WO2011099778A2 - 하드코팅 형성용 수지 조성물 - Google Patents
하드코팅 형성용 수지 조성물 Download PDFInfo
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- WO2011099778A2 WO2011099778A2 PCT/KR2011/000878 KR2011000878W WO2011099778A2 WO 2011099778 A2 WO2011099778 A2 WO 2011099778A2 KR 2011000878 W KR2011000878 W KR 2011000878W WO 2011099778 A2 WO2011099778 A2 WO 2011099778A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- G02B1/105—
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Definitions
- the present invention relates to a hard coat forming resin composition, a hard coat forming sheet and a hard coat forming method.
- hard coatings sometimes referred to as protective layers
- various methods are used to form hard coatings (sometimes referred to as protective layers) that are excellent in wear resistance, chemical resistance, and the like on various molded articles such as resin molded articles or woodwork molded articles.
- molded articles such as resin molded articles or woodwork molded articles.
- seat a "transfer material”
- the coating layer was formed with the photocurable resin composition on the release surface of the base material which has mold release property.
- the coating layer is first attached to the surface of the molded article, and then the substrate is peeled off to form a hard coat.
- a sheet in which the coating layer is formed on a substrate having no releasability and an adhesive layer or the like is formed on the opposite side of the substrate as necessary (hereinafter referred to as a "surface protective sheet").
- the hard-coating is formed by sticking the base material side of a surface protection sheet to the surface of a molded article.
- a layer having a decorative effect such as a design layer or a vapor deposition layer may be formed at an appropriate location as necessary.
- a pattern layer or a deposition layer is mainly formed between the substrate and the coating layer, and in the case of a surface protective sheet, a pattern layer, a deposition layer, or the like is generally formed on the opposite surface on which the coating layer is formed on the substrate.
- the coating layer is left uncured, and after the coating layer is adhered to the molded article surface, a method of curing it (after cure method) is mainly used.
- a method of curing it (after cure method) is mainly used.
- the following problems occur in the post-curing method.
- the transfer material or surface protective sheet is manufactured using a device such as a gravure rotoprinter.
- a device such as a gravure rotoprinter.
- the post-curing method for example, in the process of manufacturing the transfer material, in the case of forming a pattern layer, a deposition layer, or an adhesive layer on the coating layer, or in the process of manufacturing the surface protective sheet, the sheet is wound, etc.
- the phenomenon that the component of the coating layer is transferred to the guide roll or the like, or the component used for forming the pattern layer or the adhesive layer is transferred onto the coating layer.
- a phenomenon so-called back trap phenomenon in which the components of the coating layer are retransmitted rather than the guide roll for forming the pattern layer or the adhesive layer also occurs.
- a special equipment is used or a coating layer is formed through a separate process such as a drying process.
- the coating layer, the design layer, or the adhesive layer cannot be formed in one step, and the cost of designing a separate equipment, etc., is high, so that the productivity of the transfer material or the surface protective sheet is reduced, and the manufacturing cost is reduced. It will rise greatly.
- An object of the present invention is to provide a resin composition for forming a hard coat, a sheet for forming a hard coat, and a hard coat forming method.
- the present invention relates to a resin composition for hard coating formation, comprising a resin having an epoxy group and a (meth) acryloyl group and a thiol-based curing agent.
- the term “hard coating” refers to a high hardness functional layer capable of imparting physical properties such as abrasion resistance, scratch resistance, scratch resistance and chemical resistance to the surface of various molded articles such as resin, woodworking, metal or composite molded articles. In some cases, it may mean a functional layer applied to various display devices. In the present invention, the term “hard coating” may be used in the same sense as the protective layer in some cases.
- the composition of this invention contains resin which has an epoxy group and a (meth) acryloyl group.
- the term "(meth) acryloyl group”, “(meth) acrylate”, or “(meth) acrylic acid” is acryloyl group or methacryloyl group; Acrylates or methacrylates; Or acrylic acid or methacrylic acid.
- epoxy equivalent weight (g / eq) used in the present invention means a numerical value obtained by dividing the molecular weight of an epoxy group by the number of epoxy groups contained in the resin. Such epoxy equivalents can be analyzed by various chemical titration methods known in the art.
- thermosetting efficiency thermosetting efficiency
- adhesiveness or adhesiveness is appropriately suppressed after thermosetting, and excellent in physical properties such as solvent resistance and chemical resistance.
- a resin layer can be provided.
- the resin may also have a (meth) acryloyl equivalent of about 100 g / eq to 1,000 g / eq, preferably about 200 g / eq to 500 g / eq.
- (meth) acryloyl equivalent weight (g / eq) used in the present invention refers to a (meth) acryloyl group in which the molecular weight of the (meth) acryloyl group is contained in the resin.
- the number divided by In the present invention, such (meth) acryloyl equivalents can be analyzed by various chemical titration methods known in the art.
- the present invention by controlling the (meth) acryloyl equivalent of the resin in the above-described range, it is excellent in process efficiency such as photocuring efficiency, and provides a hard coating having excellent physical properties such as wear resistance, abrasion resistance and chemical resistance after curing. can do.
- the resin comprising an epoxy group and a (meth) acryloyl group may also have a weight average molecular weight of about 5,000 to 100,000, preferably about 10,000 to 80,000, more preferably about 20,000 to 70,000.
- weight average molecular weight (Mw) means a polystyrene conversion value measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the method for producing such a resin is not particularly limited.
- the monomer mixture containing the monomer (for example, glycidyl (meth) acrylate) which has an epoxy group is polymerized, for example, the polymer which has an epoxy group is manufactured, and a (meth) acryloyl group is mentioned to the said polymer.
- Compounds having, for example, ⁇ , ⁇ -unsaturated monocarboxylic acids (ex. (Meth) acrylic acid, etc.) may be added to react to prepare resins as described above.
- the monomer mixture may comprise glycidyl (meth) acrylate alone or, if necessary, include glycidyl (meth) acrylate and other comonomers.
- the type of comonomer which can be included in the monomer mixture in the above is not particularly limited as long as it contains an ⁇ , ⁇ -unsaturated carbon carbon double bond in its molecular structure.
- alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms; Styrene; Vinyl acetate or (meth) acrylonitrile and the like can be used, but are not limited thereto.
- the monomer mixture in the present invention includes glycidyl (meth) acrylate and comonomer
- the ratio of each monomer is not particularly limited, and may be appropriately adjusted in consideration of the desired effect.
- the monomer mixture may include 5 parts by weight to 70 parts by weight of glycidyl (meth) acrylate and 5 parts by weight to 70 parts by weight of comonomer.
- the method of preparing the polymerized product by polymerizing such monomer mixture is not particularly limited, and without limitation to general polymerization methods in this field such as, for example, solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization. Applicable
- the polymer formed as described above is reacted with a compound having a (meth) acryloyl group, for example, ⁇ , ⁇ -unsaturated monocarboxylic acid (ex. A resin as can be prepared.
- a compound having a (meth) acryloyl group for example, ⁇ , ⁇ -unsaturated monocarboxylic acid
- the method, conditions, etc. which make addition reaction of the said polymer and a compound are not restrict
- the amount of the (meth) acryloyl group-containing compound applied to the addition reaction in the present invention is not particularly limited, and is suitably within the range in which the aforementioned epoxy equivalents and (meth) acryloyl equivalents can be satisfied. Can be selected.
- the reaction equivalent of ⁇ , ⁇ -unsaturated monocarboxylic acid is 100% based on the amount of the monomer having an epoxy group participating in the reaction, the remaining amount of the epoxy group included in the polymer during the addition reaction , About 50% or less, preferably about 30% or less, more preferably about 5% or less.
- the resin composition of this invention contains a thiol type hardening
- thiol-based curing agent refers to a thiol group capable of reacting with a carbon-carbon double bond of an epoxy group or a compound included in the composition contained in the above-described resin and primarily thermally curing the resin composition.
- the above-mentioned means a compound.
- the kind of thiol-based curing agent that can be used in the present invention is not particularly limited as long as it has at least one thiol group, preferably at least two thiol groups in the molecular structure.
- ethoxylated trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropane) as the thiol-based curing agent Cypionate)) (trimethylolpropane tris (3-mercaptopropionate)), glycol di (3-mercaptopropionate) (glycol di (3-mercaptopropionate)), pentaerythritol tetrakis (3-mercaptopropionate) (pentaerythritol tetrakis (3-mercapto-propionate)), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (4-mercaptomethyl-3,6-dithia-1,8-octanedithiol), Pentaerythritol tetrakis (3-mercaptoacetate), trimethylolpropane tris (3-mercaptoacetate), trimethylol
- curing agent represented by following formula (1) can be used.
- R 1 to R 4 each independently represent a hydrogen, alkyl, alkoxy, alkenyl, alkynyl or thiol-containing group, at least two, preferably at least three of R 1 to R 4 contain a thiol Group.
- alkyl or “alkoxy” refers to a straight or branched chain having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms; Or cyclic or acyclic alkyl or alkoxy, and such alkyl or alkoxy may be optionally substituted by one or more substituents.
- alkenyl or “alkynyl” used herein refers to a straight or branched chain having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms; Or cyclic or acyclic alkenyl or alkynyl, and such alkenyl or alkynyl may be optionally substituted with one or more substituents.
- examples of the substituent which may be substituted by alkyl, alkoxy, alkenyl or alkynyl, etc. include all substituents generally applied in the chemical field, and specifically, thiol, amine, amide, halogen , Hydroxy, carboxy, glycidyl, cyano, nitro, heterocycloalkyl or aryl, and the like.
- the type of thiol-containing group is not particularly limited as long as it is a monovalent moiety having a thiol group (-SH) at the terminal of the substituent structure.
- the thiol-containing group for example, may be a monovalent residue represented by the formula (2).
- A is a single bond or alkylene
- C is a single bond or alkylene
- D is a single bond or a divalent residue of the formula (3), wherein E represents alkylene.
- P represents divalent aryl
- n represents an integer of 0 to 10.
- the term "single bond” means a case where no other atom is present at the position of A, C or D.
- the thiol containing group is represented by -BCD-SH
- C is a single bond
- the thiol containing group is represented by -ABD-SH
- D is a single bond
- the thiol containing It may mean that the group is represented by -ABC-SH.
- alkylene is a straight or branched chain having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms; Or it may mean a cyclic or acyclic alkylene, such alkylene may be optionally substituted by one or more substituents.
- bivalent aryl means a bivalent moiety derived from an aromatic ring compound or including the compound in a skeleton, and specifically, 6 to 22 or 6 members. Or a divalent moiety derived from or including in the skeleton of an 18 to 18, 6 to 14 or 6 to 10 membered aromatic ring compound, wherein such aryl is optionally substituted by one or more substituents. It may be substituted.
- n may preferably represent 0 to 7, more preferably 0 to 5, and more preferably 0 to 3.
- R 1 to R 4 are each independently hydrogen, alkyl having 1 to 4 carbon atoms or -ABCD-SH, more preferably, each independently hydrogen, Methyl, ethyl or -ABCD-SH.
- R 1 to R 4 may be -ABCD-SH, wherein A is preferably a single bond or 1 to 4 carbon atoms.
- A is preferably a single bond or 1 to 4 carbon atoms.
- C is a single bond or alkylene having 1 to 4 carbon atoms
- D is a single bond or a divalent compound of formula (4) Residue, wherein E may be alkylene having 1 to 4 carbon atoms.
- N in the formula (4) represents an integer of 0 to 10, preferably 0 to 7, more preferably 0 to 5, still more preferably 0 to 3.
- Examples of the thiol curing agent represented by the above formula include alkoxylated trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) or alkylene glycol bis (3 Mercaptopropionate) and the like, and more specifically, ethoxylated trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) or ethylene glycol Bis (3-mercaptopropionate) and the like, but are not limited thereto.
- the content of the thiol-based curing agent may be appropriately selected in consideration of the equivalent of epoxy groups contained in the resin and the desired degree of curing, and is not particularly limited.
- the resin composition of this invention can contain the said thiol type hardening
- the content ratio of the thiol-based curing agent to the resin is controlled as described above to induce an appropriate reaction with an epoxy group or a carbon-carbon double bond during thermosetting, and to appropriately suppress the expression of adhesiveness after thermosetting.
- the physical properties such as coating properties can be kept excellent.
- the resin composition of this invention can further contain a photoinitiator further.
- the kind of photoinitiator that can be used in the present invention is not particularly limited, and a general kind known in the art can be used without limitation.
- a compound such as benzoin, hydroxyketone, amino ketone or phosphine oxide can be used. More specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzo Phosphorus isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenyl Acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-die
- the photoinitiator may be included in an amount of 1 part by weight to 15 parts by weight, preferably 3 parts by weight to 12 parts by weight, and more preferably 5 parts by weight to 10 parts by weight, based on 100 parts by weight of the aforementioned resin. have.
- the content of the photoinitiator in the above range, it is possible to maintain excellent photocuring efficiency of the composition, and to prevent a decrease in physical properties due to the remaining components after curing.
- the resin composition of this invention can also contain polyfunctional acrylate further. Since the resin composition of the present invention contains a polyfunctional acrylate, the hard coating after the photocuring implements a dense crosslinked structure, thereby improving physical properties such as hardness, abrasion resistance, scratch resistance and chemical resistance of the hard coating. have.
- the kind of the multifunctional acrylate in the present invention is not particularly limited, and for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl promisvalic acid neopentylglycol di (meth) acrylate, dicyclo Pentanyl (dicyclopentanyl) di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allyl ( allyl) cyclohexyl di (meth) acrylate, tricyclodecanedimethanol
- the multifunctional acrylate it is preferable to use an acrylate including a cyclic structure and / or a urethane bond in the molecular structure.
- the ring structure included in the acrylate may be a carbocyclic structure or a heterocyclic structure; Or any of a monocyclic or polycyclic structure.
- examples of the ring structure included in the multifunctional acrylate include a cycloalkyl ring structure having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, such as cyclopentane, cyclohexane, or cycloheptane.
- One or more ring structures may be included in the acrylate, preferably 1 to 5, more preferably 1 to 3, and one or more hetero atoms such as O, S or N may also be included.
- the monomer which has isocyanurate structures such as a tris (meth) acryloxy ethyl isocyanurate, isocyanurate Of modified urethane acrylates (e.g., isocyanate compounds having a ring structure in a molecule (ex. Isoborone diisocyanate) and acrylate compounds (e.g. trimethylolpropane tri (meth) acrylate or pentaerythritol tri (meth) acrylate) Reactants, etc.), but is not limited thereto.
- modified urethane acrylates e.g., isocyanate compounds having a ring structure in a molecule (ex. Isoborone diisocyanate) and acrylate compounds (e.g. trimethylolpropane tri (meth) acrylate or pentaerythritol tri (meth) acrylate) Reactants, etc.
- the multifunctional acrylate may be included in an amount of 30 parts by weight or less, preferably 5 parts by weight to 15 parts by weight, based on 100 parts by weight of the resin described above.
- the content of the multifunctional acrylate in the above-described range, it is possible to provide a coating layer having physical properties such as hardness, hard coating is more excellent.
- the resin composition of this invention can further contain antioxidant, and can suppress yellowing phenomenon etc. which may arise in a coating layer by this.
- the kind of antioxidant which can be used by this invention is not specifically limited, The common antioxidant known in this field can be used.
- phenolic antioxidants ex. IRGANOX; RONOTEC; ETANOX
- phosphorus antioxidants ex. CYANOX; ULTRANOX
- chelate antioxidants IGAFOS
- the content of the antioxidant is not particularly limited and may be appropriately selected in consideration of the physical properties of the coating layer.
- the resin composition of the present invention may include, for example, 0.1 parts by weight to 2 parts by weight of the antioxidant based on 100 parts by weight of the aforementioned resin.
- the resin composition of the present invention may further include a lubricant.
- the lubricant can improve the winding efficiency, blocking resistance, abrasion resistance, and scratch resistance of the coating layer formed from the resin composition.
- the type of lubricant used in the present invention is not particularly limited, and examples thereof include waxes such as polyethylene wax, paraffin wax, synthetic wax or montan wax; Synthetic resins, such as silicone resin or fluorine resin, can be used.
- the content of the lubricant in the resin composition of the present invention is not particularly limited, and may be, for example, 0.5 parts by weight to 15 parts by weight, preferably 1 part by weight to 6 parts by weight, based on 100 parts by weight of the aforementioned resin. By controlling the content of the lubricant in the above range, it is possible to provide excellent blocking resistance, friction resistance and scratch resistance to the coating layer, while maintaining excellent transparency.
- the resin composition of the present invention may further contain an ultraviolet absorbent in an appropriate amount for the purpose of improving light resistance.
- ultraviolet absorbers examples include hydroxyphenyl benzotriazole, hydroxyphenyl-S-triazine or 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzo Triazoles, and the like, but is not limited thereto.
- the ultraviolet absorber is included in the present invention, the content thereof is not particularly limited and may be appropriately selected in consideration of desired physical properties.
- thermosetting catalyst such as DMAP (dimethylaminopyridine) or the like, nano silica, etc. It may further include a filler component or an isocyanate compound.
- the invention is also described; And a coating layer formed on the base material and having a coating layer containing a thermoset of the resin composition of the present invention.
- the sheet for forming a hard coat of the present invention may be a transfer material or a surface protective sheet or the like, which forms a hard coat on the surfaces of various molded articles in various ways.
- the hard coat forming sheet 1 of the present invention may include a substrate 11 and a coating layer 12 formed on one surface of the substrate. If necessary, the sheet 1 of the present invention may further include a layer formed on the coating layer 12 or on the opposite side of the coating layer 12 of the substrate 11.
- the type of the additional layer includes a layer known in the art such as a design layer, a deposition layer or an adhesive layer.
- the expression "B formed on A”, “B formed on the top of A”, or “B formed on the surface of A”, or the like means that B is directly attached to the surface of A, or an adhesive or an adhesive is used.
- the other layer is formed in the surface of A, and also the case where B is formed in the surface of the other layer (ex. ACB) is included.
- the coating layer may be of a photocuring type containing the above-mentioned thermosetting of the resin composition of the present invention as an active ingredient.
- thermosetting of the resin composition means a state in which the epoxy group and the thiol group of the thiol curing agent contained in the resin form an addition reactant via a ring-opening addition reaction or the like.
- the term "photocuring type” means a state in which a curing reaction by a reaction such as a (meth) acryloyl group included in the resin may proceed when the electromagnetic wave is irradiated, in which case the electromagnetic wave is microwave (microwaves), infrared (IR), ultraviolet (UV), X-rays and gamma rays ( ⁇ -rays), as well as ⁇ -particle beams, proton beams, neutron beams and It is used generically to refer to a particle beam such as an electron beam.
- the coating layer of the present invention as described above, for example, by treating the resin composition containing each component described above under appropriate conditions, the epoxy group of the resin in the composition and the thiol group of the thiol-based curing agent reacts to form an addition reactant
- the composition comprising the addition reactant may be formed by coating on a substrate in a suitable manner.
- the conditions for forming the addition reactant are not particularly limited, and appropriate reaction conditions may be set in consideration of the content or type of the epoxy group or the thiol group included in the resin or the curing agent.
- the resin composition may be blended and treated for about 30 seconds to 2 minutes at about 100 ° C to 170 ° C to form the addition reactant.
- a coating layer in the form as described above by forming a coating layer in the form as described above, it is possible to form a coating layer having no adhesiveness even without performing a separate drying process. Accordingly, in the present invention, without using a special equipment for the formation of the coating layer, or performing a separate drying process, other layers such as a design layer, a deposition layer or an adhesive layer, or hard coating on the coating layer further It is possible to wind up the sheet
- the thickness of the coating layer is not particularly limited, and may be set to an appropriate thickness in consideration of the desired physical properties.
- the kind of base material which can be used by this invention is not specifically limited.
- a resin film mainly composed of polypropylene resin, polyethylene resin, polyamide resin, polyester resin, polyacrylic resin, or polyvinyl chloride resin; Cellulose sheets such as metal foil such as aluminum foil or copper foil, glassine paper, coated paper or cellophane; Or a composite sheet of two or more of the above can be used as the substrate.
- the sheet for forming a hard coat of the present invention is composed of a surface protective sheet
- the base material does not have releasability, and may be an acrylic resin, a polycarbonate resin, a vinyl chloride resin, a urethane resin, or a polyester.
- the resin sheet mainly containing system resin etc. can also be used.
- the thickness of the substrate in the present invention is also not particularly limited and may be appropriately selected depending on the intended use.
- a release treatment may be performed on one or both surfaces of the substrate, and the coating layer may be formed on the release treatment surface.
- the manner of forming the release layer is not particularly limited.
- epoxy, epoxy-melamine, aminoalkyd, acrylic, melamine, silicone, fluorine, cellulose, urea resin, polyolefin, paraffin It can be formed using various printing methods, coating methods, etc. using the system or 2 or more types of complex mold release agents.
- the said base material or a release surface can also be comprised in a matte state as needed.
- the matte state can be formed by embossing or by including fine powders such as calcium carbonate, silica, zinc oxide, magnesium carbonate, polyethylene wax or glass beads in the release layer. have.
- corrugation formed in the release surface is transferred to the surface of a coating layer, and the molded article which has a matte surface can be obtained.
- the matt state as described above may be formed entirely on the substrate or the release layer or partially formed.
- the material containing the fine powder of the same material as what is used for formation of the above-mentioned release layer can be used.
- the thickness of the release layer or the matte layer is not particularly limited, and may be set to an appropriate thickness as necessary.
- the hard coat forming sheets 2 and 3 of the present invention further include adhesive layers 21 and 31 formed on top of the coating layer 12 or on the base 11. It can be included as.
- Such adhesive layers 21 and 31 may be used, for example, when the hard coating-forming sheet 2 of the present invention is used as a transfer material or a surface protective sheet, to provide adhesion to molded articles. .
- the adhesive layers 21 and 31 as described above can be formed using various thermosensitive or pressure-sensitive resins known in the art.
- the adherend to which the adhesive layers 21 and 31 adhere for example, in polyacrylic resin, polystyrene resin, polyamide resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, rubber resin or the like.
- the adhesive layers 21 and 31 may be formed of appropriate components.
- the adhesive layers 21 and 31 formed on the layers 41 and 51 may be included.
- the method for forming the pattern layers 41 and 51 as described above is not particularly limited.
- the pattern layer can be formed by using a resin of the above as a binder and using a coloring ink containing a pigment or a dye of a suitable color.
- the formation method and the thickness of the pattern layer as described above are not particularly limited, and means known in the art may be appropriately employed.
- the hard coating-forming sheets 6 and 7 may further include deposition layers 61 and 71 formed on the design layers 41 and 51.
- deposition layers 61 and 71 may be directly formed on the coating layer 12 or the substrate 11 without the design layers 41 and 51.
- the material for forming the deposition layer and its formation method are not particularly limited, and the deposition layer may be formed by a general method using a material generally used in this field, for example, vacuum deposition or sputtering. It can be formed.
- one or more anchor layers may be provided at appropriate locations between the above-described layers.
- the anchor layer as described above may play a role of increasing the adhesion between the layers of the hard coat forming sheet and protecting the molded article and the pattern layer from chemicals and the like.
- the anchor layer as described above can be formed by using conventional means using, for example, a thermosetting resin such as a conventional two-component urethane resin, melamine-based or epoxy-based resin, or a thermoplastic resin such as vinyl chloride copolymer resin. .
- the present invention also relates to a method for forming a hard coat in which a hard coat is formed on the surface of a molded article using the sheet for forming a hard coat of the present invention described above.
- the method of forming the hard coating may include various steps according to the shape of the sheet for forming the hard coating.
- the method includes: adhering the coating layer of the hard coat forming sheet or the adhesive layer formed on the coating layer to the surface of a molded article; Peeling the substrate; And photocuring the coating layer through light irradiation.
- the transfer material may also be used to produce a molded article through injection molding, and at the same time, a hard coat may be formed on the surface thereof.
- the method may include, for example, when the adhesive layer is formed on the coating layer or the coating layer of the hard coat forming sheet, installing the adhesive layer inward and installing the mold in the molding die; Injecting molten resin into a cavity in the mold; Peeling the substrate from the sheet; And photocuring the coating layer through light irradiation.
- the method of the present invention further comprises the steps of: arranging a sheet for forming a hard coat on the substrate side or when the adhesive layer is formed on the substrate when the sheet is composed of a surface protective sheet, the adhesive layer facing the surface of the molded article; Heating the sheet to soften the substrate; Vacuum sucking the sheet from below and adhering to the surface of the molded article; And photocuring the coating layer through light irradiation.
- a hard coat may be formed on the surface of the molded article through injection molding using the surface protective sheet.
- the method includes, for example, when the adhesive layer is formed on the base material or the base material of the hard coat forming sheet, the step of installing the adhesive layer inwards and forming in the molding die; Injecting molten resin into a cavity in the mold; And photocuring the coating layer through light irradiation.
- the order is not particularly limited.
- the substrate may be first peeled off, and light may be irradiated to perform photocuring.
- a process of first curing the coating layer using a light-transmissive substrate as the substrate and then peeling the substrate may be performed.
- FIG. 8 is a view schematically showing a transfer method according to one example of the present invention, the method shown in Figure 8 is, for example, the sheet of the present invention is a transfer material (for example, 2, 4 or 6), but may be usefully applied, but is not limited thereto.
- a transfer material for example, 2, 4 or 6
- the coating layer 12 side of the sheet for hard coating forming (not shown in the drawing, when the adhesive layer or the like is formed on the coating layer 12, the lower side of the adhesive layer), It is arrange
- a heat transfer rubber-like elastic body 82 for example, a transfer machine such as a roll transfer machine equipped with silicon rubber or the like, an up-down transfer machine, a temperature of about 80 ° C to 260 ° C and a pressure of about 50 Kg / m 2 Under conditions of about 200 Kg / m 2 , heat and / or pressure are applied to the substrate 11 side of the sheet via the heat-resistant rubbery elastic body 82.
- the coating layer 12 or the adhesive layer is adhered to the surface of the molded article 81. Subsequently, if the base material 11 is peeled off after passing through a cooling process suitably as needed, peeling will arise in the interface surface of the base material 11 and the coating layer 12. Thereafter, the coating layer 12 transferred to the molded article 81 is photocured through light irradiation or the like. As described above, the photocuring process may be performed before peeling off the substrate 11.
- the conditions of light irradiation are not particularly limited in the above, and may be appropriately controlled in consideration of the composition of the coating layer used.
- the material of the molded article is not particularly limited.
- the molded article may be a resin molded article, a woodworking product, a metal product, a composite product of two or more of the above, or any kind of molded article requiring hard coating.
- resin of a resin molded article general-purpose resin, such as polystyrene resin, polyolefin resin, ABS resin, AS resin, or AN resin, is mentioned above.
- polysulfone resins polysulfone resins, polyphenylene sulfide resins, polyphenylene oxide resins, polyacrylate resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, and polyaryl heat-resistant resins.
- Engineering resins can also be used.
- the composite resin which added reinforcing materials such as glass fiber and an inorganic filler, can also be used.
- FIG. 9 is a diagram showing a transfer method according to another example of the present invention, which is a schematic diagram showing a method of transferring a coating layer to the surface of a molded article using a simultaneous molding method of injection molding.
- a sheet for forming a hard coat in a molding die including a movable mold 91 and a fixed mold 92 is formed on the coating layer 12 side (not shown in the drawing, but an adhesive layer or the like is formed on the coating layer).
- the adhesive layer side is set to the inside, and the sheet is provided so that the base material 11 is in contact with the fixing die 92.
- molten resin is injected into the mold 93 from the gate formed in the movable mold 91 to form a molded article, and at the same time, a coating layer is adhered to the molded article surface.
- the coating layer may be cured through light irradiation before or after peeling off the substrate 11 to form a hard coating.
- FIG. 10 is a schematic diagram showing a method of forming a hard coat that may be usefully applied when the hard coat forming sheet of the present invention is configured as a surface protective sheet.
- the molded article 101 is made with the hard coating-forming sheet on the base 11 side (not shown in the drawing, but when the adhesive layer or the like is formed on the base 11) as the bottom. Place on the surface of).
- the sheet is heated by the heater 103 or the like to soften the substrate 11, vacuum suction 102 from the lower side, and the sheet is attached to the molded product 101. Thereafter, by hardening the coating layer through light irradiation, a hard coating can be formed.
- the heating and vacuum suction process of the sheet may be simultaneously performed, or the vacuum efficiency may be simultaneously applied from the bottom and pressurized from the top to increase the adhesion efficiency.
- the pressing of the hard coat forming sheet may be performed directly using a fluid or the like, or may be performed through a plastic sheet.
- FIG. 11 is a schematic diagram showing another method of forming a hard coat when the sheet for hard coat formation is composed of a surface protective sheet, and showing a method of forming a hard coat simultaneously with molding by injection molding.
- a sheet for forming a hard coat is provided in the forming die including the movable die 112 and the stationary die 111 so that the coating layer 12 contacts the stationary die 111.
- molten resin is injected 113 from the gate provided in the movable metal mold 112, and a molded article is shape
- the hard coating can be formed by passing the cooling step of the molded article and the like, opening the mold, taking out the molded article, and curing the coating layer through light irradiation or the like.
- the method of forming the hard coating of the present invention in addition to the above-described method, it is possible to form a hard coating through a variety of methods known in the art.
- the present invention it is possible to provide a composition which is excellent in physical properties such as hardness, friction resistance, scratch resistance and chemical resistance, and can form a hard coat or protective layer having excellent glossiness and high refractive index.
- the composition of the present invention when applied as a transfer material or a surface protective sheet, for example, exhibits excellent adhesion with other layers such as a print layer, a deposition layer or an adhesive layer in a cured or thermoset state, and has excellent hardness and friction resistance. By exhibiting scratch resistance and chemical resistance, it is possible to effectively form a hard coating or a protective layer of excellent physical properties on the surface of various molded articles.
- 1 to 7 are cross-sectional views of sheets for forming a hard coat according to various examples of the present invention.
- FIGS. 8 to 11 are diagrams schematically showing a method of forming a hard coating according to various examples of the present invention.
- a mixture comprising 43 parts by weight of GMA, 12 parts by weight of MMA, 25 parts by weight of SM, 0.5 parts by weight of lauryl mercaptan and 1 part by weight of AIBN was added dropwise using a dropping lot over about 2 hours to the reaction apparatus under a nitrogen stream. It dripped and kept warm at the same temperature for about 3 hours. Then, 0.25 parts by weight of AIBN was added and kept warm for 2 hours. The temperature was then adjusted to about 105 ° C. and the nitrogen inlet tube was replaced with an air inlet tube, followed by 37 parts by weight of acrylic acid (AA), 0.05 parts by weight of p-methoxyphenol and dimethylaminopyridine (DMAP).
- AA acrylic acid
- DMAP dimethylaminopyridine
- ethoxylated trimethylolpropane tris (3-mercaptopropionate) as a thiol-based curing agent
- 20 parts by weight of dipentaerythritol hexaacrylate (DPHA), 1,6 5 parts by weight of hexaisocyanate trimer, 8 parts by weight of photoinitiator, 1 part by weight of antioxidant, 20 parts by weight of nano silica and 70 parts by weight of methyl ethyl ketone were mixed to prepare a coating solution.
- a melamine-based mold release agent As a substrate, a melamine-based mold release agent was coated to a thickness of about 1 ⁇ m by a gravure coating method on one surface of a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m to form a release layer. Subsequently, the coating solution prepared on the release layer was applied to a thickness of about 6 ⁇ m by a microgravure coating method. Thereafter, the applied coating solution was heated at 150 ° C. for 30 seconds to react the epoxy group of the resin and the thiol group of the thiol-based curing agent to form a thermoset.
- PET polyethylene terephthalate
- an anchor layer (acrylic anchor layer), a pattern layer (acrylic-urethane ink), a vacuum deposition layer (acrylic resin deposition primer) and an adhesive layer (acrylic adhesive) were coated on the coating layer containing thermosetting by a microgravure printing method. Forming sequentially, a sheet for forming a hard coat was prepared.
- the sheet prepared above was subjected to the method shown in Figure 9 to form a hard coating on the surface of the molded article. Specifically, the sheet was placed so that the substrate was in contact with the fixing mold 92, the molten resin was injected, and then the hard coating was formed through the peeling and ultraviolet irradiation process of the substrate.
- the molding conditions were about 280 degreeC of resin, the mold temperature of about 60 degreeC, and the resin pressure was about 1,600 Kg / cm ⁇ 2> .
- the irradiation conditions of ultraviolet-ray were set to 1,000 w / cm, lamp height about 10 cm, and irradiation time about 3 second.
- Hard coating in the same manner as in Example 1 except for using pentaerythritol tetrakis (3-mercaptopropionate) instead of ethoxylated trimethylolpropane tris (3-mercaptopropionate) as a thiol-based curing agent A forming composition and a sheet were prepared and used to form a hard coat on the surface of the molded article.
- Example 2 Prepared in the same manner as in Example 1, by using a diisocyanate as a urethane-based curing agent instead of a thiol-based curing agent to prepare a composition and a sheet for forming a hard coating, it was used to form a hard coating on the surface of the molded article.
- compositions prepared in Examples 1 to 5 and Comparative Examples were coated on a 2 mm thick PMMA (Poly (methyl methacrylate)) substrate using a bar coating method with a thickness of 6 ⁇ m. Thereafter, the mixture was thermally cured at 160 ° C. for 40 seconds, and further irradiated with ultraviolet rays to cure (1,000 mW). Then, pencil hardness was measured in the state which the load of 1 Kg was applied using the pencil hardness tester (the coretech company make), and the Mitsubishi pencil for hardness measurement.
- PMMA Poly (methyl methacrylate)
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Comparative example Pencil hardness (H) 5 5 5.5 6 5.8 4
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Abstract
Description
실시예1 | 실시예2 | 실시예3 | 실시예4 | 실시예5 | 비교예 | |
연필경도(H) | 5 | 5 | 5.5 | 6 | 5.8 | 4 |
Claims (19)
- 에폭시기 및 (메타)아크릴로일기를 가지는 수지 및티올계 경화제를 포함하는, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 수지는 에폭시 당량이 200 g/eq 내지 20,000 g/eq인, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 수지는 (메타)아크릴로일 당량이 100 g/eq 내지 1,000 g/eq인, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 수지는 중량평균분자량이 5,000 내지 100,000인, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 티올계 경화제가 에톡시화 트리메틸롤프로판 트리스(3-머캅토프로피오네이트), 트리메틸롤프로판 트리스(3-머캅토프로피오네이트)), 글리콜 디(3-머캅토프로피오네이트), 펜타에리쓰리톨 테트라키스(3-머캅토프로피오네이트), 4-머캅토메틸-3,6-디티아-1,8-옥탄디티올, 펜타에리쓰리톨 테트라키스(3-머캅토아세테이트), 트리메틸롤프로판 트리스(3-머캅토아세테이트), 4-t-부틸-1,2-벤젠디티올, 2-머캅토에틸술피드, 4,4'-티오디벤젠티올, 벤젠디티올, 글리콜 디머캅토아세테이트, 글리콜 디머캅토프로피오네이트에틸렌 비스(3-머캅토프로피오네이트), 폴리에틸렌글리콜 디머캅토아세테이트 및 폴리에틸렌 글리콜 디(3-머캅토프로피오네이트)로 이루어진 군으로부터 선택되는 하나 이상인, 하드코팅 형성용 수지 조성물.
- 제 6 항에 있어서, R1 내지 R4는, 각각 독립적으로 수소, 탄소수 1 내지 4의 알킬 또는 -A-B-C-D-SH이고, R1 내지 R4 중 2개 이상은 -A-B-C-D-SH이며,상기에서 A는 단일 결합 또는 탄소수 1 내지 4의 알킬렌이고, B는 -OC(=O)- 또는 -O-E-OC(=O)-이며, C는 단일 결합 또는 탄소수 1 내지 4의 알킬렌이고, D는 단일 결합 또는 하기 화학식 4의 2가 잔기이며, 상기에서 E는 탄소수 1 내지 4의 알킬렌인, 하드코팅 형성용 수지 조성물:[화학식 4]상기 화학식 4에서 n은 0 내지 10의 정수를 나타낸다.
- 제 1 항에 있어서, 티올계 경화제가 수지 100 중량부에 대하여, 0.1 중량부 내지 10 중량부로 포함되는, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 광개시제를 추가로 포함하는, 하드코팅 형성용 수지 조성물.
- 제 10 항에 있어서, 광개시제는, 수지 100 중량부에 대하여, 1 중량부 내지 15 중량부로 포함되는, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 다관능성 아크릴레이트를 추가로 포함하는, 하드코팅 형성용 수지 조성물.
- 제 12 항에 있어서, 다관능성 아크릴레이트는, 수지 100 중량부에 대하여, 30 중량부 이하로 포함되는, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 산화 방지제를 추가로 포함하는, 하드코팅 형성용 수지 조성물.
- 제 14 항에 있어서, 산화 방지제가 페놀계 산화 방지제, 인계 산화 방지제 또는 킬레이트계 산화 방지제인 하드코팅 형성용 수지 조성물.
- 제 14 항에 있어서, 산화 방지제는 수지 100 중량부에 대하여 0.1 중량부 내지 2 중량부로 포함되는, 하드코팅 형성용 수지 조성물.
- 제 1 항에 있어서, 활제, 자외선 흡수제, 열경화용 촉매 또는 필러를 추가로 포함하는, 하드코팅 형성용 수지 조성물.
- 기재; 및 상기 기재상에 형성되고, 제 1 항 내지 제 17 항 중 어느 한 항에 따른 수지 조성물의 열경화물을 포함하는 코팅층을 가지는 하드코팅 형성용 시트.
- 제 18 항에 따른 하드코팅 형성용 시트를 사용하여, 성형품의 표면에 하드코팅을 형성하는 단계를 포함하는 하드코팅 형성 방법.
Priority Applications (4)
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US13/395,206 US8937116B2 (en) | 2010-02-10 | 2011-02-09 | Resin composition for forming hard coating |
CN2011800036718A CN102482529A (zh) | 2010-02-10 | 2011-02-09 | 硬涂层形成用树脂组合物 |
JP2012541034A JP5602240B2 (ja) | 2010-02-10 | 2011-02-09 | ハードコーティング形成用樹脂組成物、ハードコーティング形成用シート及びその製造方法、並びにハードコーティング形成方法 |
EP11742470.5A EP2535383B1 (en) | 2010-02-10 | 2011-02-09 | Resin composite for forming hard coat layer |
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KR10-2010-0012460 | 2010-02-10 | ||
KR1020100012460A KR101585269B1 (ko) | 2010-02-10 | 2010-02-10 | 하드코팅 형성용 수지 조성물 |
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WO2011099778A3 WO2011099778A3 (ko) | 2011-12-29 |
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EP (1) | EP2535383B1 (ko) |
JP (1) | JP5602240B2 (ko) |
KR (1) | KR101585269B1 (ko) |
CN (1) | CN102482529A (ko) |
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- 2011-02-09 US US13/395,206 patent/US8937116B2/en not_active Expired - Fee Related
- 2011-02-09 EP EP11742470.5A patent/EP2535383B1/en not_active Not-in-force
- 2011-02-09 JP JP2012541034A patent/JP5602240B2/ja not_active Expired - Fee Related
- 2011-02-09 WO PCT/KR2011/000878 patent/WO2011099778A2/ko active Application Filing
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CN102443139A (zh) * | 2011-09-22 | 2012-05-09 | 福建省东协橡塑实业有限公司 | 一种聚硫醇固化剂及其制备方法 |
US8748081B2 (en) * | 2011-12-29 | 2014-06-10 | Korea Kumho Petrochemical Co., Ltd. | Organic anti reflective layer composition |
Also Published As
Publication number | Publication date |
---|---|
EP2535383A2 (en) | 2012-12-19 |
TWI438217B (zh) | 2014-05-21 |
US20120184640A1 (en) | 2012-07-19 |
CN102482529A (zh) | 2012-05-30 |
TW201130879A (en) | 2011-09-16 |
JP5602240B2 (ja) | 2014-10-08 |
WO2011099778A3 (ko) | 2011-12-29 |
JP2013512305A (ja) | 2013-04-11 |
KR20110092818A (ko) | 2011-08-18 |
KR101585269B1 (ko) | 2016-01-14 |
EP2535383B1 (en) | 2018-08-08 |
EP2535383A4 (en) | 2013-08-21 |
US8937116B2 (en) | 2015-01-20 |
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