WO2016122191A1 - Produit revêtu, et procédé de revêtement dur de surface courbée à dureté élevée - Google Patents

Produit revêtu, et procédé de revêtement dur de surface courbée à dureté élevée Download PDF

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Publication number
WO2016122191A1
WO2016122191A1 PCT/KR2016/000825 KR2016000825W WO2016122191A1 WO 2016122191 A1 WO2016122191 A1 WO 2016122191A1 KR 2016000825 W KR2016000825 W KR 2016000825W WO 2016122191 A1 WO2016122191 A1 WO 2016122191A1
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methyl
pomma
phenyl
glyp
eche
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PCT/KR2016/000825
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English (en)
Korean (ko)
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김호종
이인철
이성현
김진호
윤영민
신규순
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주식회사 동진쎄미켐
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Priority claimed from KR1020160009452A external-priority patent/KR20160092507A/ko
Publication of WO2016122191A1 publication Critical patent/WO2016122191A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a coating product and a high hardness curved hard coating method, in particular, to improve the hard coating method for the existing product having a curved surface coating to prevent problems such as cracking, peeling of the bent portion during the surface forming processing It relates to a product and a curved hard coating method.
  • Plastic, glass, or metal products have a hard coating layer formed on the surface, thereby providing excellent physical properties such as impact resistance and scratch resistance.
  • a molded article having a curved surface has a disadvantage in that when hard coating is performed after vacuum forming, roll coating is impossible or coating property is poor during flow coating.
  • a molded article having a curved surface has a problem of causing cracks in a bent portion during molding when hard coating is performed on a disc.
  • the molding of a molded article having a curved surface is hard-coated by a spray method or a dipping method after molding a non-coated disc.
  • Curved hard coating has a problem that the smoothness of the coating surface is lower than the flat surface hard coating, and the high gloss texture of the coating is reduced, and the hard coating layer is broken due to lack of elongation of the hard coating layer.
  • the present invention improves the hard coating method for the existing product having a curved surface coating product and curved hard coating method to prevent problems such as cracking, peeling of the bent portion during the surface forming process
  • the purpose is to provide.
  • the material forming the hard coating layer is a coating composition containing the silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9.
  • Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
  • Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
  • R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40
  • a and d are each independently an integer of 1 to 100,000, specifically a is 3 to 1000, d is 1 to 500, more specifically a is 5 to 300, d is 2 to 100,
  • b are each independently an integer of 1 to 500
  • e are each independently 1 or 2, specifically 1,
  • n is each independently an integer of 1 to 20, and specifically 3 to 10.
  • It has a hard coating layer in which the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 and a hot melted material are integrated on one or both surfaces of the curved product.
  • the present invention has an effect of preventing the problem of cracking, peeling, etc. of the bent portion during the surface forming process by improving the hard coating method for the existing product having a curved surface.
  • the present invention has the effect of obtaining a coating quality superior to spray and dipping coating by improving the hard coating method for the existing curved products.
  • the present invention has the effect of improving the smoothness of the curved product coating surface and forming a high gloss texture, such as flat plate hard coating.
  • the present invention can replace the coating material coated on the product having a curved surface with a new one to implement the insulation function and the adhesion function of the insulating material at the same time to slim down the thickness of the coated product, shorten the manufacturing process of the coated product, raw material cost and process This can greatly reduce the cost.
  • FIG. 1 is a flow chart briefly showing a high hardness curved hard coating method according to an embodiment of the present invention.
  • FIG. 2 is a view showing a high hardness curved hard coating method according to an embodiment of the present invention.
  • Figure 1 is a flow chart briefly showing a high hardness curved hard coating method according to an embodiment of the present invention
  • Figure 2 is a view showing a high hardness curved hard coating method according to an embodiment of the present invention.
  • High hardness curved hard coating method by applying a coating composition 110 to one surface of the base film 120 to form a hard coating layer 100 (S100), injection mold (200, 210) Attaching the hard coating layer 100 to the inside of the mold (S102), injecting the hot-melted material 211 into the injection molds 200 and 210, and performing injection molding (S104) and the injection molds 200 and 210.
  • the hard coating layer 100 of the present invention is illustrated as an example of a hard coating film, but is not limited to this, hereinafter will be described by describing the hard coating layer 100 as a hard coating film for convenience of description.
  • the coating composition 110 is prepared and the prepared coating composition 110 is applied onto the base film 120.
  • the coating composition 110 is coated on the base film 120 by spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, and saliva. It can be selected and applied arbitrarily by those skilled in the art from known methods such as paper coating, impregnation, gravure coating.
  • the base film 120 is made of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyamides (PA, nylon), Polyester (PES), polyvinyl chloride (PVC), polyurethane (PU), polycarbonate (PC), high hardness polycarbonate (PC), polyvinylidene chloride
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PET polyethylene terephthalate
  • PA nylon
  • Polyester PET
  • PVC polyvinyl chloride
  • PVC polyurethane
  • PC polycarbonate
  • PC high hardness polycarbonate
  • PC polyvinylidene chloride
  • a mixture of two or more plastic materials as well as a single plastic material such as chloride, PVDC), polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), polyetherimide (PEI), and acrylic
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene ter
  • the hard coating film 100 may be formed by applying the coating composition 110 onto the base film 120 using the above-described coating method, and then curing the coating layer by ultraviolet rays irradiated by an ultraviolet curing machine. 100) is formed.
  • Ultraviolet rays are irradiated with ultraviolet lamps such as high pressure mercury lamps, metal halide lamps, xenon lamps, and microwave electrodeless lamps.
  • the typical wavelength range required for curing the coating layer is 211-400 nm and the amount of light is 100-3000 mJ. / m 2 .
  • the coating composition 110 of the present invention includes a silsesquioxane composite polymer.
  • the silsesquioxane composite polymer includes a cage-type silsesquioxane composite polymer or a ladder-type silsesquioxane composite polymer having a cage structure, and a cage-type silsesquioxane composite polymer and a ladder-type silsesquioxane composite polymer.
  • Mixed forms are also possible.
  • the silsesquioxane composite polymer of the present invention is represented by any one of the following Chemical Formulas 1 to 9 in the form of a cage and a ladder, which will be described later.
  • Step S102 is a step of attaching the hard coating film 100 to the surface forming the curved surface in the injection mold (200, 210) to manufacture a product having a curved shape, heating attachment, N 2 gas injection attachment, adhesive layer use attachment, Use various methods of attachment, including physical attachment.
  • the injection molds 200 and 210 may include an upper mold 200 having a concave portion corresponding to the convex shape of the curved product 212 and a lower mold 210 having a convex portion corresponding to the concave shape of the curved product 212. It includes.
  • the hard coating film 100 is attached to the concave portion of the upper mold 200 and the convex portion of the lower mold 210, respectively.
  • the upper mold 200 and the lower mold 210 are provided with a plurality of adsorption holes (not shown), and the adsorption holes are connected to the vacuum pump (not shown) by a suction tube (not shown).
  • the vacuum pump When the vacuum pump is driven, the hard coating film 100 may be fixed to the bottom surface by pulling the suction force of the suction hole.
  • step S104 the hot-melt material 211 is injected into the injection molds 200 and 210 to be integrated with the hard coating film 100 and simultaneously injection molded.
  • the hot melted material 211 is injected into the space between the upper mold 200 and the lower mold 210.
  • the hot melt material 211 may be a known hot melt material, and may be a hot melt polymer material, a hot melt composite material, a solid metal, a solid plastic, a solid composite material and a mixture of two or more thereof.
  • polymer materials include polycarbonate (PC), polymethylmethacrylate (PMMA), polyethersulfone (PES), polyethylene terephtalate (PET), polyethylenenaphthalate (PEN), cyclic olefin copolymer (COC), polyacrylate (PAC), polyethylene (PE), and PEEK (PEEK).
  • Polyetheretherketone (PEI), Polyetherimide (PEI), Polyimide (PI), Polysulfone (PSF), Polyvinylalcohol (PVA), Polyvinylcinnamate (PVC), Triacetylcellulose (TAC), Polysilicon, Polyurethane and Epoxy Resin) may be selected from the group consisting of, more specifically, PC, PET, acrylic resin.
  • the material injected into the injection molds 200 and 210 may be a solid plate including a solid metal, a solid plastic, and a solid composite material as well as the hot melted material 211 described in the present invention.
  • solid materials such as curved vehicle bonnets are possible.
  • the hot-melted material 211 When the hot-melted material 211 is injected into the injection molds 200 and 210, the hot melted material 211 is bonded to the silsesquioxane composite polymer of the hard coating film 100 so that the interface is integrated without being separated.
  • step S106 the injection molds 200 and 210 are removed and cooled, thereby producing a curved-shaped product 212 having a hard coating film 100 which is an injection molded product integrated with the hard coating film 100.
  • the silsesquioxane composite polymer of the hard coating film 100 is heterogeneous and thus helps to separate from the injection molds 200 and 210.
  • a mold release agent may be applied to the injection molds 200 and 210.
  • the hard coating film 100 integrated with the hot-melted material 211 is cooled by removing the upper mold 200 and the lower mold 210, and the curved coating products 100 and 212 having the hard coating film 100 formed on both surfaces thereof. ) Is manufactured.
  • the injection-molded product according to the present invention is manufactured by forming a hard coat film 100 on one or both surfaces of the curved form product 212, and a silsesquioxane of the hot melted material 211 and the hard coat film 100.
  • the composite polymer will have an integrated hard coating layer.
  • the base film 120 may be separated from the integrated hard coating layer.
  • the coating composition 110 is formed of a coating composition containing the silsesquioxane composite polymer represented by any one of the following Chemical Formulas 1 to 9.
  • Each Y is independently O, NR 21 or [(SiO 3/2 R) 4 + 2n O], at least one is [(SiO 3/2 R) 4 + 2n O],
  • Each X is independently R 22 or [(SiO 3/2 R) 4 + 2n R], at least one is [(SiO 3/2 R) 4 + 2n R],
  • R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C 1 -C 40 alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C 2 -C 40 alkenyl group; C 1 ⁇ C 40 Alkoxy group; C 3 -C 40
  • a and d are each independently an integer of 1 to 100,000, specifically a is 3 to 1000, d is 1 to 500, more specifically a is 5 to 300, d is 2 to 100,
  • b are each independently an integer of 1 to 500
  • e are each independently 1 or 2, specifically 1,
  • n is each independently an integer of 1 to 20, and specifically 3 to 10.
  • R 1 , R 2 , R 16 , D, a and d are the same as defined in Chemical Formulas 1 to 9.
  • the pH of the reaction solution of the first step of the present invention is preferably 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, the third step It is preferable that the pH of the reaction solution of 8 to 11.5, the pH of the reaction solution of the fourth step of introducing the Ee is 1.5 to 4.
  • the pH of the reaction solution of the first step of the present invention is preferably 9 to 11.5
  • the pH of the reaction solution of the second step is preferably 2 to 4
  • the third step It is preferable that the pH of the reaction solution of 8 to 11.5, the pH of the reaction solution of the fourth step of introducing the Ee is 1.5 to 4.
  • step 1 Mixing a basic catalyst and an organic solvent in a reactor, and then adding an organic silane compound and preparing two types of Chemical Formula 10 in which the degree of condensation is controlled;
  • the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added.
  • a second step of stirring A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR 13 ) 2 after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.
  • the pH of the reaction solution of the first step is preferably 9 to 11.5, the pH of the reaction solution of the second step is preferably 2 to 4, the third step of The pH of the reaction solution is preferably 8 to 11.5, the pH of the reaction solution of the fourth step is preferably 9 to 11.5, the pH of the reaction solution of the fifth step is preferably 2 to 4, the reaction solution of the sixth step Is preferably 8 to 11.5, and the pH of the reaction solution of the seventh step of introducing Ee is preferably 1.5 to 4.
  • the pH of the reaction solution of the seventh step of introducing Ee is preferably 1.5 to 4.
  • the terminal may further include a repeating unit of [E] e.
  • a mixed catalyst of two or more basic catalysts is specifically used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.
  • the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba.
  • the amine basic catalyst may be tetramethylammonium hydroxide (TMAH)
  • the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO 3 ).
  • the content of each component may be arbitrarily adjusted at a ratio of 10 to 90:10 to 90 parts by weight of the amine based catalyst and the metal based catalyst.
  • the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation.
  • the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H 2 SO 4 , HNO 3 , CH 3 COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.
  • the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art.
  • organic solvent commonly used in the art.
  • polar solvents such as 2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile,
  • solvents such as methylene
  • the silsesquioxane composite polymer of the present invention may be R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Organosilanes comprising R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 can be used Specifically, the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the curing density of the composite polymer to increase the mechanical strength and hardness of the cured layer An organic silane compound containing an epoxy group or a (meth) acryl group having an effect of improving can be used.
  • organosilane compound examples include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane,
  • N of the [(SiO 3/2 R) 4 + 2n O] structure introduced into the repeating unit [D] d of the above formulas may be substituted with an integer of 1 to 20, specifically 3 to 10, more specifically As an average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by the following formula (11):
  • R is as defined above.
  • N of the [(SiO 3/2 R) 4 + 2n R] structure introduced into the repeating units [B] b or [E] e of the above formulas may be substituted with an integer of 1 to 20, specifically 3 to 10, and more specifically, the average n value is 4 to 5, for example, when n is 4, the substituted structure is represented by the following Formula 12:
  • R is as defined above.
  • the silsesquioxane polymer may be a polymer in Tables 1 to 18 below.
  • ECHE Epoxycyclohexyl
  • GlyP means Glycidoxypropyl
  • POMMA means (methacryloyloxy) propyl, and when two or more are described, it means mixed use.
  • n is 1-8 each independently.
  • the silsesquioxane composite polymer of Chemical Formula 1 may be a polymer described in Table 1 or 2 below.
  • the silsesquioxane composite polymer of Chemical Formula 2 may be a polymer described in Tables 3 and 4 below.
  • silsesquioxane composite polymer of Chemical Formula 3 is shown in Table 5 or 6 below.
  • the silsesquioxane composite polymer of Chemical Formula 4 may be a polymer described in Tables 7 and 8 below.
  • the silsesquioxane composite polymer of Chemical Formula 7 may be a polymer described in Tables 13 and 14 below.
  • the silsesquioxane composite polymer of Chemical Formula 8 may be a polymer described in Tables 15 and 16 below.
  • the silsesquioxane composite polymer of Chemical Formula 9 may be a polymer described in Tables 17 and 18 below.
  • the silsesquioxane composite polymer may be adjusted to 1 to 99.9% or more in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.
  • the weight average molecular weight of the silsesquioxane composite polymer may be 1,000 to 1,000,000, specifically 5,000 to 100,000, and more specifically 7,000 to 50,000. In this case, the processability and physical properties of the silsesquioxane can be improved simultaneously.
  • the coating composition 110 including the silsesquioxane composite polymer represented by any one of Formulas 1 to 9 may use two or more kinds of composite polymers, specifically, any one of Formulas 3 to 9 It is preferable to use the silsesquioxane composite polymer shown.
  • the physical properties of the coating can be further improved by including the repeating unit [B] b or [E] e.
  • the coating composition 110 may be coated alone as a solventless type when the silsesquioxane composite polymer is in a liquid state, and may include an organic solvent in the case of a solid phase.
  • the coating composition may further include an initiator or a curing agent.
  • the coating composition 110 includes a silsesquioxane composite polymer represented by any one of Formulas 1 to 9, an organic solvent commonly used in the art having compatibility with the composite polymer, and an initiator.
  • additives such as hardeners, plasticizers, sunscreens, and other functional additives may be further included to improve curability, heat resistance, UV protection, plasticizing effects, and the like.
  • the silsesquioxane composite polymer may be included at least 5 parts by weight or more based on 100 parts by weight of the coating composition, specifically 5 to 90 parts by weight, and more specifically 10 to 50 parts by weight. It is good to be included in negative amounts. If within the above range can further improve the mechanical properties of the cured film of the coating composition.
  • organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol,
  • polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform
  • polar solvents such as furan-based compounds such as tetrahydrofuran, dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform
  • solvents such as dichloro
  • the initiator or the curing agent may be appropriately selected and used according to the organic functional group included in the silsesquioxane composite polymer.
  • an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group
  • various curing using heat or light is possible.
  • the change due to heat or light can be achieved in the polymer itself, but specifically, the curing step can be achieved by diluting with the organic solvent as described above.
  • various initiators may be used for curing and post-reaction of the composite polymer, and the initiator may be included in an amount of 0.1-20 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, curing After transmission and coating stability can be satisfied at the same time.
  • a radical initiator may be used, and the radical initiator may include trichloro acetophenone, diethoxy acetophenone, and 1-phenyl-2-hydride.
  • sulfoniums such as triphenylsulfonium and diphenyl-4- (phenylthio) phenylsulfonium, diphenyliodonium and bis (dode) are used as photopolymerization initiators (cations).
  • Iodonium such as silphenyl) iodonium, diazonium, such as phenyldiazonium, ammonium, such as 1-benzyl-2-cyanopyridinium and 1- (naphthylmethyl) -2-cyanofridinium, (4- Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate iodonium, bis (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltrifluoro Romethanesulfonate iodonium, triphenylsulfonium tetrafuluroborate, tri-p-toylsulfonium hexafulurophosphate, tri-p-toylsulfonium trifluoromethanesulfonate and (2,4- cyclopent
  • cationic or protonic acid catalysts such as triflate, boron trifluoride ether complex, boron trifluoride, etc.
  • various onium salts such as ammonium salt, phosphonium salt and sulfonium salt and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation, and these initiators can also be added in various mixed forms, and can be mixed with the various radical initiators specified above. Do.
  • phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, methylhydride anhydride, trialkyltetra Acid anhydride hardeners, such as hydrophthalic anhydride, dodecenyl succinic anhydride, and 2, 4- diethyl glutaric anhydride, can also be used widely.
  • the hardener may be included in an amount of 0.1-20 parts by weight based on the weight of the coating composition 110.
  • triazine-based compounds such as acetoguanamine, benzoguanamine, 2,4-diamino-6-vinyl-s-triazine, imidazole, 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, and 1-methylimidazole, 1, 5-diazabicyclo [4.3.0] nonene-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p-tril) phosphine, tris (alkylphenyl Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutyl
  • the coating composition 110 may also include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, adhesion improving agents, etc., for the purpose of improving hardness, strength, durability, formability, etc., through curing or post-reaction. It may further comprise. Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the substrate, that is, properties such as flexibility, light transmittance, heat resistance, hardness, and strength. Each of the additives is preferably included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the composition.
  • Additives usable in the present invention include polyether-modified polydimethylsiloxane (eg, BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK-306, BYK-330, BYK-341, BYK-344, BYK-307, BYK-333, BYK-310, etc.), polyether hydroxy polydimethylsiloxanes (e.g., manufactured by BYK BYK-308, BYK-373, etc.), polymethylalkylsiloxane (e.g., BYK-077, BYK-085, etc.), polyether polymethylalkylsiloxane (e.g., BYK- 320, BYK-325, etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315, etc.), allylalkyl polymethylalkylsiloxane (aral
  • polyester hydroxy polydimethylsiloxane Polydimethylsiloxane (Polyester modified hydroxy functional polydimethylsiloxane, such as BYK-370), polyester acrylic polydimethylsiloxane (Acrylic functional polyester modified polydimethylsiloxane, such as BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxy Polyeher-polyester modified hydroxy functional polydimethylsiloxane (e.g., BYK-375, etc.), polyether polydimethylsiloxane (e.g., BYK-345, BYK-348, BYK-346) , BYK-UV3510, BYK-332, BYK-337, etc.), nonionic polyacrylic (Non-ionic acrylic copolymer, such as BYK-380, etc.), Ionic acrylic copolymer (eg, BYK -381, etc
  • thermosetting Even in the method of curing the coating composition 110, photocuring or thermosetting may be appropriately selected and applied according to the functional group of the composite polymer. Specifically, in the case of thermosetting, the curing temperature is 50 to 200 °C, more specifically 80 to 120 °C.
  • the coating thickness may be arbitrarily adjusted, specifically 0.01 to 500 um, more specifically 0.1 to 300 um, and even more specifically 1 to 100 um range is good. Within the above range, not only can the surface hardness of 7H or more be stably secured, but also excellent physical properties of the substrate surface properties. In particular, when the coating layer is laminated to a thickness of 10um or more, the surface hardness can be represented stably 9H.
  • the coated product according to the present invention has a curved portion having a hard coating layer, and particularly has a hard coating layer in which a hot melt material and a coating material are integrated, and has a large effect of preventing a problem of cracking, peeling, etc. of curved portions during curved surface forming. It is excellent in smoothness and hardness of the curved product coated surface, and can form a high gloss texture.
  • ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • GPTMS is Glycidoxypropytrimethoxysilane
  • MAPTMS is (methacryloyloxy) propyltrimethoxysilane
  • PTMS is Phenyltrimethoxysilane
  • MTMS is Methyltrimethoxysilane
  • ECHETMDS is Di (epoxycyclohexyethyl) Di (glycidoxypropyl) tetramethoxy disiloxane
  • MAPTMDS stands for Di (methacryloyloxy) propy
  • PTMDS stands for Di (phenyl) tetramethoxy disiloxane
  • MTMDS stands for Di
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the chemical formula 4 had a molecular weight of 8,000 styrene.
  • thermosetting coating composition 50 g of the silsesquioxane composite polymer obtained in Preparation Example 1-c was dissolved in methyl ethyl ketone at 50% by weight to prepare 100 g of a coating composition. Thereafter, 3 parts by weight of 1,3-diaminopropane and 1 part by weight of BYK-357 and BYK-348 were added to 100 parts by weight of the prepared coating composition, followed by stirring for 10 minutes to prepare a thermosetting coating composition.
  • Preparation Example 1-c alone constitute a coating composition without a separate composition.
  • a coating composition was prepared by a method similar to that described in Preparation Example 1.
  • the preparation of the catalyst and the linear structure was used in the same manner as in Preparation Examples 1-a and 1-b, and then prepared in the following manner to produce a continuous D-A-D structure.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 20 below. At this time, the manufacturing method was equally applied to the method used in Preparation Example 2.
  • a coating composition was prepared by a method similar to that described in Preparation Example 1.
  • the preparation of the catalyst and the linear structure was used in the same manner as in Preparation Example 1, and then prepared in the following manner to produce the E-A-D structure.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Preparation Example 3-a in progress at a time to achieve stable hydrolysis.
  • 3 parts by weight of the catalyst prepared in Preparation Example 1-a was added again to give a basic state.
  • PH of the mixed solution was adjusted.
  • the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (3).
  • a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 3 was obtained along with various byproducts by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was 17,000 in terms of styrene
  • n value was 4-6
  • the results of formula (3) are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 21 below. At this time, the manufacturing method was equally applied to the method used in Preparation Example 3.
  • a continuous hydrolysis and condensation were carried out step by step to prepare a composite polymer having an E-A-D structure, and a coating composition was prepared by a method similar to that described in Preparation Example 1.
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
  • XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
  • the reaction was carried out dropwise addition of 0.36 wt% HCl aqueous solution very slowly 5 parts by weight to the mixed solution of Preparation Example 4-b, pH was adjusted to have an acidic, and stirred for 30 minutes at a temperature of 4 °C. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Preparation Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-type structure was introduced into the polymer chain separately from the linear structure, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum, and the overall reactant was converted into the aqueous mixture. It was made. After 4 hours of mixing, some of the alkoxy groups in the B structure were changed to 0.025 mmol / g as a result of partial extraction and analysis by 29 Si-NMR and 1 H-NMR. It was confirmed that the ratio was introduced at 5: 5. In addition, the styrene reduced molecular weight was measured to 10,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Preparation Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Preparation Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Formula 4 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 12,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 4 results are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 22 below. At this time, the production method was equally applied to the method used in Preparation Example 4.
  • the reaction was carried out dropwise addition of 0.36 wt% HCl aqueous solution very slowly 5 parts by weight to the mixed solution of Preparation Example 4-b, pH was adjusted to have an acidic, and stirred for 30 minutes at a temperature of 4 °C. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared in 25 parts by weight, which is 5 times the amount of Preparation 4-b, and added dropwise at one time. After stirring for 1 hour, 5 parts by weight of the catalyst prepared in Preparation Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Preparation Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Preparation Example 4-a was added again to adjust the pH of the mixed solution in a basic state.
  • the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 16,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 5 results are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 23 below. At this time, the manufacturing method was equally applied to the method used in Preparation Example 5.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Preparation Example 6-a in progress at a time to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Preparation Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted.
  • the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6).
  • a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained along with various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 21,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 6 results are as follows.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 24 below. At this time, the manufacturing method was equally applied to the method used in Preparation Example 6.
  • Synthesis step was carried out step by step, hydrolysis and condensation step by step, to prepare a coating composition in the same manner as in Preparation Example 1.
  • a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).
  • KOH Potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • the mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm -1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.
  • the mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through 1 H-NMR analysis. This was then used to introduce the cage into the continuous reaction.
  • XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight in terms of 8,000 styrene.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Preparation Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was a styrene conversion value of 24,000
  • the n value of X was 4-6
  • the n value of Y was 4-6.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 25 below. At this time, the manufacturing method was equally applied to the method used in Preparation Example 7.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 100 parts by weight of the material obtained in Preparation Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 1 was obtained without various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 36,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 8 results are as follows.
  • silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 26 below. At this time, the production method was equally applied to the method used in Preparation Example 8.
  • the terminal was converted into a cage structure using a trifunctional monomer.
  • 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Preparation Example 9-a in progress at a time to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Preparation Example 7-a was added again to give a basic state. PH of the mixed solution was adjusted.
  • the cage-type polymer is introduced at the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.
  • the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained along with various by-products by vacuum reduction.
  • the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was.
  • the molecular weight was obtained in the styrene conversion value of 28,000, the n value of X was 4-6, the n value of Y was 4-6.
  • silsesquioxane composite polymer was prepared by applying the monomers described in Table 27 below. At this time, the production method was equally applied to the method used in Preparation Example 9.
  • a hard coating layer was formed on the curved portion of the injection molded product having the curved portion by using the coating composition prepared in Preparation Example. Specifically, the coating composition of Preparation Example 1 was coated with a thickness of 20 um on a PET or PC base film and cured to prepare a hard coat film. The hard coat film was attached to the curved portion of the injection mold having the curved portion. After that, the injection material (PC) was injected into the injection mold to which the hard coating film was attached, and injection molding was performed. Thereafter, the injection mold was removed to complete a coating product having a hard coating layer formed on a curved portion.
  • PC injection material
  • the coating product of the present invention was found to be excellent in crack resistance, peeling resistance, smoothness and hardness at the same time, even though the hard coating layer was formed on the curved portion.
  • the coating compositions of other preparation examples of the present invention also showed comparable results to the coating compositions of Tables 28 to 30.
  • the present invention has an effect of preventing the problem of cracking, peeling, etc. of the bent portion during the surface forming process by improving the hard coating method for the existing product having a curved surface.
  • the present invention has the effect of obtaining a coating quality superior to spray and dipping coating by improving the hard coating method for the existing curved products.
  • the present invention has the effect of improving the smoothness of the curved product coating surface and forming a high gloss texture, such as flat plate hard coating.
  • the present invention can replace the coating material coated on the product having a curved surface with a new one to implement the insulation function and the adhesion function of the insulating material at the same time to slim down the thickness of the coated product, shorten the manufacturing process of the coated product, raw material cost and process This can greatly reduce the cost.

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Abstract

La présente invention concerne un produit revêtu, et un procédé de revêtement dur à dureté élevée et, en particulier, le procédé de revêtement dur à dureté élevée comprend les étapes de : adhésion d'une couche de revêtement dur à une surface formant une forme de surface courbée dans un moule à injection pour fabriquer un produit ayant la forme de surface courbée ; et formation d'une couche de revêtement dur sur une surface ou les deux surfaces du produit ayant la forme de surface courbée par intégration d'un matériau fondu à chaud et d'un matériau, qui forme la couche de revêtement dur, et simultanément, conduite d'un moulage par injection sur celui-ci par injection du matériau fondu à chaud dans le moule par injection.
PCT/KR2016/000825 2015-01-26 2016-01-26 Produit revêtu, et procédé de revêtement dur de surface courbée à dureté élevée WO2016122191A1 (fr)

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