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WO2020091321A1 - Stratifié à revêtement dur - Google Patents

Stratifié à revêtement dur Download PDF

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Publication number
WO2020091321A1
WO2020091321A1 PCT/KR2019/014201 KR2019014201W WO2020091321A1 WO 2020091321 A1 WO2020091321 A1 WO 2020091321A1 KR 2019014201 W KR2019014201 W KR 2019014201W WO 2020091321 A1 WO2020091321 A1 WO 2020091321A1
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WO
WIPO (PCT)
Prior art keywords
group
hard coating
carbon atoms
formula
substituted
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2019/014201
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English (en)
Korean (ko)
Inventor
이은선
김하늘
백승일
김우한
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
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 KR1020190131740A external-priority patent/KR102147481B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201980032322.5A priority Critical patent/CN112118961B/zh
Priority to EP19879995.9A priority patent/EP3778224B1/fr
Priority to US16/973,339 priority patent/US12151456B2/en
Priority to JP2020560436A priority patent/JP7060202B2/ja
Publication of WO2020091321A1 publication Critical patent/WO2020091321A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters

Definitions

  • the present invention relates to a hard coating laminate having a high pencil hardness, excellent adhesion, impact resistance, external bending resistance and bending resistance.
  • Glass or tempered glass is generally used as a material having excellent mechanical properties in a window or front panel for display of such a mobile device.
  • the glass causes the mobile device to become heavy due to its own weight, and there is a problem of damage due to external impact.
  • plastic resin has been studied as a material that can replace glass.
  • the plastic resin composition is suitable for the trend of pursuing a lighter mobile device due to its light weight and low risk of breaking.
  • a composition for coating a hard coating layer on a supporting substrate has been proposed to achieve a composition having properties of high hardness and wear resistance.
  • an acrylate-based resin capable of UV curing is mainly used as a hard coating film required for a foldable display material.
  • the acrylate-based resin has a high curing shrinkage, so that the curl is severe, and thus a double-sided coating or a thin coating must be performed.
  • a method of increasing the thickness of the hard coating layer may be considered as a method of improving the surface hardness of the hard coating layer.
  • a method of improving the surface hardness of the hard coating layer In order to secure a surface hardness sufficient to replace glass, it is necessary to implement a constant thickness of the hard coating layer.
  • the surface hardness may increase, but wrinkles or curls increase due to hardening shrinkage of the hard coating layer and poor external flexibility, so that cracking or peeling of the hard coating layer is likely to occur. Therefore, it is not easy to apply practically.
  • the present invention is to provide a hard coating laminate suitable for application to a foldable display material, as well as exhibiting high pencil hardness, excellent adhesion, impact resistance, and bending resistance.
  • the support substrate layer In the present specification, the support substrate layer; And
  • a hard coating layer having a thickness of 50 to 240 ⁇ m; includes,
  • the hard coating layer includes a cured product of a resin composition including a siloxane resin and an elastic polymer,
  • the elastomer is contained in an amount of 20 to 80 parts by weight based on 100 parts by weight of the siloxane resin,
  • the siloxane resin comprises 70 mol% or more of the repeating unit represented by Formula 1 with respect to 100 mol% of the total molar ratio content of the units constituting the entire siloxane resin,
  • a hard coating laminate having flex resistance and outer flex resistance is provided.
  • R 1 is a functional group represented by the following formula (a), a is a positive number,
  • R a is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or -R b OR c- ,
  • R b to R c are each independently, a single bond, or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms)
  • a weight average molecular weight means the weight average molecular weight (unit: g / mol) of polystyrene conversion measured by GPC method.
  • detectors and analytical columns such as a commonly known analytical device and a differential index detector, can be used, and the temperature is usually applied.
  • Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 35 ° C, a chloroform solvent (Chloroform) and a flow rate of 1 mL / min.
  • the hard coating film may mean a hard coating layer including a cured product formed using a hard coating composition.
  • the hard coating composition includes a resin composition containing a siloxane resin and an elastomer.
  • the support substrate layer And a hard coating layer formed on the support substrate layer and having a thickness of 50 to 240 ⁇ m, wherein the hard coating layer includes a cured product of a resin composition including a siloxane resin and an elastomer, and the elastomer is the 20 to 80 parts by weight based on 100 parts by weight of the siloxane resin, the siloxane resin is 70 mol% or more of the repeating unit represented by the following formula (1) with respect to 100 mol% of the total molar ratio of the units constituting the entire siloxane resin Including, a hard coating laminate having bending resistance and bending resistance can be provided.
  • the hard coating layer includes a cured product of a resin composition including a siloxane resin and an elastomer, and the elastomer is the 20 to 80 parts by weight based on 100 parts by weight of the siloxane resin, the siloxane resin is 70 mol% or more of the repeating unit represented by the following formula (1) with respect to 100
  • R 1 is a functional group represented by the following formula (a), a is a positive number,
  • R a is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or -R b OR c- ,
  • R b to R c are each independently a single bond or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms)
  • the hardness of the hard coating layer is 5H or more, excellent rigidity can be secured in manufacturing a foldable display device.
  • the conventional hard coating film has a hardness of 5H or more, but it is difficult to secure impact resistance and scratch resistance.
  • the hard coating laminate may include the meaning of a hard coating film. Accordingly, although the hard coating laminate of the present invention may include at least one hard coating layer on at least one side of the supporting substrate layer, more preferably, the hard coating laminate includes a structure including a hard coating layer having a single-sided coating formed on the supporting substrate layer.
  • the hard coating layered product can form a thick film-type hard coating layer on which a single-sided coating is performed on a substrate, and thus can realize an effect of improving adhesiveness, bending resistance, etc. as well as high pencil hardness. .
  • the hard coating laminate is formed by using a resin composition comprising a siloxane resin and an elastomer having a glycidoxypropyl-modified silicone structure including the silsesquioxane repeating unit of Chemical Formula 1 as a hard coating composition.
  • a resin composition comprising a siloxane resin and an elastomer having a glycidoxypropyl-modified silicone structure including the silsesquioxane repeating unit of Chemical Formula 1
  • the hard coating layer that is, hard coating film
  • the hard coating layer containing the cured product of the resin composition containing the two components, while having a high pencil hardness of 5H or more, does not deteriorate adhesion and scratch resistance, impact resistance, external bending resistance and It is possible to provide an effect having excellent bending characteristics.
  • the siloxane resin having a glycidoxypropyl-modified silicone structure is characterized in that it comprises a compound represented by the following formula (2).
  • R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • R 1 is a functional group represented by the following formula (a),
  • R a is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or -R b OR c- ,
  • R b to R c are each independently a single bond, or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms,
  • Recurring unit containing a substituent of R 1 with respect to the total molar ratio of the formula (2) contains 70 mol% or more
  • R 2 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted carbon number 2 to 20, Alkynyl group, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted alkyl aryl group having 7 to 20 carbon atoms, epoxy group, hydrogen atom, amino group , Selected from the group consisting of mercapto group, ether group, ester group, carbonyl group, carboxyl group and sulfone group,
  • the hard coating layered product may include a hard coating layer having a thickness greater than or equal to a certain level compared to the support substrate layer, but may have high impact resistance, flex resistance, and exoskeleton resistance.
  • the ratio of the thickness of the hard coating layer to the support substrate layer is not limited, but, for example, the thickness of the hard coating layer compared to the support substrate layer may be 25% or more, or 30% or more, or 25% to 100%. .
  • the hard coating laminate has a thickness of 50 ⁇ m or more, for example, about 50 to about 240 ⁇ m, or about 70 to about 200 ⁇ m, or about 50 ⁇ m to about 150 ⁇ m, or about 70 to about 150 ⁇ m It may include a hard coating layer having a.
  • a thickness improvement of 100 ⁇ m or more can be expected. Accordingly, in the present invention, a laminate including a hard coating layer having good pencil hardness (5H or more) and having good adhesiveness, impact resistance, bending resistance, and external bending characteristics can be provided in a thick film type implementation. In addition, by improving the overall thickness through a double coating (dual coating) to improve the impact resistance, it is possible to provide a laminate including a hard coating layer that is advantageous in bending resistance.
  • the thickness of the hard coating layer in the hard coating layer is 50 ⁇ m or less, impact resistance may be deteriorated, and if it is 240 ⁇ m or more, crack resistance may be deteriorated by hard coating.
  • the hard hard coating composition it is possible to provide a laminate including a hard coating layer having excellent bending durability by satisfying both the bending resistance and the outer bending resistance as well as the thickness range showing excellent mechanical properties.
  • a dynamic folding machine tester was used to observe the appearance when the support substrate layer or the surface coated on the lower side of the base was folded inward by radius, to evaluate bending resistance and external bending resistance. have.
  • the hard-coated laminate according to the present specification was folded into the inside of the hard-coated layer-formed surface at an angle of 90 degrees so that the hard-coated layer-formed side faces the middle of the hard-coated laminate at 200 ° C. It has flex resistance that does not crack when repeated.
  • the hard coating layered product according to the present specification based on the middle of the hard coating layered, the support substrate layer for forming a hard coating layer or the surface coated on the lower side of the hard coating layer is formed at an angle of 90 degrees toward the inside When it is folded outwards and then repeated 200,000 times at 25 ° C, it has an external bendability that does not cause cracking.
  • the surface on which the hard coating layer is formed is folded inward, and then folded and unfolded at 200 ° C. for 200,000 times.
  • R inner radius of curvature
  • the upper coating layer is folded so as to be folded inwards, and then repeated 200,000 times at 25 ° C., the inner radius of curvature (R) of the folded portion is measured and cracks are generated
  • the flex resistance can be evaluated by checking.
  • the hard coating layered product of the above embodiment was spaced at a distance of 5 mm in the middle of the hard coat layered product (so that the radius was 2.5 mm) using a dynamic folding machine tester at a 90 degree angle so that the hard coat layer faced each other.
  • a dynamic folding machine tester at a 90 degree angle so that the hard coat layer faced each other.
  • the hard coating layer of the embodiment is a hard coating layer with a predetermined distance, for example, 8 mm interval, in the middle of the hard coating laminate using a dynamic folding machine tester.
  • a predetermined distance for example, 8 mm interval
  • the support substrate layer for forming or the surface coated on the lower side is folded outward of the hard coating layer at an angle of 90 degrees toward the inside, and then repeated 200,000 times at 25 ° C., it may have an external bending property that does not generate cracks.
  • the hard coating laminate of the embodiment is supported at a predetermined interval, for example, 8 mm spacing, in the middle of the hard coating laminate using a dynamic folding machine tester.
  • a predetermined interval for example, 8 mm spacing
  • the lower coating layer of the base material layer faces inward, it is folded outward of the upper hard coating layer at an angle of 90 degrees, and when it is folded and repeated 200,000 times at 25 ° C, it may have an external bending property that does not generate cracks.
  • both sides of the hard-coated laminate were folded at an angle of 90 degrees with respect to the bottom surface and repeated 200,000 times at 25 ° C at a rate of about 1 to about 3 times / sec. It is possible to measure the durability against bending in a manner. At this time, in the case of bending resistance, the hard coating layer may be folded toward the surface on which it is formed, and in the case of external bending resistance, it may be tested by folding toward the supporting substrate layer, which is the opposite side of the hard coating layer.
  • the hard-coated laminate of the present invention does not generate cracks of 1 cm or more or 5 mm or more even after bending 200,000 times, and virtually no cracks are generated.
  • the hard-coated laminate can be suitably applied for a foldable display since there is a very low risk of cracking even in an actual use state such as repeatedly folding, rolling, or bending.
  • the siloxane resin is a compound represented by Chemical Formula 2 including the repeating unit of Chemical Formula 1, and may be an epoxy polysiloxane, and mechanical properties such as hardness and rigidity according to the definition of Chemical Formula 2 This is improved, and excellent internal and external bending properties can be secured.
  • R 1 is a functional group containing a substituent represented by the formula (a) containing 70 mol% or more with respect to the total molar ratio content of the total siloxane resin.
  • R 1 SiO 3/2 includes silsesquioxane structural units.
  • R a in Chemical Formula a may be a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or -R b OR c- . More specifically, R a may be methylene, ethylene, or propylene.
  • each of R b to R c may be independently a single bond, or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, and more specifically, a single bond or methylene, ethylene, propylene, and butyl. It may be a linear alkylene group having 1 to 6 carbon atoms such as ren.
  • R is a methylene, ethylene, or -R a OR b - may be of, wherein R a and R b is either a bond or methylene, having from 1 to 6 carbon atoms or 1 to 3 carbon atoms, such as propylene It may be a linear alkylene group.
  • R 1 SiO 3/2 includes silsesquioxane structural units.
  • R a in Chemical Formula a may be a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or -R b OR c- . More specifically, R a may be methylene, ethylene, propylene or -R b OR c- . In this case, the R b to R c may be each independently, a single bond, or a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms.
  • R 1 is a glycidyl group, or Ra of Formula 2 is -R b OR c- , wherein R b is alkylene having 1 to 3 carbon atoms, and Rc is methylene
  • R 1 includes a glycidoxy group, and may be, for example, a glycidoxypropyl group.
  • R a when R a is substituted, specifically, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an amino group, an acrylic group (Or acryloyl group), methacrylic group (or methacryloyl group), acrylate group (or acryloyloxy group), methacrylate group (or methacryloyloxy group), halogen group, mercapto group, ether group , Ester group, acetyl group, formyl group, carboxyl group, nitro group, sulfonyl group, urethane group, epoxy group, may be substituted with one or more substituents selected from the group consisting of oxetanyl group and phenyl group, more specifically methyl , Alkyl groups having 1 to 6 carbon atoms such as
  • Formula 2 may further include a silsesquioxane unit of (R 2 SiO 3/2 ) together with the silsesquioxane unit of Formula 1 of (R 1 SiO 3/2 ) described above.
  • the silsesquioxane unit of (R 2 SiO 3/2 ) may improve the surface hardness characteristics of the coating layer by increasing the curing density of the siloxane resin.
  • R 2 is specifically a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, substituted Or unsubstituted aryl group having 6 to 12 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 12 carbon atoms, substituted or unsubstituted alkyl aryl group having 7 to 12 carbon atoms, epoxy group, oxetanyl group, acrylate group, meta It may be selected from the group consisting of acrylate groups and hydrogen atoms.
  • R 2 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an amino group, an acrylic group, a methacryl group, or an acrylate.
  • substituents and more specifically, one or more selected from the group consisting of an acrylic group, a methacryl group, an acrylate group, a methacrylate group, a vinyl group, an allyl group, an epoxy group and an oxetanyl group. It may be substituted with a substituent.
  • R 2 is more specifically an acrylic group, a methacryl group, an acrylate group, a methacrylate group, a vinyl group, in that the curing hardness of the siloxane resin is further increased to further improve the surface hardness properties of the coating layer.
  • R 2 may be an unsubstituted phenyl group or an epoxy group.
  • the 'epoxy group' is a functional group containing an oxirane ring, and unless otherwise specified, an unsubstituted epoxy group containing only the oxirane ring, an alicyclic epoxy group having 6 to 20 carbon atoms, or 6 to 12 carbon atoms. (Eg, epoxycyclohexyl, epoxycyclopentyl, etc.); And an aliphatic epoxy group having 3 to 20 carbon atoms or 3 to 12 carbon atoms (such as a glycidyl group).
  • R 2 is an epoxy group, the same functional group represented by Chemical Formula 2 is excluded.
  • the 'oxetanyl group' is a functional group containing an oxetane ring, and unless otherwise specified, an unsubstituted oxetanyl group containing only the oxetane ring, 6 to 20 carbon atoms, or 6 to 6 carbon atoms. And an alicyclic oxetanyl group of 12, and an aliphatic oxetanyl group of 3 to 20 carbon atoms, or 3 to 12 carbon atoms.
  • the said siloxane resin may contain the structural unit of (OR).
  • the R may be specifically a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms or 1 to 12 carbon atoms, and more specifically, a hydrogen atom, or a methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl It may be a linear or branched alkyl group having 1 to 4 carbon atoms such as a group.
  • R is hydrogen or an alkyl group having 1 to 3 carbon atoms
  • R 1 includes a glycidoxypropyl group
  • R 2 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an epoxy Can be.
  • the siloxane resin containing the above-described structural units may be prepared by a hydrolysis and condensation reaction between a siloxane monomer of each structural unit, specifically, an alkoxysilane having a functional group represented by Formula 2, or between these alkoxysilanes and heterogeneous alkoxysilanes.
  • the molar ratio of each constituent unit may be controlled by controlling the content ratio of the alkoxysilane.
  • a, b, and c are respectively the molar ratio of the (R 1 SiO 3/2 ) unit, (R 2 SiO 3/2 ) unit, and (OR) unit constituting the siloxane resin Shows.
  • a / (a + b) ⁇ 0.7 a is a positive number
  • b and c may each independently or simultaneously be 0 or a positive number.
  • the siloxane resin may contain 70 mol% or more of the repeating unit represented by Formula 1 including a substituent of R 1 with respect to 100 mol% of the total molar ratio of the units constituting the siloxane resin. have. Therefore, the siloxane resin of the present invention can contribute to improving the mechanical properties of the hard coating layered product including the hard coating layer.
  • the siloxane resin is 70 mol% of the repeating unit represented by the formula (1) including a substituent of R 1 with respect to 100 mol% of the total molar ratio of the units constituting the siloxane resin. To 100 mol%.
  • the repeating unit containing a substituent of R 1 is 70 mol% or less, there is a problem that impact resistance is lowered.
  • the molar content of the structural unit is less than 70 mol%, it is difficult to exhibit a sufficient surface hardness of the hard coating layer due to a decrease in curing density.
  • the repeating unit including the substituent of the R 1 is (R 1 SiO 3/2) as meaning that it comprises a constituent unit, 70 mol% or more based on 100 mol% of the total amount of monomers constituting the siloxane resin, more Specifically, it may mean to include 70 mol% or more and 100 mol% or less.
  • the hardening density is increased when forming the hard coat layer, and as a result, the hard coat film may exhibit significantly improved surface hardness.
  • the siloxane resin of Formula 1 may include at least 70 mol% or 70 mol% to 100 mol% of glycidoxypropyl-modified silicone in the structure.
  • the siloxane resin of Chemical Formula 1 may be prepared through condensation polymerization of siloxane monomers of each repeating unit, and if the conditions include a (R 1 SiO 3/2 ) structure including a functional group of Chemical Formula 2 at least 70 mol% or more, Conditions are not limited.
  • the siloxane resin of Formula 1 may have a weight average molecular weight (Mw) of 1,000 to 50,000 g / mol.
  • the hard coating composition of the present invention can improve the warpage characteristics and improve the flexibility of the hard coating laminate including the hard coating layer by using a certain amount of the elastic polymer serving to provide flexibility.
  • the hard coating composition may include 20 to 80 parts by weight of the elastomer relative to 100 parts by weight of the siloxane resin.
  • the elastomer may include 20 to 70 parts by weight or 20 to 50 parts by weight based on 100 parts by weight of the siloxane resin. If the content of the elastic polymer is 20 parts by weight or less, there is a problem that it is insufficient to implement the physical properties of the elastic polymer, and if it is 80 parts by weight or more, there is a problem that it is difficult to secure high hardness.
  • the elastomer may include at least one selected from the group consisting of alkanediol, polyolefin polyol, polyester polyol, polycaprolactone polyol, polyether polyol and polycarbonate polyol.
  • the elastomer can also be obtained by ring-opening polymerization of caprolactone or a reaction using a small amount of diol, triol or amine as an initiator.
  • the elastomer is a polycaprolactone polyol represented by Chemical Formula 3 formed by a ring-opening polymerization reaction as in Reaction Scheme 1 below.
  • the R 'substituent is not limited to the reaction formula 1, and if the sock end is a compound using a form having a hydroxy group (-OH), the type can be used without limitation.
  • a more specific example may be polycaprolactone diol.
  • the elastic polymer may include a polycaprolactone polyol of Mn 300 or more to Mn 10,000 or less
  • the hard coating composition may further include an initiator, or an initiator and an organic solvent.
  • the initiator may contain 0.1 to 10 parts by weight based on 100 parts by weight of the siloxane resin. Preferably, the initiator may be used in an amount of about 0.5 to 5 parts by weight or 1 to 2 parts by weight based on 100 parts by weight of the siloxane resin. If the initiator content is less than 0.1 parts by weight, only surface hardening or epoxy hardening does not occur sufficiently, resulting in low hardness. In addition, if the initiator content exceeds 10 parts by weight, it may cause cracking and peeling of the hard coating layer due to the rapid curing speed.
  • the initiator may be a photopolymerization or thermal polymerization initiator well known in the art, and the type is not particularly limited.
  • the photopolymerization initiator may be a cationic polymerization initiator, a sulfonium salt compound well known in the art.
  • the photopolymerization initiator is aryl sulfonium hexafluoroantimonate salt, aryl sulfonium hexafluorophosphate salt, diphenyldiodonium hexafluorophosphate salt, diphenyldiodonium hexaantimonium salt, Ditorliodonium hexafluorophosphate salt and 9- (4-hydroxyethoxyphenyl) cyanrenium hexafluorophosphate salt may be one or more selected from the group consisting of, but is not limited to.
  • the thermal polymerization initiator is 3-methyl-2-butenyltetramethylenesulfonium hexaflooroantimonate salt, ytterbium trifluoromethenesulfonate salt, samarium trifluoromethenesulfonate salt, erbium trifluoromethene Sulfonate salt, disprosium trifluoromethenesulfonate salt, lanthanum trifluoromethenesulfonate salt, tetrabutylphosphonium methenesulfonate salt, ethyltriphenylphosphonium bromide salt, benzyldimethylamine, dimethyl Aminomethylphenol, triethanolamine, Nn-butylimidazole and 2-ethyl-4-methylimidazole may include one or more selected from the group consisting of, but is not limited thereto.
  • the hard coating laminate can be formed with a solvent-free when there is no process problem.
  • an organic solvent may be optionally included in order to control the viscosity and fluidity of the hard coating composition used to form the hard coating laminate and to increase the coating property of the composition to the supporting substrate.
  • the organic solvent includes an alcohol-based solvent such as methanol, ethanol, isopropyl alcohol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 1-methoxy-2 -Alkoxy alcohol solvents such as propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, ketone solvents such as cyclohexanone, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monopropyl ether, diethyl glycol monobutyl ether, diethylene glycol-2-ethylhexyl ether and The same ether-based solvent such as methanol, ethanol,
  • the hard coating composition may further include one or more additives commonly used in the technical field to which the present invention pertains, such as an antioxidant, a coating aid, a surfactant, an anti-yellowing agent, and an anti-oxidant.
  • the content can be variously adjusted within a range that does not degrade the physical properties of the hard coating film of the present invention, but is not particularly limited, for example, with respect to 100 parts by weight of the siloxane resin, contained in about 0.1 to about 10 parts by weight Can be.
  • the antioxidant may include a mixture of one or more selected from the group consisting of phenolic, phosphate, amino, thioester, etc., but may not be limited thereto.
  • the surfactant may be a 1 to 2 functional fluorine-based acrylate, a fluorine-based surfactant, or a silicone-based surfactant.
  • the surfactant may be included in a form dispersed or crosslinked in the crosslinked copolymer.
  • an anti-yellowing agent may be included as the additive, and the anti-yellowing agent may include a benzophenone-based compound or a benzotriazole-based compound.
  • the antioxidant can be used to suppress the oxidation reaction caused by polymerization of the siloxane resin.
  • the manufacturing conditions of the siloxane resin may include the step of performing a condensation polymerization for 1 hour to 20 hours at a temperature of 25 °C to 100 °C.
  • the hard coating layer may be a cured product formed on one side or both sides of the supporting substrate layer.
  • the cured product may be a photocured product or a thermocured product.
  • a single-sided coating or two or more layers may be formed. Further, if necessary, two or more layers can be formed even when the hard coating layer is formed on both sides of the base layer.
  • the hard coating layer may include one or more layers on only one surface of the supporting substrate layer.
  • the hard coating layer may be formed to a thickness of 50 ⁇ m to 240 ⁇ m.
  • the hard coating layered product may be prepared by performing curing according to a general method using a hard coating composition, and the method is not limited.
  • the hard-coated laminate formed by the above method may provide an effect of greatly improving curl characteristics in addition to high pencil hardness of 5H or more.
  • the hard coating laminate refers to a flexible transparent film or a foldable transparent film, and can be usefully used as a material for a front portion, a display portion, etc. in various flexible or foldable display elements.
  • the present invention can provide a hard coating laminate comprising both sides by coating on a film or a substrate including one or more hard coating layers or one or more lower and lower layers by performing one or more coatings as necessary.
  • the above-mentioned hard coating composition may be coated once or one or more times on one surface of the support substrate layer, and then heat or photocured to provide a hard coating laminate in which one or more hard coating layers are formed.
  • the hard coating layer may mean a cured product of the hard coating composition described above.
  • the hard coating laminate may further include a hard coating layer containing a common acrylate-based resin on the other surface of the supporting substrate layer, if necessary.
  • the hard coating laminate may include a first hard coating layer comprising one or more siloxane resins formed on one surface of the supporting substrate and a second hard coating layer comprising acrylate-based resins formed on the other surface of the supporting substrate. Therefore, the hard coating laminate according to the above embodiment includes a base layer; Two or three hard coating layers formed on one surface of the base layer; And two or three hard coating layers formed on both sides of the base layer.
  • the support base layer is used to support the hard coating layer, and a commonly used transparent plastic material may be used.
  • the support substrate layer may include a thermoplastic resin of a plastic material, and a stretched film or a non-stretched film containing a plastic resin may be used without particular limitation on the manufacturing method or material.
  • the support substrate layer is a polyester such as polyethylene terephthalate (polyethylene terephtalate, PET), cyclic olefin copolymer (cyclic olefin copolymer, COC), polyacrylate (polyacrylate, PAC), polycarbonate ( polycarbonate, PC), polyethylene, PE, polymethylmethacrylate (PMMA), polyetheretherketon (PEK), polyethylenenaphthalate (PEN), polyetherimide (PEI) , Polyamide imide (PAI), polyimide (PI), triacetylcellulose (TAC) and methyl methacrylate (MMA, methyl methacrylate) may include at least one thermoplastic resin selected from the group consisting of .
  • the support substrate layer may be a single layer or a multi-layer structure including two or more substrates made of the same or different materials, if necessary, and is not particularly limited.
  • the support substrate layer may be a substrate having a multi-layer structure of polyethylene terephthalate (PET), a substrate having a structure of two or more layers formed by coextrusion of polymethyl methacrylate (PMMA) / polycarbonate (PC).
  • PET polyethylene terephthalate
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the support substrate layer may be a substrate comprising a copolymer of polymethyl methacrylate (PMMA) and polycarbonate (PC).
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the support substrate layer may be subjected to plasma or corona surface treatment as necessary, and the method is not particularly limited.
  • the support substrate layer may have a thickness of 40 to 800 ⁇ m, or 50 to 500 ⁇ m or 100 to 200 ⁇ m.
  • the hard-coated laminate provided by the above method as well as exhibiting a high pencil hardness of 5H or more, has improved adhesion, bending resistance, external bending resistance and impact resistance.
  • the hard coating laminate may be evaluated for bending resistance or external bending resistance using a Mandrel bending test method according to a method of measurement standard JIS K5600-5-1, or a dynamic folding tester.
  • the bending resistance means that the hard coating surface is folded inward
  • the outer bending resistance means folding the support substrate layer inward.
  • folding and unfolding after setting a certain diameter value, folding and unfolding (angles 90 degrees-180 degrees) can be repeated to check whether cracks are present and to evaluate flexibility.
  • the mandrel flexure test method according to the method of the measurement standard JIS K5600-5-1, or the dynamic folding tester is excellent in both internal and external flexural properties and external flexural properties. Can show improved results.
  • the hard coating laminate of the present invention may be formed using a hard coating composition comprising an elastomer in addition to a siloxane resin of a specific structure comprising at least 70 mol% or more of glycidyl groups in the structure. Accordingly, the present invention provides a hard coating layered product having high pencil hardness of 5H or more, and having excellent adhesiveness, bending resistance, outer bending resistance, and impact resistance while being capable of coating one or more layers on one side of the supporting substrate layer, and exhibiting high pencil hardness of 5H or more. It works. Therefore, the hard coating laminate of the present invention can be effectively used in the front portion of the foldable display material, the display portion, etc., thereby contributing to the improvement of device performance.
  • glycidoxypropyl modified silicone (hereinafter referred to as glycidoxypropyl modified silicone).
  • TMAH trimethylammonium hydroxide
  • glycidoxypropyl modified silicone (hereinafter referred to as glycidoxypropyl modified silicone).
  • TMAH trimethylammonium hydroxide
  • glycidoxypropyl modified silicone (hereinafter referred to as glycidoxypropyl modified silicone).
  • TMAH trimethylammonium hydroxide
  • R 1 is a glycidoxypropyl group
  • Ra is -R b OR c-
  • R b is a propylene group
  • R c is a methylene group
  • R is a hydrogen atom
  • a 0.94
  • a basic catalyst (ammonia) was added to 1 part by weight of 100 parts by weight of the silane monomer and reacted at 100 ° C. for 2 hours to prepare a siloxane resin having the following composition (Mw: 3000 g / mol, Epoxy group equivalent: 5.9 mmol / g).
  • R 1 is a glycidoxypropyl group
  • Ra is -R b OR c-
  • R b is a propylene group
  • R c is a methylene group
  • R 2 is 2- ( 3,4-epoxycyclohexyl) ethyl group)
  • a basic catalyst (ammonia) was added to 1 part by weight of 100 parts by weight of the silane monomer, and reacted at 100 ° C for 2 hours to prepare a siloxane resin having the following composition (Mw: 3000 g / mol). , Epoxy group equivalent: 4.5 mmol / g).
  • R 1 is a glycidoxypropyl group
  • Ra is -R b OR c-
  • R b is a propylene group
  • R c is a methylene group
  • R 2 is a phenyl group
  • R is a hydrogen atom or a methyl group
  • a basic catalyst (ammonia) was added to 1 part by weight of 100 parts by weight of the silane monomer, and reacted at 100 ° C for 2 hours to prepare a siloxane resin having the following composition (Mw: 3000 g / mol). , Epoxy group equivalent: 5.8 mmol / g).
  • R 1 is a glycidoxypropyl group
  • Ra is -R b OR c-
  • R b is a propylene group
  • R c is a methylene group
  • R 2 is a phenyl group
  • R is a hydrogen atom
  • a basic catalyst trimethylammonium hydroxide (TMAH) was added to 1 part by weight of 100 parts by weight of the silane monomer and reacted at 100 ° C. for 6 hours, resulting in glycidoxypropyl modified silicone, GP)
  • TMAH trimethylammonium hydroxide
  • a siloxane resin having the following composition containing 100 mol% was prepared (Mw: 50,000 g / mol, epoxy group equivalent: 6.0 mmol / g).
  • R 1 is a glycidoxypropyl group
  • Ra is -R b OR c-
  • R b is a propylene group
  • R c is a methylene group
  • R is a hydrogen atom
  • Hard coating compositions of Examples 1 to 8 were prepared using 100 parts by weight of the siloxane resins of Preparation Examples 1 to 5, an elastomer (polycaprolactone diol, Mn 530, Sigma Aldrich), an initiator, and an organic solvent. At this time, Irgacure-250 (BASF) was used as an initiator.
  • Each hard coating composition was applied only to one side of a PET substrate having a thickness of 15 cm to 20 cm and a thickness of 188 ⁇ m.
  • a hard coating laminate including a hard coating layer having a coating thickness of 80 ⁇ m or 50 ⁇ m or 150 ⁇ m was prepared by photocuring using a UV lamp (irradiation amount: 1000 mJ / cm 2).
  • a hard coating laminate was prepared in the same manner as in Example 1, except that the content of the elastomer in the hard coating composition was changed to 10 parts by weight.
  • a hard coating laminate was prepared in the same manner as in Example 1, except that the content of the elastomer in the hard coating composition was changed to 100 parts by weight.
  • a hard coating laminate was manufactured in the same manner as in Example 1, except that the thickness of the hard coating layer was 30 ⁇ m.
  • the inner radius of curvature (R) of the folded portion was measured, and the smallest radius of curvature (R) without cracking was determined.
  • the impact resistance of the hard coating laminate was measured by a method using a ball drop (SUS ball 22g).
  • Examples 1 to 8 specifically include the siloxane resin of Formula 2 and the elastic polymer containing glycidoxy containing at least 70 mol% of the repeating unit of Formula 1 in at least 70 mol% of the total siloxane resin. Including a specific ratio range, as well as exhibiting a hardness equal to or greater than that of Comparative Examples 1 to 7, the flexural resistance, the external flexural resistance, and the impact resistance were all excellent.
  • the above embodiments can be usefully applied to a foldable display material because cracks do not occur in bending tests of bending resistance and bending resistance.

Landscapes

  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un stratifié à revêtement dur comprenant : une couche de base de support comprenant une résine thermoplastique ; et une couche de revêtement dur comprenant un produit durci d'une composition de résine comprenant un polymère élastique et une résine de siloxane ayant une structure de silicone modifiée par du glycidoxypropyle prédéterminée, la couche de revêtement dur ayant une épaisseur de 50-240 µm, le stratifié revêtu dur ayant une excellente flexibilité interne et externe.
PCT/KR2019/014201 2018-10-31 2019-10-25 Stratifié à revêtement dur Ceased WO2020091321A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201980032322.5A CN112118961B (zh) 2018-10-31 2019-10-25 硬涂层层合体
EP19879995.9A EP3778224B1 (fr) 2018-10-31 2019-10-25 Stratifié à revêtement dur
US16/973,339 US12151456B2 (en) 2018-10-31 2019-10-25 Hard coating laminate
JP2020560436A JP7060202B2 (ja) 2018-10-31 2019-10-25 ハードコーティング積層体

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2018-0132342 2018-10-31
KR20180132342 2018-10-31
KR1020190131740A KR102147481B1 (ko) 2018-10-31 2019-10-22 하드 코팅 적층체
KR10-2019-0131740 2019-10-22

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WO2020091321A1 true WO2020091321A1 (fr) 2020-05-07

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022537795A (ja) * 2019-09-25 2022-08-30 エルジー・ケム・リミテッド 光学積層体およびこれを含むフレキシブルディスプレイ装置
KR102921256B1 (ko) 2020-06-03 2026-02-03 주식회사 엘지화학 적층체

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150068240A (ko) * 2013-12-11 2015-06-19 한국과학기술원 에폭시 실록산 수지 조성물을 이용한 하드코팅막 및 이의 제조 방법
KR20160115612A (ko) * 2015-03-27 2016-10-06 동우 화인켐 주식회사 하드코팅층 형성용 조성물
KR20170000065A (ko) * 2015-06-22 2017-01-02 삼성에스디아이 주식회사 윈도우 필름용 조성물, 이로부터 형성된 플렉시블 윈도우 필름 및 이를 포함하는 플렉시블 디스플레이 장치
KR20180019115A (ko) * 2015-06-17 2018-02-23 주식회사 다이셀 경화성 조성물 및 성형체
KR20180019117A (ko) * 2015-06-17 2018-02-23 주식회사 다이셀 흠집 회복 필름

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150068240A (ko) * 2013-12-11 2015-06-19 한국과학기술원 에폭시 실록산 수지 조성물을 이용한 하드코팅막 및 이의 제조 방법
KR20160115612A (ko) * 2015-03-27 2016-10-06 동우 화인켐 주식회사 하드코팅층 형성용 조성물
KR20180019115A (ko) * 2015-06-17 2018-02-23 주식회사 다이셀 경화성 조성물 및 성형체
KR20180019117A (ko) * 2015-06-17 2018-02-23 주식회사 다이셀 흠집 회복 필름
KR20170000065A (ko) * 2015-06-22 2017-01-02 삼성에스디아이 주식회사 윈도우 필름용 조성물, 이로부터 형성된 플렉시블 윈도우 필름 및 이를 포함하는 플렉시블 디스플레이 장치

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3778224A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022537795A (ja) * 2019-09-25 2022-08-30 エルジー・ケム・リミテッド 光学積層体およびこれを含むフレキシブルディスプレイ装置
JP7287599B2 (ja) 2019-09-25 2023-06-06 エルジー・ケム・リミテッド 光学積層体およびこれを含むフレキシブルディスプレイ装置
US12060496B2 (en) 2019-09-25 2024-08-13 Lg Chem, Ltd. Optical laminate and flexible display device including the same
KR102921256B1 (ko) 2020-06-03 2026-02-03 주식회사 엘지화학 적층체

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