다.In the present application, the term "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. Examples of the alkyl group 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. In addition, the alkyl group may be optionally substituted with one or more substituents.
본 출원에서 용어 「알케닐기」는, 특별히 달리 규정하지 않는 한, 탄소수 2 내지 20, 탄소수 2 내지 16, 탄소수 2 내지 12, 탄소수 2 내지 8, 2 내지 6 또는 탄소수 2 내지 4의 알케닐기를 의미할 수 있다. 상기 알케닐기는 직쇄형, 분지쇄형 또는 고리형일 수 있다. 알케닐기는 비닐기, 1-프로페닐기, 2-프로페닐기, 1-부테닐기, 2-부테닐기 또는 3-부테닐기 등이 예시될 수 있다. 또한, 알케닐기는 임의적으로 하나 이상의 치환기로 치환되어 있을 수 있다.In the present application, the term "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. In addition, the alkenyl group may be optionally substituted with one or more substituents.
본 출원에서 용어 「아릴기」는, 특별히 달리 규정하지 않는 한, 벤젠 고리 또는 2개 이상의 벤젠 고리가 축합 또는 결합된 구조를 포함하는 화합물 또는 그 유도체로부터 유래하는 1가 잔기를 의미할 수 있다. 아릴기의 범위에는 통상적으로 아릴기로 호칭되는 관능기는 물론 소위 아르알킬기(aralkyl group) 또는 아릴알킬기 등도 포함될 수 있다. 아릴기는, 예를 들면, 탄소수 6 내지 25, 탄소수 6 내지 21, 탄소수 6 내지 18 또는 탄소수 6 내지 12의 아릴기일 수 있다. 아릴기로는, 페닐기, 페녹시기, 페녹시페닐기, 페녹시벤질기, 디클로로페닐, 클로로페닐, 페닐에틸기, 페닐프로필기, 벤질기, 톨릴기, 크실릴기(xylyl group) 또는 나프틸기 등이 예시될 수 있다. 또한, 상기 아릴기는 임의적으로 하나 이상의 치환기로 치환되어 있을 수 있다.The term "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. Examples of the aryl group 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. In addition, the aryl group may be optionally substituted with one or more substituents.
본 출원에서 용어 「실라놀기」는 Si-OH 단위를 포함하는 관능기를 의미하는 것이다.The term "silanol group" in the present application means a functional group including a Si-OH unit.
본 출원에서 용어 「실릴기」는 실리콘 원자를 포함하는 관능기의 총칭을 의미한다.As used herein, the term "silyl group" refers to a generic term for a functional group containing a silicon atom.
본 출원에서 특정 관능기, 예를 들면, 상기 알킬기, 알케닐기 또는 아릴기에 치환되어 있을 수 있는 치환기로는, 알킬기, 알콕시기, 알케닐기, 에폭시기, 시아노기, 티올기, 카복실기, 아크릴로일기, 메타크릴로일기, 아크릴로일옥시기, 메타크릴로일옥시기 또는 아릴기 등이 예시될 수 있으나, 이에 제한되는 것은 아니다.As a substituent 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.
제 1 실리콘 검(gum)은, 예를 들면 수 평균 분자량이 400,000 내지 800,000의 범위 내에 있을 수 있다. 상기 수 평균 분자량의 범위 내에서 저장 탄성률의 급진적인 변화를 방지하고 적절한 응집력을 가지는 점착제 조성물을 제공할 수 있다.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.
상기에서 수 평균 분자량은 겔상 크로마토그래피(GPC)를 이용하여 공지의 측정방법에 의해 측정된 값일 수 있다.The number average molecular weight may be a value measured by a known measuring method using gel phase chromatography (GPC).
다른 예시에서, 실리콘 검(gum)은 수 평균 분자량이 500,000 내지 800,000 또는 700,000 내지 800,000의 범위 내에 있을 수 있다.In another example, 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.
제 1 실리콘 검(gum)은 또한, 우수한 가교도를 가지기 위해 적절한 가교성 관능기를 가질 수 있다.The first silicone gum may also have a suitable crosslinkable functional group to have a good degree of crosslinking.
하나의 예시에서, 제 1 실리콘 검(gum)은 가교성 관능기, 예를 들면 비닐기의 함량이 0.5 mol% 내지 1.5 mol% 또는 0.5mol% 내지 1mol%의 범위 내에 있는 것일 수 있다. 상기와 같은 가교성 관능기의 함량 범위 내에서 우수한 가교도를 가지고, 적절한 점착력 및 응집성을 확보할 수 있다.In one example, 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.
제 1 점착제는 또한, MQ 수지를 포함할 수 있다.The first pressure-sensitive adhesive may also include an MQ resin.
또한, 상기에서 용어 「MQ 수지」는, 일관능성 실록산 단위(이하, "M 단위")와 4관능성 실록산 단위(이하, "Q 단위")를 포함하는 3차원 망상의 입체적 분자 구조를 가지는 실리콘 화합물을 의미한다. 또한, 상기 MQ 수지는 기타 이관능성 실록산 단위(이하, "D 단위") 또는 3관능성 실록산 단위(이하, "T 단위")를 추가로 포함할 수 있다.In addition, the term "MQ resin" as described above, 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. In addition, the MQ resin may further include other difunctional siloxane units (hereinafter referred to as "D units") or trifunctional siloxane units (hereinafter referred to as "T units").
상기에서, M단위는 업계에서 식 (R3SiO1 / 2)로 표시되는 단위를 의미하고, D 단위는 업계에서 식(R2SiO2/2)로 표시되는 단위를 의미하며, T 단위는 업계에서 식 (RSiO3 / 2)로 표시되는 단위를 의미하고, 「Q 단위」는 식 (SiO4 / 2)로 표시되는 단위를 의미한다. 상기에서 R은 규소 원자(Si)에 결합되어 있는 관능기를 의미한다.In the above, M represents a unit of units represented by the formula (R 3 SiO 1/2) in the industry, and 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), and "Q unit" means a unit of the formula (SiO 4/2). In the above, R means a functional group bonded to the silicon atom (Si).
상기 MQ 수지는 점착제 내에 점착력을 부여하는 역할을 수행하는 것으로써, 제 1 점착제는 제 2 점착제에 비해 상대적으로 유리 기판에 대한 낮은 박리력을 가지는 저 점착제이기 때문에, MQ 수지의 함량이 매우 낮을 수 있다.The MQ resin plays a role of imparting adhesive force in the pressure-sensitive adhesive, and since the first pressure-sensitive adhesive has a low peel strength with respect to the glass substrate relative to the second pressure-sensitive adhesive, the content of the MQ resin may be very low. have.
하나의 예시에서, 제 1 점착제는 제 1 MQ 수지를 5wt% 미만의 함량으로 포함할 수 있다. 제 1 MQ 수지의 함량이 5wt% 이상일 경우, 점착력이 지나치게 증대될 수 있고, 또한 저장 탄성률의 급진적인 변화를 가져올 수도 있으므로, 바람직하지 않다.In one example, the first pressure-sensitive adhesive may include the first MQ resin in an amount of less than 5 wt%. When the content of the first MQ resin is 5 wt% or more, the adhesive force may be excessively increased, and also may cause a radical change in storage modulus, which is not preferable.
다른 예시에서, 제 1 점착제는 제 1 MQ 수지를 4wt% 미만, 3wt% 미만, 2wt% 미만 또는 1wt% 미만의 함량으로 포함할 수 있다. 상기 제 1 MQ 수지 함량의 상한값은, 예를 들면 0.0001wt% 이상, 0.001wt% 이상 또는 0.01wt% 이상일 수 있다.In another example, 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.
구체적인 예시에서, 제 1 점착제는 제 1 실리콘 검(gum) 100 중량부 대비 제 1 MQ 수지 0.0001 내지 5 중량부를 포함할 수 있다. 다른 예시에서, 제 1 MQ 수지 0.001 내지 4.5 중량부 또는 0.01 내지 4 중량부를 포함할 수 있다.In a specific example, 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. In another example, the first MQ resin may include 0.001 to 4.5 parts by weight or 0.01 to 4 parts by weight.
상기 제 1 MQ 수지는, 예를 들면 하기 화학식 2로 표현될 수 있으나, 이에 제한되는 것은 아니다.The first MQ resin may be, for example represented by Chemical Formula 2, but is not limited thereto.
[화학식 2][Formula 2]
Figure PCTKR2017009876-appb-I000002
Figure PCTKR2017009876-appb-I000002
상기 화학식 2에서, R은 수소, 1가 탄화수소기 또는 알케닐기이다.In Formula 2, R is hydrogen, a monovalent hydrocarbon group or an alkenyl group.
상기 1가 탄화수소기는, 알킬기, 지방족 고리기, 또는 방향족 고리기 등이 예시될 수 있다.An alkyl group, an aliphatic ring group, an aromatic ring group, etc. can be illustrated as said monovalent hydrocarbon group.
보다 구체적으로, 알킬기는 메틸, 에틸, 프로필 또는 펜틸 등의 알킬기 일 수 있고, 지방족 고리기는 시클로 헥실 등이 예시될 수 있으며, 방향족 고리기는, 페닐, 톨릴, 크실릴 또는 벤질 등이 예시될 수 있으나 이에 제한되는 것은 아니다.More specifically, the alkyl group may be an alkyl group such as methyl, ethyl, propyl, or pentyl, and the aliphatic ring group may be exemplified by cyclohexyl, and the aromatic ring group may be phenyl, tolyl, xylyl, or benzyl. It is not limited to this.
또한, 상기 알케닐기는, 비닐, 알릴, 부테닐, 헥세닐 또는 시클로헥세닐 등이 예시될 수 있다.In addition, the alkenyl group may be exemplified by vinyl, allyl, butenyl, hexenyl or cyclohexenyl.
한편, 상기 1가 탄화수소기 또는 알케닐기는 라디칼 형태로 존재할 수 있다.Meanwhile, the monovalent hydrocarbon group or alkenyl group may be present in radical form.
상기 제 1 MQ 수지는, 예를 들면 D 단위 또는 T단위를 추가로 포함할 수 있는데, 상기 추가로 포함되는 D 단위 및 T 단위의 비율이 5 몰% 미만인 것이 바람직하다.For example, 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%.
제 1 MQ 수지는, 예를 들면 M 단위와 Q 단위의 비율(M : Q)가 0.6 : 1 내지 1.7 : 1 또는 0.7 : 1 내지 1.0 : 1의 범위 내에 있을 수 있다. M 단위가 Q단위 대비 0.6 미만일 경우 초기 점착력이 떨어질 수 있고, 1.7을 초과하는 경우 응집력이 저하될 수 있어 바람직하지 못하다.For example, the first MQ resin may have a ratio (M: Q) of M units and Q units in the range of 0.6: 1 to 1.7: 1 or 0.7: 1 to 1.0: 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.
제 1 MQ 수지는, 실라놀기를 포함할 수 있는데, 상기 실라놀기의 함량은, 예를 들면 0.1 몰% 내지 8 몰% 또는 0.2 몰% 내지 5 몰%의 범위 내에 있을 수 있다. 실라놀기의 함량이 0.1몰% 미만일 경우, 가교 밀도가 저하되어 응집력이 떨어지기 때문에, 바람직하지 못하고, 8몰%를 초과하는 경우 접착력이 저하되어 바람직하지 못하다.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.
제 1 MQ 수지는, 예를 들면 수소 원자를 규소 원자에 결합하고 있는 전체 관능기 대비 1 내지 3몰%의 비율로 포함할 수 있다. 수소 원자의 비율을 상기 범위 내로 조절하여, 미경화 문제나 저장 안정성 등의 저하를 방지할 수 있다.For example, 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.
제 1 MQ 수지는, 예를 들면 수 평균 분자량이 3,000 내지 7,000의 범위 내에 있을 수 있다. 상기 범위 내의 수 평균 분자량을 가지는 MQ 수지를 이용하는 경우, 응집력 및 접착력의 우수성을 달성할 수 있다.The first MQ resin may, for example, have a number average molecular weight in the range of 3,000 to 7,000. When using MQ resin which has a number average molecular weight in the said range, the outstanding of cohesion force and adhesive force can be achieved.
전술한 제 1 점착제는 낮은 점착력을 가지는 저점착제로써, 0.3m/min의 박리 속도 및 180도의 박리 각도에서 측정한 유리 기판에 대한 박리력이 10 gf/in 이하이다. 다른 예시에서, 상기 유리 기판에 대한 박리력은 9 gf/in 이하, 8 gf/in 이하, 7 gf/in 이하, 6 gf/in 이하, 5 gf/in 이하, 4 gf/in 이하, 또는 3 gf/in 이하 일 수 있다. 상기 제 1 점착제의 유리 기판에 대한 박리력의 하한 값은 특별히 제한되는 것은 아니나, 예를 들면 0.1gf/in 이상 일 수 있다.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. In another example, 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. Although 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.
상기 제 1 점착제는, 조성물의 총 고형분 대비 5wt% 내지 50wt%의 범위 내로 조성물에 포함될 수 있다. 다른 예시에서, 제 1 점착제는 조성물의 총 고형분 대비 8wt% 내지 45wt% 또는 10wt% 내지 30wt%의 범위 내로 조성물에 포함될 수 있다.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.
본 출원의 점착제 조성물은 또한, 제 2 점착제를 포함한다. 상기 제 2 점착제는 0.3 m/min의 박리 속도 및 180도의 박리 각도에서 측정한 유리 기판에 대한 박리력이 200gf/in 내지 400gf/in 이다.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.
상기 제 2 점착제는 제 1 점착제에 비해 상대적으로 높은 점착력을 가지는 고점착 성분으로써, 유리기판에 대한 높은 박리력을 가진다.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.
상기 제 2 점착제는, 제 2 실리콘 검(gum) 및 제 2 MQ 수지를 포함한다.The second pressure sensitive adhesive contains a second silicone gum and a second MQ resin.
상기 제 2 점착제는, -40℃에서 측정한 저장 탄성률이 107Pa 이하일 수 있다. 상기와 같은 저장 탄성률을 가지는 제 2 점착제를 제 1 점착제와 혼합하는 경우, 목적하는 불소계 이형 필름에 대한 이형 박리력 문제를 개선할 수 있고, 또한 -40℃ 내지 90℃의 온도 구간에서 경화 후 저장 탄성률이 5.0 x 106 Pa 이하인 점착제 조성물을 제공할 수 있다.The second pressure-sensitive adhesive, the storage modulus measured at -40 ℃ may be 10 7 Pa or less. When the second pressure-sensitive adhesive having a storage modulus as described above is mixed with the first pressure-sensitive adhesive, it is possible to improve the release peel force problem for the desired fluorine-based release film, and also to store after curing in the temperature range of -40 ℃ to 90 ℃ An adhesive composition having an elastic modulus of 5.0 × 10 6 Pa or less can be provided.
상기 제 2 실리콘 검(gum)은 전술한 제 1 실리콘 검(gum)과 같거나 다른 종류의 것일 수 있다.The second silicon gum may be the same as or different from the aforementioned first silicon gum.
하나의 예시에서, 제 2 실리콘 검(gum)은 전술한 제 1 실리콘 검(gum)과 다른 구조를 가질 수 있다.In one example, the second silicon gum may have a structure different from that of the first silicon gum described above.
보다 구체적으로, 제 2 실리콘 검(gum)은 제 2 점착제가 낮은 MQ 수지 함량에도 불구하고, 높은 점착력을 가지는 특성을 확보하기 위하여, 가교도는 낮으며, 가교 밀도가 높은 구조를 가질 수 있다.More specifically, the second silicone gum may have a structure having a low crosslinking degree and a high crosslinking density in order to secure a property having a high adhesive force despite the low MQ resin content of the second adhesive.
일 예시에서, 제 2 실리콘 검(gum)은 양 말단에 히드록시기를 포함하는 선형 폴리디메틸실록산 일 수 있다. 양 말단에 히드록시기를 포함하는 선형 폴리디메틸실록산은, 상기 화학식 1에서, R2내지 R5가 모두 메틸기이고, R1및 R6가 Si(CH3)2OH인 선형 구조의 폴리디메틸실록산을 의미한다.In one example, 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.
상기 선형 폴리디메틸실록산은, 예를 들면 히드록시기가 폴리디메틸실록산에 포함되어 있는 전체 메틸기 대비 0.5 몰% 내지 5 몰% 또는 1 몰% 내지 4몰%의 범위 내에 있는 것일 수 있다. 히드록시기가 상기 범위 내에 있는 경우, 적절한 가교도를 달성하여 미경화 등의 경화 문제를 방지하고, 또한 저장성 등의 장기 물성을 개선할 수 있다.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. When 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.
제 2 실리콘 검(gum)은 또한, 수 평균 분자량이 500,000 내지 1,000,000의 범위 내에 있는 것일 수 있다. 다른 예시에서, 제 2 실리콘 검(gum)은 수 평균 분자량이 500,000 내지 900,000 또는 700,000 내지 900,000의 범위 내에 있을 수 있다. 상기 범위 내의 수 평균 분자량을 가지는 실리콘 검(gum)을 이용하는 경우, 40℃의 저온 및 90℃의 고온 구간에서 저장 탄성률의 급진적인 변화를 방지하고 적절한 응집력을 가지는 점착제 조성물을 제공할 수 있다.The second silicone gum may also be one having a number average molecular weight in the range of 500,000 to 1,000,000. In another example, 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. When using 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 at a low temperature of 40 ℃ and a high temperature zone of 90 ℃.
제 2 실리콘 검(gum)은 점착력, 작업성 및 MQ 수지와의 반응성 등을 고려하여 적절한 점도를 가질 수 있다.The second silicone gum may have an appropriate viscosity in consideration of adhesion, workability, reactivity with the MQ resin, and the like.
제 2 실리콘 검(gum)은 예를 들면 25℃ 온도 및 50%의 상대습도 조건에서 측정된 점도가 1,000,000 cP 내지 100,000,000 cP의 범위 내에 있을 수 있다. 다른 예시에서, 제 2 실리콘 검(gum)은 25℃ 온도 및 50%의 상대습도 조건에서 측정된 점도가 1,500,000 cP 내지 70,000,000 cP의 범위 내에 있을 수 있다. 만약, 점도가 1,000,000 cP미만일 경우 반응성이나 점착력 등이 저하될 수 있고, 점도가 100,000,000 cP를 초과할 경우 작업성이 현저하게 떨어질 수 있다.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. In another example, 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.
상기 제 2 MQ 수지는 전술한 제 1 MQ 수지와 같거나 다른 종류의 것일 수 있다.The second MQ resin may be of the same or different type as the above-described first MQ resin.
제 2 MQ 수지는 제 1 MQ 수지와 마찬가지로, 점착제의 접착력 및 응집력을 제공하는 요소이며, 또한 그 함량에 따라 저장 탄성률의 변동을 가져올 수 있는 구성이다.Like the 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.
한편, 제 2 점착제는 고점착 특성을 가지는 것으로써, 제 1 점착제 대비 MQ 수지 함량이 많을 수 있다. 다만, 제 2 MQ 수지의 함량이 지나치게 많을 경우, 제 2 점착제의 저장 탄성률이 -40℃에서 107Pa을 초과하게 될 수 있으므로, 제 2 점착제는 적정 범위 내의 제 2 MQ 수지를 포함할 수 있다.On the other hand, the second pressure-sensitive adhesive having a high adhesive property, may be more MQ resin content than the first pressure-sensitive adhesive. However, when the content of the second MQ resin is too large, since the storage elastic modulus of the second pressure sensitive adhesive may exceed 10 7 Pa at −40 ° C., the second pressure sensitive adhesive may include the second MQ resin within an appropriate range. .
하나의 예시에서, 제 2 점착제는 제 2 MQ 수지를 40wt%이하의 함량으로 포함할 수 있다. 다른 예시에서, 제 2 점착제는 제 2 MQ 수지를 38wt%이하, 36wt%이하, 34wt%이하, 32wt%이하 또는 30wt% 이하의 비율로 포함할 수 있고, 바람직하게는 36wt% 이하가 좋다. 상기 제 2 MQ 수지 함량의 하한 값은, 예를 들면 5wt% 이상, 10wt% 이상 또는 15wt% 이상일 수 있다. 제 2 점착제 내에 제 2 MQ 수지의 함량을 상기 범위 내로 조절하는 경우, -40℃ 에서 1.0 x 107Pa이하의 저장 탄성률을 가지는 제 2 점착제를 제공할 수 있다.In one example, the second pressure-sensitive adhesive may include the second MQ resin in an amount of 40 wt% or less. In another example, 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. When adjusting the content of the second MQ resin in the second pressure-sensitive adhesive within the above range, it is possible to provide a second pressure-sensitive adhesive having a storage modulus of less than 1.0 x 10 7 Pa at -40 ℃.
구체적인 예시에서, 제 2 점착제는 제 2 실리콘 검(gum) 60 내지 95 중량부 및 제 2 MQ 수지 5 내지 40 중량부를 포함할 수 있다. 다른 예시에서, 제 2 점착제는 제 2 실리콘 검(gum) 64 내지 90 중량부 및 제 2 MQ 수지 10 내지 36 중량부 또는 제 2 실리콘 검(gum) 70 내지 85 중량부 및 제 2 MQ 수지 25 내지 30 중량부를 포함할 수 있다.In a specific example, 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. In another example, 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.
본 출원의 점착제 조성물은 전술한 제 1 점착제 및 제 2 점착제를 소정 비율로 포함한다.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.
하나의 예시에서, 점착제 조성물은 제 1 점착제를 조성물의 총 고형분 대비 5wt% 내지 50wt%의 범위 내로 포함한다. 다른 예시에서, 점착제 조성물은 제 1 점착제를 총 고형분 대비 8wt% 내지 40wt% 또는 9wt% 내지 35wt%의 범위 내로 포함할 수 있다.In one example, 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. In another example, 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.
제 2 점착제는 상기 점착제 조성물 내 제 1 점착제의 함량에 따라 그 함량이 변경될 수 있으며, 예를 들면 제 2 점착제는 조성물의 총 고형분 대비 50wt% 내지 95wt%, 55wt% 내지 94wt% 또는 70wt% 내지 90wt%의 범위 내의 함량으로 점착제 조성물에 포함될 수 있다.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%.
본 출원에 따른 폴더블(foldable) 디스플레이용 점착제 조성물은, 유기 용매를 추가로 포함할 수 있다.The pressure-sensitive adhesive composition for foldable display according to the present application may further include an organic solvent.
상기 유기 용매는, 실리콘 검(gum) 및 MQ 수지에 대한 용해성을 가지는 것으로써, 예를 들면 포화 탄화 수소계 유기 용매, 할로겐화 탄화수소 용매, 또는 방향족 탄화 수소계 유기 용매가 예시될 수 있다.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.
포화 탄화 수소계 유기 용매는, 예를 들면 펜탄, 이소펜탄, 시클로펜탄, 헥산, 시클로헥산, 헵탄, 이소헵탄, 시클로헵탄, 옥탄, 이소옥탄 또는 시클로 옥탄 등이 예시될 수 있고, 할로겐화 탄화수소 용매는 트리클로로에탄 또는 클로로포름 등이 예시될 수 있으며, 방향족 탄화 수소계 유기 용매는, 예를 들면 벤젠, 자일렌 또는 톨루엔 등이 예시될 수 있으나 이에 제한되는 것은 아니다.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.
본 출원에 따른 폴더블(foldable) 디스플레이용 점착제 조성물은, 산화 억제제, 또는 경화 촉매 등의 공지의 첨가제를 추가로 포함할 수 있으며, 그 종류 및 함량은 제 1 및 제 2 점착제의 경화 타입이나, 본 출원의 목적을 고려하여 당업자가 쉽게 설계 변경할 수 있다.The pressure-sensitive adhesive composition for foldable display according to the present application may further include a known additive such as an oxidation inhibitor or a curing catalyst, and the type and content thereof may be a curing type of the first and second pressure-sensitive adhesives, Given the purpose of the present application, those skilled in the art can easily make design changes.
한편, 본 출원에 따른 폴더블(foldable) 디스플레이용 점착제 조성물은 제 1 점착제와 같은 저점착제의 첨가로 인하여, 낮은 온도에서의 목적하는 저장 탄성률 범위를 달성할 수 있는 이점이 있으나, 접착력이 낮아질 우려가 있다. 따라서, 점착제 조성물은 보란 화합물, 보레이트 화합물 및 이들의 혼합물로 이루어진 군에서 선택되는 어느 하나의 첨가제를 포함함으로써, 전술한 문제점을 극복할 수도 있다.Meanwhile, the pressure-sensitive adhesive composition for foldable display according to the present application has an advantage of achieving a desired storage elastic modulus range at a low temperature due to the addition of a low pressure-sensitive adhesive, such as the first pressure-sensitive adhesive, but the adhesive force may be lowered. There is. Therefore, the pressure-sensitive adhesive composition may overcome the above problems by including any one additive selected from the group consisting of borane compounds, borate compounds, and mixtures thereof.
본 출원의 폴더블(foldable) 디스플레이용 점착제 조성물은 전술한 제 1 및 제 2 점착제를 포함함으로써, -40℃ 내지 90℃의 온도 범위 내에서 경화 후 5.0 x 106Pa 이하의 저장 탄성률(G')을 가질 수 있다.The pressure-sensitive adhesive composition for foldable display of the present application includes the above-described first and second pressure-sensitive adhesives, and thus a storage modulus (G ′) of 5.0 × 10 6 Pa or less after curing within a temperature range of −40 ° C. to 90 ° C. )
상기 저장 탄성률은, 예를 들면 0.1rad/s 내지 100rad/s의 주파수 및 10% 이하의 변형율 조건에서 유변 물성 측정기(Advanced Rheometric Expansion System, Ta Instruments)를 이용하여 매뉴얼에 따라 측정된 값일 수 있다.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.
하나의 예시에서, 상기 저장 탄성률은 TA사의 G2 series Rheometer를 이용하여 6.2rad/s의 주파수 및 10% 이하의 변형율 조건에서, -40℃에서 90℃까지 온도를 변형시켜가며 온도에 따라 측정하여 도출될 수 있다.In one example, the storage modulus is derived by measuring the temperature by varying the temperature from -40 ℃ to 90 ℃ at a frequency of 6.2rad / s and less than 10% strain conditions using TA G2 series Rheometer Can be.
또한, 점착제 조성물의 상기 온도 범위 내에서 경화 후 저장 탄성률의 하한 값은, 예를 들면 1.0 x 103Pa 일 수 있다.In addition, 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.
보다 구체적인 예시에서, 본 출원의 점착제 조성물은 -40℃ 내지 90℃의 온도 구간에서 1.0 x 103Pa 내지 5.0 x 106Pa, 5.0 x 103Pa 내지 3.0 x 106Pa 또는 1.0 x 104Pa 내지 1.0 x 106Pa 범위 내의 저장 탄성률 값을 가질 수 있다. 상기 저장 탄성률 변화율 범위 내에서, 폴더블(foldable) 디스플레이에 적합한 굽힘 신뢰성의 우수성을 확보할 수 있다.In a more specific 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 ℃ to 90 ℃ 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.
본 출원은 또한, 폴더블(foldable) 디스플레이에 대한 것이다. 본 출원의 폴더블(foldable) 디스플레이는 전술한 점착제 조성물의 경화물인 점착제층을 포함하여, 폴더블(foldable) 디스플레이에서 요구되는 굽힘 신뢰성의 우수성을 확보할 수 있다.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.
즉, 본 출원은 피착제에 부착되어 있는 폴더블(foldable) 디스플레이용 점착제 조성물의 경화물인 점착제층을 포함하는 폴더블(foldable) 디스플레이에 대한 것이다. 상기 점착제 조성물은, 제 1 점착제 및 제 2 점착제를 포함하고, 하기 수식 1을 만족한다. That is, 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 said adhesive composition contains a 1st adhesive and a 2nd adhesive, and satisfy | fills following formula (1).
[수식 1][Equation 1]
A<20gf/inA <20gf / in
수식 1에서, A는 점착제 조성물이 경화되어 형성된 점착제층의 0.3m/min의 박리 속도 및 180도의 박리 각도에서 측정한 불소계 이형필름에 대한 박리력을 의미한다.In Formula 1, A means the peeling force with respect to the fluorine-type release film measured at the peeling speed of 0.3 m / min and the peeling angle of 180 degrees of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition.
본 출원의 폴더블(foldable) 디스플레이 내 점착제층은 피착제 상에 부착되어 있다.The adhesive layer in the foldable display of the present application is attached on the adherend.
상기 피착제는, 예를 들면 기재 필름 일 수 있다.The adherend may be, for example, a base film.
상기 기재 필름은, 예를 들면 10%이하, 또는 5% 이하의 헤이즈를 가지는 투명 기재 필름일 수도 있고, 또한 헤이즈가 30% 이상인 유색 기재 필름 일 수도 있다.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.
상기 기재 필름은, 예를 들면 폴리에틸렌 또는 폴리프로필렌 등의 폴리올레핀; 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등의 폴리 에스테르; 트리아세틸 셀룰로오스, 디아세틸셀룰로오스, 프로피오닐 셀룰로오스, 부틸 셀룰로오스 또는 아세틸 셀룰로오스 등의 셀룰로오스; 6-나일론 또는 6,6-나일론 등의 폴리아미드; 폴리메틸메타크릴레이트 등의 아크릴 폴리머; 폴리스티렌, 폴리염화비닐, 폴리이미드, 폴리비닐알코올, 폴리카보네이트 또는 에틸렌비닐알코올 등의 유기 고분자로 형성된 것을 이용할 수 있으나, 이에 제한되는 것은 아니다.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.
기재 필름은 상기 1종 또는 2종 이상의 혼합물 또는 중합체로 형성된 것일 수도 있고, 복수의 층을 적층시킨 구조의 것일 수도 있다.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.
기재 필름은, 예를 들면 표면이 개질 된 것일 수 있다. 상기 표면 개질은 점착제층과의 점착력을 증대시킬 목적으로 수행될 수 있으며, 구체적으로 화학적 처리, 코로나 방전 처리, 기계적 처리, 자외선(UV) 처리, 활성 플라즈마 처리 또는 글로우 방전 처리 등의 처리방식을 채택할 수 있으나 이에 제한되는 것은 아니다.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.
하나의 예시에서, 피착제가 기재 필름일 경우, 상기 기재 필름의 표면 처리 및 후술하는 점착제층의 표면 처리 공정에 의해 상기 기재 필름과 점착제층은 접착력이 증대될 수 있다. In one example, when the adherend is a base film, the adhesive force between the base film and the pressure-sensitive adhesive layer may be increased by the surface treatment of the base film and the surface treatment process of the pressure-sensitive adhesive layer described later.
즉, 기재 필름의 표면 처리 공정을 수행하는 경우, 기재 필름 상에 -OH와 같은 관능기가 유도되고, 상기 관능기가 점착제층의 표면 처리에 의해 형성되는 실라놀기와 공유 결합을 형성하여, 전체적으로 기재 필름과 점착제층 사이에 결합을 견고하게 유지시키는데 도움을 줄 수 있다.That is, when performing the surface treatment process of the base film, 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.
구체적으로, 피착제에 화학적 처리, 코로나 방전 처리, 기계적 처리, 자외선(UV) 처리, 활성 플라즈마 처리 또는 글로우 방전 처리 등의 처리를 수행하는 경우, 상기 피착제에 -OH 등의 관능기가 형성되고, 점착제층에 상기 처리 방식 중 어느 하나를 이용하여 표면 처리를 수행하는 경우, 상기 점착제층에 실라놀기가 형성되어, 두 층을 적층 했을 때 실라놀기를 매개로 기재 필름과 점착제층이 공유 결합을 형성할 수 있다.Specifically, in the case of performing a treatment such as chemical treatment, corona discharge treatment, mechanical treatment, ultraviolet (UV) treatment, active plasma treatment or glow discharge treatment to the adherend, a functional group such as -OH is formed on the adherend, When surface treatment is performed on the pressure sensitive adhesive layer using any one of the above treatment methods, silanol groups are formed on the pressure sensitive adhesive layer, and when the two layers are laminated, the base film and the pressure sensitive adhesive layer form covalent bonds through the silanol groups. can do.
위와 같은 표면 처리 공정의 수행을 통해, 굽힘 신뢰성뿐만 아니라, 계면 접착력이나 응집력의 우수성을 동시에 확보할 수 있다.By performing the above surface treatment process, it is possible to secure not only bending reliability but also excellent interfacial adhesion and cohesion.
또한, 기재 필름은 공지의 첨가제, 예컨대, 대전 방지제, 자외선 흡수제, 적외선 흡수제, 가소제, 윤활제, 착색제, 산화방지제 또는 난연제 등이 포함되어 있을 수 있다.In addition, the base film may contain known additives such as antistatic agents, ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants or flame retardants.
상기 점착제층은, 제 1 점착제 및 제 2 점착제를 포함하는 폴더블(foldable) 디스플레이용 점착제 조성물이 경화되어 형성된 층 일 수 있다.The pressure-sensitive adhesive layer may be a layer formed by curing a pressure-sensitive adhesive composition for a foldable display including a first pressure-sensitive adhesive and a second pressure-sensitive adhesive.
상기 점착제층은 예를 들면 표면이 개질 될 것일 수 있다. 상기 표면 개질은 피착제, 예를 들면 기재 필름과의 견고한 접착력을 유지하기 위해 수행될 수 있다. 상기 표면 개질의 방법은, 전술한 기재 필름의 표면 개질 방식 중에 적절한 것이 채택될 수 있다.The pressure-sensitive adhesive layer may be, for example, the surface will 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.
상기 표면 개질을 통해 점착제층은 실라놀기가 형성될 수 있고, 상기 실라놀기는 기재 필름 상의 -OH 등과 같은 관능기와 공유 결합을 형성할 수 있다.Through the surface modification, 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.
상기와 같은 피착제 및 접착제층의 표면 처리에 의해, 피착제와 점착제층은 우수한 접착력을 확보할 수 있다.By the surface treatment of the above-mentioned adherend and adhesive layer, the adherend and the pressure-sensitive adhesive layer can secure excellent adhesion.
하나의 예시에서, 폴더블(foldable) 디스플레이에 포함되는 점착제층은 180°의 박리각도 및 0.3mm/min의 박리속도로 측정한 피착제에 대한 박리력이 2,000gf/in이상 일 수 있다.In one example, the pressure-sensitive adhesive layer included in the foldable display may have a peel force of 2,000 gf / in or more with respect to the adherend measured at a peel angle of 180 ° and a peel rate of 0.3 mm / min.
다른 예시에서, 상기 점착제층은 180°의 박리각도 및 0.3mm/min의 박리속도로 측정한 피착제에 대한 박리력이 2,200gf/in이상 또는 2,400gf/in 이상 일 수 있다. In another example, the pressure-sensitive adhesive layer may have a peel force of 2,200 gf / in or more than 2,400 gf / in of the adherend measured at a peel angle of 180 ° and a peel rate of 0.3 mm / min.
상기 점착제층을 형성하는 방법은, 예를 들면 제 1 점착제, 제 2 점착제, 첨가제 및 기타 용매 등을 포함하는 조성물에을 임의의 지지체 상에 코팅 한 후, 경화시키는 방식을 이용할 수 있다.As 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.
상기 코팅 및 경화 시키는 방식은 특별히 제한되는 것은 아니며, 예를 들면 공지의 바 코팅, 그라비아 코팅, 리버스 롤 코팅, 리버스 그라비아 코팅, 슬롯다이 코팅, 콤마코팅, 스프레이 코팅, 나이프 코팅, 다이코팅, 딥 코팅, 마이크로 그라비아 코팅 또는 와이어 바코팅 등의 방법을 이용하여 도포 한 후, 적절한 열을 가하여 경화시키는 것을 포함할 수 있다.The coating and curing methods are not particularly limited. For example, 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.
본 출원은 폴더블(foldable) 디스플레이에 적용하기에 적합한 굽힘 신뢰성을 가지고, 또한 점착 물성이나 응집력이 우수한 점착제 조성물 및 이의 용도를 제공할 수 있다. 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.
이하, 본 출원에 따른 폴더블(foldable) 디스플레이용 점착제 조성물 및 이를 포함하는 디스플레이에 대하여, 실시예 및 비교예를 들어 보다 상세하게 설명하지만, 하기 예시들은 본 출원에 따른 일례에 불과할 뿐, 본 출원의 기술적 사상을 제한하는 것은 아니다. Hereinafter, an adhesive composition for a foldable display and a display including the same according to the present application will be described in more detail with reference to Examples and Comparative Examples, but the following examples are merely examples according to the present application. It is not intended to limit the technical spirit of the.
본 출원의 점착제 조성물의 물성은 하기 방식에 의해 평가 하였다.Physical properties of the pressure-sensitive adhesive composition of the present application was evaluated by the following method.
1. 저장 탄성률 측정1. Measurement of storage modulus
이형필름 사이에 실시예 및 비교예에서 제조된 점착제 조성물을 코팅 및 경화한 후, 15 cm × 25 cm의 크기로 재단하고, 편면의 이형 필름을 제거한 다음, 여러번 적층 시켜서, 두께를 약 1mm가 되도록 하였다. 이어서, 상기 적층체를 지름 8 mm의 원형으로 재단하고, 글래스(glass)를 이용하여, 압축한 다음, 밤새 방치하여, 각 층간의 계면에서의 웨팅(wetting)을 향상시켜, 적층시 생긴 기포를 제거하여 시료를 제조하였다. 이어서, 시료를 패러랠 플레이트(parallel plate) 위에 놓고, 갭(gap)을 조정한 후, Normal & Torque의 영점을 맞추고, Normal force의 안정화를 확인한 후, 저장 탄성률을 측정하였다.After coating and curing the pressure-sensitive adhesive composition prepared in Examples and Comparative Examples between the release film, and cut to a size of 15 cm × 25 cm, remove the release film on one side, and laminated several times, so that the thickness is about 1mm It was. Subsequently, the laminate was cut into a circle having a diameter of 8 mm, compressed using glass, and left overnight to improve wetting at the interface between the layers, thereby improving bubbles produced during lamination. The sample was prepared by removal. Subsequently, the sample was placed on a parallel plate, the gap was adjusted, the zero point of Normal & Torque was set, the stability of the normal force was confirmed, and the storage modulus was measured.
(1) 측정 기기 및 측정 조건 (1) measuring instruments and measuring conditions
측정 기기: 강제 대류 오븐을 구비한 ARES-RDA, TA Instruments Inc.(G2 series Rheometer)Measuring instrument: ARES-RDA with forced convection oven, TA Instruments Inc. (G2 series Rheometer)
(2) 측정 조건(2) measurement conditions
Geometry : 8 mm parallel plateGeometry: 8 mm parallel plate
간격: 약 1 mmThickness: about 1 mm
test type : dynamic strain frequency sweeptest type: dynamic strain frequency sweep
변형(Strain) = 0.1 [%]Strain = 0.1 [%]
초기 온도 : -40℃, 최종 온도 : 90℃Initial temperature: -40 ° C, final temperature: 90 ° C
주파수 : 6.2rad/sFrequency: 6.2rad / s
2. 2. 박리력Peel force 측정 Measure
실시예 및 비교예에 따라 제조된 점착제층을 유리 기판 또는 표면처리된 PI 기재 필름을 피착체로 부착 시킨 후, 50℃ 및 5기압 조건에서 1시간 동안 또는 상온에서 3일 동안 에이징(aging)시켰다. 에이징 (aging) 후, 인장시험기(Texture Analyzer)를 사용하여 상온에서 0.3m/min의 박리 속도 및 180도의 박리각도로 박리력을 측정하였다.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.
3. 이형 3. Deformation 박리력Peel force 측정 Measure
실시예 또는 비교예에 따른 점착제층의 폭을 1 inch로 하여 25℃, 50% 상대습도 하에서 1주일 동안 보관한 후에 상기 점착제층의 중박리 타입 및 경박리 타입의 불소계 이형 필름(TACS사 TS-502S)에 대한 박리력(박리 속도: 0.3m/min, 박리 각도: 180)을 측정하였다.After the adhesive layer according to the embodiment or comparative example was stored for 1 week at 25 ℃, 50% relative humidity with a width of 1 inch, the delaminated film of the heavy peeling type and light peeling type of the pressure-sensitive adhesive layer (TS- Peeling force (peel rate: 0.3 m / min, peel angle: 180) for 502S) was measured.
상기 측정은 항온 항습 조건하에서 측정하였으며, 상기 박리력은 texture analyzer를 이용하며, ASTM3330에 근거하여 측정하였다.The measurement was measured under constant temperature and humidity conditions, the peel force was measured using a texture analyzer, based on ASTM3330.
실시예Example 1. One.
점착제 조성물의 제조 (A1)Preparation of Pressure-Sensitive Adhesive Composition (A1)
비닐기 함량이 0.5mol%이고, 수 평균 분자량이 약 600,000인 제 1 폴리 실록산 검(gum) 및 화학식 2의 구조(R은 탄소수 1 내지 2의 알킬기)를 갖는 MQ 수지를 약 0.001wt% 정도 포함하여, 유리 기판에 대한 박리력이 약 2gf/in인 제 1 점착제와 양 말단에 히드록시기를 포함하고, 수평균 분자량이 700,000인 제 2 폴리디메틸실록산 실리콘 검(gum) 및 MQ 수지를 약 38 중량 % 포함하고, 유리 기판에 대한 박리력이 약 337gf/in인 제 2 점착제를 용매와 혼합하되, 제 1 점착제의 함량을 약 10wt%로 조절하여 점착제 조성물(A1)을 제조하였다.Contains about 0.001 wt% of a first polysiloxane gum having a vinyl group content of 0.5 mol% and 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). About 38% by weight of the first pressure-sensitive adhesive having a peel force on the glass substrate and the second polydimethylsiloxane silicone gum and MQ resin having a hydroxyl group at both ends and a number average molecular weight of 700,000 And a second pressure sensitive adhesive having a peeling force of about 337 gf / in on a glass substrate and a solvent, but adjusting the content of the first pressure sensitive adhesive to about 10 wt% to prepare a pressure sensitive adhesive composition (A1).
점착제층(B1)의Of pressure-sensitive adhesive layer (B1) 형성 formation
프라이머 처리된 PET 기재 상에 상기 점착제 조성물(A1)을 코팅 및 경화시켜, 점착제층(B1)을 형성하고, 상기 점착제층(B1)에 표면 개질을 수행하였다.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).
실시예Example 2. 2.
제 1 점착제의 함량을 약 30wt%로 조절한 것을 제외하고는 실시예1과 동일하게 점착제 조성물(A2)을 제조하고, 이를 이용하여 점착제층(B2)을 형성하고, 표면 개질을 수행하였다. The pressure-sensitive adhesive composition (A2) 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%, and the pressure-sensitive adhesive layer (B2) was formed using the same, and surface modification was performed.
비교예Comparative example 1. One.
실시예 1에 따른 제 1 점착제와 용매만으로 이루어진 점착제 조성물(A3)을 제조하고, 이를 이용하여 실시예 1과 동일한 방식으로 점착제층(B3)을 형성하고, 표면 개질을 수행하였다.The pressure-sensitive adhesive composition (A3) consisting of only the first pressure-sensitive adhesive and the solvent according to Example 1 was prepared, and the pressure-sensitive adhesive layer (B3) was formed in the same manner as in Example 1, and surface modification was performed.
비교예Comparative example 2. 2.
실시예 1에 따른 제 2 점착제와 용매만으로 이루어진 점착제 조성물(A4)를 제조하고, 이를 이용하여 실시예 1과 동일한 방식으로 점착제층(B4)을 형성하고, 표면 개질을 수행하였다.A pressure-sensitive adhesive composition (A4) consisting of only the second pressure-sensitive adhesive and the solvent according to Example 1 was prepared, and the pressure-sensitive adhesive layer (B4) was formed in the same manner as in Example 1, and surface modification was performed.
실험예 1 - 유리 기판 또는 PI 기재 필름에 대한 박리력 측정 Experimental Example 1 - Peel force measurement on a glass substrate or PI substrate film
실시예 1 및 2와 비교예 1 및 2에 따른 점착제층의 유리 기판 또는 PI 기재필름에 대한 박리력을 측정하였고, 그 결과를 하기 표 1에 도시하였다. Peel force on the glass substrate or PI substrate film of the pressure-sensitive adhesive layer according to Examples 1 and 2 and Comparative Examples 1 and 2 was measured, and the results are shown in Table 1 below.
실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2
유리 기판에 대한 접착력(gf/in)Adhesion to Glass Substrate (gf / in) 3232 2828 22 337337
PI 기재 필름에 대한 접착력(gf/in)Adhesive force to PI base film (gf / in) 2,2002,200 2,7002,700 -- 12001200
상기 표 1에 기재되어 있는 바와 같이, 본 출원에 실시예 1 및 2에 따른 점착제 조성물을 이용하여 점착제층을 형성한 경우, 유리 기판 또는 PI 기재 필름에 대하여 우수한 접착력을 가지고 있으나, 비교예 1에 따른 저점착제층의 경우, 하기 표 2와 같이 비록 저장 탄성률의 변화는 작지만, 거의 측정되지 않는 낮은 점착력으로 인하여, 폴더블 디스플레이용 점착제 조성물로 적합하지 않음을 확인할 수 있었다.As described in Table 1, when the pressure-sensitive adhesive layer is formed by using the pressure-sensitive adhesive composition according to Examples 1 and 2 in the present application, it has excellent adhesion to the glass substrate or PI substrate film, but in Comparative Example 1 In the case of the low pressure-sensitive adhesive layer, as shown in Table 2, although the change in storage modulus is small, due to the low adhesive strength that is hardly measured, it could be confirmed that it is not suitable as a pressure-sensitive adhesive composition for foldable display.
실험예Experimental Example 2 - 저장 탄성률의 측정 2-measurement of storage modulus
실시예 1 및 2 에 따른 조성물의 경화 후, 온도에 따른 저장 탄성률 변화율을 알아보기 위해, 강제 대류 오븐을 구비한 ARES-RDA, TA instruments 장비를 이용하여 상기 기재된 측정 방식에 따라 -40℃ 및 90℃에서의 저장 탄성률을 측정 하여 그 결과를 표 2에 나타내었다. After curing of the compositions according to Examples 1 and 2, in order to determine the rate of change in storage modulus with temperature, -40 ° C. and 90 according to the measurement method described above using ARES-RDA, TA instruments equipped with a forced convection oven The storage modulus at ℃ was measured and the results are shown in Table 2.
실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2
-40℃에서 저장 탄성률 (Pa)Storage modulus at -40 ℃ (Pa) 1.8 x 105Pa1.8 x 10 5 Pa 1.8 x 105Pa1.8 x 10 5 Pa 8 x 105Pa8 x 10 5 Pa 3 x 105Pa3 x 10 5 Pa
90℃에서 저장 탄성률 (Pa)Storage modulus at 90 ° C (Pa) 1.1 x 105Pa1.1 x 10 5 Pa 1.7 x 105Pa1.7 x 10 5 Pa 7 x 105Pa7 x 10 5 Pa 3 x 104Pa3 x 10 4 Pa
실험예Experimental Example 3 - 이형  3-variant 박리력Peel force 측정 Measure
실시예 1 및 2와 비교예 1 및 2에 따른 점착제층의 폭을 1 inch로 하여 25℃, 50% 상대습도 하에서 1주일 동안 보관한 후에 상기 점착제층을 각각 중박리 타입 및 경박리 타입의 불소계 이형 필름과 부착 시킨 후, 0.3m/min 의 박리속도 및 180도의 박리 각도에서, texture analyzer를 이용하며, ASTM3330에 근거하여 측정하였고, 그 결과를 하기 표 3에 기재하였다.The pressure-sensitive adhesive layer according to Examples 1 and 2 and Comparative Examples 1 and 2 was 1 inch in width for 1 week at 25 ° C. and 50% relative humidity, and then the pressure-sensitive adhesive layer was fluorine-based and light-peeled, respectively. After attaching with the release film, at a peel rate of 0.3 m / min and a peel angle of 180 degrees, using a texture analyzer, measured based on ASTM3330, the results are shown in Table 3 below.
조건Condition 실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2
경박리 타입 불소계이형 필름 (gf/in)Hard peel type fluorine release film (gf / in) 77 44 22 9.19.1
중박리 타입 불소계이형 필름 (gf/in)Heavy peeling type fluorine release film (gf / in) 1111 88 -- 76.876.8
실험예 1 내지 3과 표 1 내지 3에 기재되어 있는 바와 같이, 실시예 1 및 2에 따른 점착제층의 경우, 적절한 접착력 및 응집력을 가지고, 또한 -40℃의 온도에서 저장 탄성률이 5.0 x 106Pa 이하를 나타냄으로 인하여, 폴더블 디스플레이에서 요구되는 폴딩 신뢰성을 확보할 수 있음은 물론이고, 이형 박리력이 매우 낮은 범위로 유지되어 이형력이 우수할 수 있다.As described in Experimental Examples 1 to 3 and Tables 1 to 3, in the case of the pressure-sensitive adhesive layers according to Examples 1 and 2, the adhesive modulus and the cohesion force were appropriate, and the storage modulus was 5.0 × 10 6 at a temperature of −40 ° C. By showing Pa or less, not only the folding reliability required in the foldable display can be secured, but also the release force can be maintained in a very low range and the release force can be excellent.

Claims (12)

  1. 제 1 실리콘 검(gum)을 포함하고, 0.3 m/min의 박리 속도 및 180도의 박리각도에서 측정한 유리 기판에 대한 박리력이 10 gf/in 이하인 제 1 점착제;A first pressure-sensitive adhesive having a first silicon gum and having a peel force of 10 gf / in or less on a glass substrate measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees;
    제 2 실리콘 검(gum) 및 제 2 MQ 수지를 포함하고, 0.3 m/min의 박리 속도 및 180도의 박리 각도에서 측정한 유리 기판에 대한 박리력이 200gf/in 내지 400gf/in의 범위 내에 있는 제 2 점착제를 포함하고,A second silicon gum and a second MQ resin, wherein the peel force for the glass substrate measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees is in the range of 200 gf / in to 400 gf / in 2 contains an adhesive,
    상기 제 1 점착제를 조성물의 총 고형분 대비 5wt% 내지 50wt%의 범위 내로 포함하며,Including the first pressure-sensitive adhesive in the range of 5wt% to 50wt% relative to the total solids of the composition,
    하기 수식 1을 만족하는 폴더블(foldable) 디스플레이용 점착제 조성물:Pressure-sensitive adhesive composition for a foldable display that satisfies the following formula 1:
    [수식 1][Equation 1]
    A<20gf/inA <20gf / in
    수식 1에서, A는 점착제 조성물이 경화되어 형성된 점착제층의 0.3 m/min의 박리 속도 및 180도의 박리 각도에서 측정한 불소계 이형필름에 대한 박리력을 의미한다.In Formula 1, A means the peeling force with respect to the fluorine-type release film measured at the peeling speed of 0.3 m / min and the peeling angle of 180 degrees of the pressure-sensitive adhesive layer formed by curing the pressure-sensitive adhesive composition.
  2. 제 1항에 있어서,The method of claim 1,
    제 1 또는 제 2 실리콘 검(gum)은 하기 화학식 1로 표현되는 폴더블(foldable) 디스플레이용 점착제 조성물:The first or second silicone gum (gum) is a pressure-sensitive adhesive composition for a foldable (foldable) display represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2017009876-appb-I000003
    Figure PCTKR2017009876-appb-I000003
    상기 화학식 1에서, R1 및 R6는 각각 독립적으로 알킬기, 알케닐기 또는 아릴기를 포함하거나 포함하지 않는 실릴기 또는 실라놀기이고, R2 내지 R5는 각각 독립적으로 알킬기, 알케닐기 또는 아릴기이며, n 및 m은 각각 독립적으로 1 내지 10,000의 범위 내에 있는 정수이다. In 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.
  3. 제 1항에 있어서,The method of claim 1,
    제 1 점착제는 제 1 MQ 수지를 5wt% 미만의 함량으로 포함하는 폴더블(foldable) 디스플레이용 점착제 조성물. The first pressure-sensitive adhesive composition for a foldable (foldable) display comprising a first MQ resin in an amount of less than 5wt%.
  4. 제 1항에 있어서,The method of claim 1,
    제 1 실리콘 검(gum)은 수 평균 분자량이 400,000 내지 800,000의 범위 내에 있는 폴더블(foldable) 디스플레이용 점착제 조성물.The first silicone gum (gum) has a number average molecular weight of 400,000 to 800,000 in the pressure-sensitive adhesive composition for foldable (foldable) display.
  5. 제 1항에 있어서,The method of claim 1,
    제 1 실리콘 검(gum)은 비닐기 함량이 0.5 내지 1.5mol%의 범위 내에 있는 폴더블(foldable) 디스플레이용 점착제 조성물.The first silicone gum (gum) is a pressure-sensitive adhesive composition for foldable display (vinyl group content) in the range of 0.5 to 1.5 mol%.
  6. 제 1항에 있어서,The method of claim 1,
    제 2 점착제는 -40℃에서 측정한 저장 탄성률이 107Pa 이하인 폴더블(foldable) 디스플레이용 점착제 조성물.The second pressure-sensitive adhesive is a storage modulus measured at -40 ℃ 10 7 Pa or less folder block (foldable) pressure-sensitive adhesive composition for a display.
  7. 제 1항에 있어서,The method of claim 1,
    제 2 점착제는 제 2 MQ 수지를 40wt%이하의 함량으로 포함하는 폴더블(foldable) 디스플레이용 점착제 조성물.The second pressure-sensitive adhesive composition for a foldable (foldable) display comprising a second MQ resin in an amount of 40wt% or less.
  8. 제 1항에 있어서,The method of claim 1,
    제 2 실리콘 검(gum)은 양 말단에 히드록시기를 포함하는 선형 폴리디메틸실록산인 폴더블(foldable) 디스플레이용 점착제 조성물.The second silicone gum (gum) is a linear polydimethylsiloxane containing a hydroxyl group at both ends, the adhesive composition for a foldable display.
  9. 제 1항에 있어서,The method of claim 1,
    -40℃ 내지 90℃의 온도 범위 내에서, 경화 후 저장 탄성률(G')이 5 x 106 Pa 이하인 폴더블(foldable) 디스플레이용 점착제 조성물.Pressure-sensitive adhesive composition for foldable display having a storage modulus (G ′) of 5 × 10 6 Pa or less after curing within a temperature range of −40 ° C. to 90 ° C.
  10. 피착제에 부착되어 있는 제 1항의 폴더블(foldable) 디스플레이용 점착제 조성물의 경화물인 점착제층을 포함하는 폴더블(foldable) 디스플레이.A foldable display comprising a pressure-sensitive adhesive layer which is a cured product of the pressure-sensitive adhesive composition for foldable display of claim 1 attached to an adherend.
  11. 제 10항에 있어서,The method of claim 10,
    피착제는 기재 필름이고, 상기 기재 필름과 점착제층은 상기 점착제층에 포함되는 실라놀기를 매개로 공유 결합을 형성하고 있는 폴더블(foldable) 디스플레이.The adherend is a base film, wherein the base film and the pressure-sensitive adhesive layer forms a covalent bond via a silanol group contained in the pressure-sensitive adhesive layer.
  12. 제 14항에 있어서,The method of claim 14,
    점착제층은 0.3 m/min의 박리 속도 및 180도의 박리 각도에서 측정한 피착제에 대한 박리력이 2,000gf/in이상인 폴더블(foldable) 디스플레이.The pressure-sensitive adhesive layer is a foldable display having a peel force of 2,000 gf / in or more with respect to an adhesive measured at a peel rate of 0.3 m / min and a peel angle of 180 degrees.
PCT/KR2017/009876 2016-09-09 2017-09-08 Adhesive composition for foldable display WO2018048245A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780048568.2A CN109563396B (en) 2016-09-09 2017-09-08 Pressure sensitive adhesive composition for foldable displays
JP2019500648A JP2019527745A (en) 2016-09-09 2017-09-08 Adhesive composition for foldable display
EP17849129.6A EP3511390B1 (en) 2016-09-09 2017-09-08 Pressure sensitive adhesive composition for foldable display
US16/331,743 US10920112B2 (en) 2016-09-09 2017-09-08 Pressure-sensitive adhesive composition for foldable display

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2016-0116324 2016-09-09
KR20160116324 2016-09-09
KR10-2017-0114558 2017-09-07
KR1020170114558A KR102024251B1 (en) 2016-09-09 2017-09-07 Pressure Sensitive Adhesive composition using foldable display

Publications (1)

Publication Number Publication Date
WO2018048245A1 true WO2018048245A1 (en) 2018-03-15

Family

ID=61562141

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/009876 WO2018048245A1 (en) 2016-09-09 2017-09-08 Adhesive composition for foldable display

Country Status (1)

Country Link
WO (1) WO2018048245A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019527268A (en) * 2016-09-09 2019-09-26 エルジー・ケム・リミテッド Adhesive composition for foldable display
CN115403799A (en) * 2018-12-31 2022-11-29 三星Sdi株式会社 Silicone-based adhesive protective film and optical member including same
US11987731B2 (en) 2018-08-10 2024-05-21 Dow Toray Co., Ltd. Organopolysiloxane composition for forming pressure sensitive adhesive layer, and use of same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070096278A (en) * 2006-03-23 2007-10-02 주식회사 엘지화학 Pressure sensitive adhesive composition for transferring flexible substrate
KR20120059512A (en) * 2009-08-27 2012-06-08 아사히 가라스 가부시키가이샤 Multilayer structure with flexible base material and support, panel for use in electronic device provided with support and production method for panel for use in electronic device
KR20150011230A (en) 2013-07-22 2015-01-30 삼성디스플레이 주식회사 Foldable display and method of manufacturing the same
KR20150097533A (en) * 2012-12-21 2015-08-26 다우 코닝 코포레이션 Layered polymer structures and methods
KR20160083583A (en) * 2014-12-31 2016-07-12 삼성전자주식회사 Adhesive film and optical member comprising the same
KR20160100575A (en) * 2015-02-16 2016-08-24 주식회사 엘지화학 Liquid crystal device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070096278A (en) * 2006-03-23 2007-10-02 주식회사 엘지화학 Pressure sensitive adhesive composition for transferring flexible substrate
KR20120059512A (en) * 2009-08-27 2012-06-08 아사히 가라스 가부시키가이샤 Multilayer structure with flexible base material and support, panel for use in electronic device provided with support and production method for panel for use in electronic device
KR20150097533A (en) * 2012-12-21 2015-08-26 다우 코닝 코포레이션 Layered polymer structures and methods
KR20150011230A (en) 2013-07-22 2015-01-30 삼성디스플레이 주식회사 Foldable display and method of manufacturing the same
KR20160083583A (en) * 2014-12-31 2016-07-12 삼성전자주식회사 Adhesive film and optical member comprising the same
KR20160100575A (en) * 2015-02-16 2016-08-24 주식회사 엘지화학 Liquid crystal device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019527268A (en) * 2016-09-09 2019-09-26 エルジー・ケム・リミテッド Adhesive composition for foldable display
US11987731B2 (en) 2018-08-10 2024-05-21 Dow Toray Co., Ltd. Organopolysiloxane composition for forming pressure sensitive adhesive layer, and use of same
CN115403799A (en) * 2018-12-31 2022-11-29 三星Sdi株式会社 Silicone-based adhesive protective film and optical member including same
US11767453B2 (en) 2018-12-31 2023-09-26 Samsung Sdi Co., Ltd. Silicone-based adhesive protective film and optical member comprising the same

Similar Documents

Publication Publication Date Title
KR102024253B1 (en) Pressure Sensitive Adhesive composition using foldable display
WO2019117595A1 (en) Adhesive composition for foldable display, and foldable display comprising same
WO2017171489A1 (en) Manufacturing method for barrier film
WO2011126263A2 (en) Adhesive composition, adhesive sheet, and touch panel
WO2018048245A1 (en) Adhesive composition for foldable display
KR20170130501A (en) A release agent composition for a silicone pressure-sensitive adhesive, a release film and a laminate
KR102024252B1 (en) Pressure Sensitive Adhesive composition using foldable display
KR102024251B1 (en) Pressure Sensitive Adhesive composition using foldable display
EP3645651B1 (en) A method for fabricating a flexible organic light emitting diode using a pressure sensitive adhesive composition
JP2014047310A (en) Adhesive film and method for manufacturing the same
WO2018048240A1 (en) Adhesive composition for foldable display
WO2015174679A1 (en) Non-curable rubber-based adhesive composition for touch screen panel, and non-curable rubber-based adhesive film for touch screen panel using same
WO2022097872A1 (en) Release film and preparation method therefor
WO2017183833A1 (en) Optical adhesive composition and optical adhesive layer containing cured product thereof
WO2018048243A1 (en) Adhesive composition for foldable display
WO2019045336A1 (en) Non-substrate type silicone adhesive film
WO2017073883A1 (en) Silicone adhesive composition
WO2017116201A1 (en) Release film and method for manufacturing same
KR102126687B1 (en) Pressure Sensitive Adhesive composition using foldable display
WO2017069383A1 (en) Silicone adhesive composition
KR101842832B1 (en) Silicone release composition, releasing film and protective tape for steel sheet process using the same
WO2017069382A1 (en) Silicone adhesive composition
WO2017078487A1 (en) Optical adhesive composition, method for producing optical adhesive composition, and optical adhesive film
WO2022186427A1 (en) Release film
WO2022131500A1 (en) Silicone release coating composition and release film comprising same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17849129

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019500648

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017849129

Country of ref document: EP

Effective date: 20190409