WO2020247226A1 - Résines hybrides de silicone-organiques à double durcissement - Google Patents

Résines hybrides de silicone-organiques à double durcissement Download PDF

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Publication number
WO2020247226A1
WO2020247226A1 PCT/US2020/034825 US2020034825W WO2020247226A1 WO 2020247226 A1 WO2020247226 A1 WO 2020247226A1 US 2020034825 W US2020034825 W US 2020034825W WO 2020247226 A1 WO2020247226 A1 WO 2020247226A1
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silicone
adhesive formulation
organic hybrid
meth
optically clear
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PCT/US2020/034825
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English (en)
Inventor
Laxmisha SRIDHAR
Kevin J. Welch
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Henkel IP & Holding GmbH
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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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences

Definitions

  • This present disclosure relates generally to liquid optically clear adhesives, and more particularly to liquidly clear adhesives that are dual curable and comprise silicone polyaspartic esters with silicone isocyanates.
  • LOCA Liquid Optically Clear Adhesives
  • These LOCAs typically must exhibit several properties including: being able to bond uneven surfaces; be optically clear when cured; and they must have good optical properties after aging over a wide range of environmental conditions.
  • the LOCA also fills the air gaps between the laminate layers improving the overall viewing experience and clarity of a touch screen.
  • Current LOCAs have a radiation cure mechanism that permits automated processes using visible light or UV radiation cure options thereby enabling design flexibility.
  • silicone-based LOCA polymers that are light and moisture curable have a low modulus and low glass transition temperatures. They are usable over a wide temperature range of from -40 °C to 100°C but have low compatibility with visible light photoinitiators and moisture cure catalysts. In addition, they have high moisture permeability, resulting in objectionable high haze under high temperature and/or high humidity conditions.
  • the present disclosure presents dihydroxy functional silicone-organic hybrid polymers that are fully or partially end-capped using isocyanate functional (meth)acrylates to form silicone-organic hybrid (meth)acrylate polymers.
  • These silicone-organic hybrid (meth)acrylate polymers are UV curable and possess a significant amount of organic content, which improves their compatibility with other organic polymers, organic monomers and visible light organic
  • silicone-organic hybrid (meth)acrylate polymers and the LOCA formulations containing them will have lower moisture permeation than pure silicone polymers and lower shrinkage than pure organic (meth)acrylate polymers. These features are good for LOCA applications, especially for automobile displays.
  • the present disclosure further utilizes silicone polyaspartic esters in combination with isocyanate terminated silicone-organic hybrid polymers or organic diisocyanates to provide shadow curing of the LOCA formulations.
  • this disclosure provides a dual curable LOCA formulation comprising: a UV curable silicone-organic hybrid (meth)acrylate polymer; a silicone polyaspartic ester; an isocyanate terminated silicone-organic hybrid polymer; a photoinitiator, a catalyst and, optionally, a diluent.
  • a UV curable silicone-organic hybrid (meth)acrylate polymer e.g., a silicone-aspartic ester
  • an isocyanate terminated silicone-organic hybrid polymer e.g., a photoinitiator, a catalyst and, optionally, a diluent.
  • 2K two-part
  • a combination of the silicone-organic hybrid (meth)acrylate polymer and the silicone polyaspartic ester can be a part A and the isocyanate terminated silicone-organic hybrid polymer with the photoinitiator and optional diluent can be a part B of the two-part system.
  • the UV cure in the above two-part system can come from reaction of the silicone-organic hybrid (meth)acrylate polymer along with additional reaction from the diluent if a reactive (meth)acrylate or acrylamide diluent is used.
  • the shadow cure comes from the reaction of the isocyanate terminated silicone-organic hybrid polymer with the silicone polyaspartic ester.
  • the residual hydroxyl groups on the silicone-organic hybrid (meth)acrylate polymer can also take part in a reaction with the isocyanate terminated silicone-organic hybrid polymer thereby contributing to the shadow cure.
  • the shadow cure can come solely or partially from the reaction of the isocyanate terminated silicone-organic hybrid polymers with the silicone polyaspartic esters.
  • this disclosure presents a two-part dual curable composition
  • a two-part dual curable composition comprising: a UV curable silicone-organic hybrid (meth)acrylate polymer; a silicone polyaspartic ester; an organic polyisocyanate; a photoinitiator, a catalyst and, optionally, a diluent.
  • the above described formulation components can be appropriately split into a two-part adhesive system by one skilled in the art.
  • the silicone-organic hybrid (meth)acrylate and silicone polyaspartic ester can be a part A and the organic polyisocyanate, photoinitiator and optional diluent can be a part B of the two-part system.
  • the UV cure in the above two-part system comes from the silicone- organic hybrid (meth)acrylate along with the diluent if a (meth)acrylate or acrylamide diluent is used.
  • the shadow cure comes from the reaction of the organic polyisocyanate with the silicone polyaspartic ester. If a partially end-capped silicone-organic hybrid (meth)acrylate polymer is used, the residual hydroxyl groups on the silicone-organic hybrid (meth)acrylate polymer can also take part in a reaction with the organic polyisocyanate thereby contributing to the shadow cure. Thus, the shadow cure can come solely or partially from the reaction of the organic polyisocyanate with the silicone polyaspartic ester.
  • this disclosure presents a two-part dual curable composition according to one of the above compositions further including as an additional component a silicone- organic hybrid polyol polymer having at least two hydroxy functionalities.
  • a silicone- organic hybrid polyol polymer having at least two hydroxy functionalities.
  • ком ⁇ онент functionalities can be on the ends of a linear silicone-organic hybrid polymer, appended to branches in branched chain silicone-organic hybrid polymers or combinations thereof. They can also be the result of a chain extension reaction between a dihydroxy functional silicone-organic hybrid polymer and an organic diisocyanate.
  • the optional silicone-organic hybrid polymer having at least two hydroxy functional groups also referred to as a silicone polyol
  • silicone polyaspartic ester would be found in the part A with the silicone-organic hybrid (meth)acrylate polymer. Both silicone polyol and silicone polyaspartic ester would function in the shadow cure by reaction with the isocyanate terminated silicone-organic hybrid polymer or the organic
  • the term“about 1 or“approximately” means within 25%, preferably 15%, more preferably 5%, and most preferably 1% of the given value.
  • the term“about” means the standard deviation or variance for a given value, if available.
  • alkyl or an“alkenyl” has the broadest meaning in the art and can be linear, branched, cyclic or a combination thereof having the specified number of carbon atoms and it may be substituted.
  • aliphatic means a hydrocarbon moiety having the specified number of carbon atoms and it can be linear, branched, cyclic or a combination thereof, it can be fully saturated or contain unsaturation so long as it is not aromatic.
  • aryl refers to an aromatic group having the specified number of carbon atoms.
  • aralkyl refers to an alkyl group substituted with an aryl group with the specified number of carbon atoms and it can be substituted.
  • the term“dual cure” refers to a composition comprising a first component that is radiation curable, for example curable by exposure to ultraviolet (UV) or visible light, >400nm, radiation and a second component including materials that form reaction products when mixed, for example a first material comprising an isocyanate and a second material comprising a hydroxy group.
  • a dual cure material specifically excludes compositions that rely on moisture or water initiated curing reactions.
  • The“equivalent weight” (EW) of a reactive polymer is the mass of polymer which has one equivalent of reactivity, meaning the mass of polymer which corresponds to one mole of reactive side-chain groups. As known to one of skill in the art, it is widely used to indicate the reactivity of a polyol or an isocyanate terminated polymer which would undergo crosslinking reactions through those functional groups.
  • hydrocarbylene refers to any divalent radical derived from a
  • hydrocarbylenes are linear or branched alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylcycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes,
  • bicycloalkylarylenes tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, polyoxyalkylenes and mixtures thereof.
  • Hydrocarbylene groups can be unsubstituted or substituted.
  • heterocarbylene means a divalent hydrocarbylene group that contains a heteroatom such as oxygen, sulfur, or nitrogen incorporated within the chain or ring.
  • Heterocarbylene groups can be unsubstituted or substituted.
  • hydroxyl number or value refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid taken up on acetylation of one gram of the chemical substance that has free hydroxyl groups as is known to one of skill in the art.
  • LOCA Liquid Optically Clear Adhesive.
  • an adhesive will be considered to be optically clear if it exhibits an optical transmission of at least about 85%.
  • the measurement of optical transmission is known to the person skilled in the art. It can preferably be measured on a 300 pm thick sample according to the following preferred testing method.
  • the preferred testing method for transmission includes: placing a small drop of optically clear adhesive placed on a 75 mm by 50 mm plain micro slide, such as a Gorilla glass slide from Corning, that has been wiped with isopropanol and has two 300 pm thick spacers kept on its two ends. A second glass slide is attached onto the adhesive under a force.
  • the adhesive is fully cured under a UV source and left at room temperature overnight for shadow curing.
  • the optical transmission is measured from wavelength 380 nm to 780 nm with a spectrometer Datacolor 650 from Technical color solutions.
  • One blank glass slide is used as the background.
  • the term“(meth)acrylate” means both acrylate and methacrylate monomers and combinations thereof and the polymers formed from them. Therefore a (meth)acrylate polymer can comprise methacrylate monomers, acrylate monomers or mixtures thereof.
  • molecular weight refers to number average molecular weight unless otherwise specified.
  • the number average molecular weight M n is determined according to the present invention by gel permeation chromatography (GPC, also known as SEC) at 23°C using a polystyrene standard. This method is known to one skilled in the art.
  • Shadow cure refers to the ability of a LOCA formulation to cure in areas that are not exposed to UV or visible light. Shadow curable LOCAs find use in applications wherein at least some portions of the LOCA cannot be exposed to UV or visible light.
  • silicone-organic hybrid polymer refers to polymers that comprise silicone blocks, (R.2SiO) n , wherein the R groups are organic groups such as methyl or ethyl etc., in addition to significant organic block content and at least two hydroxy functional groups.
  • the organic block content can comprise from 2 to 30 weight % based on the total weight of the silicone- organic hybrid polymer.
  • an organic group is one that includes carbon in the group.
  • silicone-organic hybrid (meth)acrylate polymer refers to silicone- organic hybrid polymers that have been fully or partially end-capped with (meth)acrylate functional groups.
  • silicone-organic hybrid polymers can be prepared by reacting isocyanate functional (meth)acrylates with hydroxy functional groups of a silicone compound.
  • substituted means the parent structure has one or more hydrogen atoms replaced with a chemical group, which does not adversely affect the desired composition.
  • Some exemplary chemical replacement groups are amino, phosphino, quaternary nitrogen (ammonium), quaternary phosphorous (phosphonium), hydroxyl, amide, alkoxy, mercapto, nitro, alkyl, halo, sulfone, sulfoxide, phosphate, phosphite, carboxylate, carbamate groups.
  • this disclosure provides a dual curable LOCA
  • formulation comprising: a UV curable silicone-organic hybrid (meth)acrylate polymer; a silicone polyaspartic ester; an isocyanate terminated silicone-organic hybrid polymer; a photoinitiator, a catalyst and, optionally, a diluent.
  • a two-part (2K) system comprises two components that are packaged and maintained separate from each other. The two components are mixed just before use. Mixing the two components initiates a cure reaction so the mixed composition has a limited pot life.
  • a combination of the silicone-organic hybrid (meth)acrylate polymer and the silicone polyaspartic ester can be a part A and the isocyanate terminated silicone-organic hybrid polymer with the photoinitiator and optional diluent can be a part B of the two-part system.
  • the UV cure in the above two-part system can come from reaction of the silicone-organic hybrid (meth)acrylate polymer along with additional reaction from the diluent if a (meth)acrylate or acrylamide diluent is used.
  • the shadow cure comes from the reaction of the isocyanate terminated silicone-organic hybrid polymer with the silicone polyaspartic ester. If a partially end-capped silicone-organic hybrid (meth)acrylate polymer is used, the residual hydroxyl groups on the silicone-organic hybrid (meth)acrylate polymer can also take part in a reaction with the isocyanate terminated silicone-organic hybrid polymer thereby contributing to the shadow cure.
  • the shadow cure can come solely or partially from the reaction of the isocyanate terminated silicone-organic hybrid polymers with the silicone polyaspartic esters.
  • Table 1 presents the preferred and most preferred ranges for the various components of this formulation presented in weight % based on the total formulation weight.
  • this disclosure presents a two-part dual curable composition
  • a two-part dual curable composition comprising: a UV curable silicone-organic hybrid (meth)acrylate polymer; a silicone polyaspartic ester; an organic polyisocyanate; a photoinitiator, a catalyst and, optionally, a diluent.
  • the above described formulation components can be appropriately split into a two-part system by one skilled in the art.
  • the silicone-organic hybrid (meth)acrylate and silicone polyaspartic ester can be a part A and the organic polyisocyanate, photoinitiator and optional diluent can be a part B of the two-part system.
  • the UV cure in the above two-part system comes from the silicone-organic hybrid (meth)acrylate along with the diluent if a (meth)acrylate or acrylamide diluent is used.
  • the shadow cure comes from the reaction of the organic polyisocyanate with the silicone polyaspartic ester. If a partially end-capped silicone-organic hybrid (meth)acrylate polymer is used, the residual hydroxyl groups on the silicone-organic hybrid (meth)acrylate polymer can also take part in a reaction with the organic polyisocyanate thereby contributing to the shadow cure. Thus, the shadow cure can come solely or partially from the reaction of the organic polyisocyanate with the silicone polyaspartic ester.
  • Table 2 presents the preferred and most preferred ranges for the various components of this formulation presented in weight % based on the total formulation weight.
  • this disclosure presents a two-part dual curable composition according to one of the above compositions further including as an additional component a silicone- organic hybrid polyol polymer having at least two hydroxy functionalities.
  • a silicone- organic hybrid polyol polymer having at least two hydroxy functionalities.
  • functionalities can be on the ends of a linear silicone-organic hybrid polymer, appended to branches in branched chain silicone-organic hybrid polymers or combinations thereof. They can also be the result of a chain extension reaction between a dihydroxy functional silicone-organic hybrid polymer and an organic diisocyanate.
  • the optional silicone-organic hybrid polymer having at least two hydroxy functional groups would be found in the part A with the silicone- organic hybrid (meth)acrylate polymer and the silicone polyaspartic ester. It would function in the shadow cure by reaction with the isocyanate terminated silicone-organic hybrid polymer or the organic polyisocyanate.
  • each R and R’ is independently hydrocarbylene segments having 1 to 30 carbon atoms or heterocarbylene segments having 1 to 30 carbon atoms and one or more of nitrogen, oxygen or sulfur atoms in the backbone.
  • R and R’ are each independently organic segments selected from the group consisting of linear or branched alkylenes,
  • cycloalkylenes bicycloalkylenes, tricycloalkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes, tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, polyoxyalkylenes, heterocycloalkylene, heterocycloarylenes and mixtures thereof; optionally, the alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes, tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, polyoxyalkylenes, heterocycloalkylene, heterocycloarylene
  • Pi and P2 can be independently H or a polymerizable group derived from reaction of a hydroxyl group with an isocyanate functional (meth)acrylate group with the proviso that only one of Pi and P2 can be H.
  • n and m are independently 1 to 10,000.
  • n is 1 to 1,000 and m is 1 to 20.
  • the silicone-organic hybrid (meth)acrylate polymers which are partially or fully (meth)acrylate end-capped according to the present disclosure are generally prepared in a two-step reaction process.
  • a first step more than a stoichiometric excess of dihydroxy functional silicone- organic hybrid polymer is reacted neat at 65 to 70° C with an organic diisocyanate to form a chain extended hydroxy -terminated silicone-organic copolymer.
  • this hydroxyl -terminated silicone-organic copolymer is end-capped by reaction with an isocyanate functional (meth)acrylate to form Structure I.
  • the useful isocyanate functional (meth)acrylates are not limited and are commercially available.
  • Increasing either the diol or the diisocyanate favors it as the terminal group and lowers the amount of chain extension and viscosity. So, for example a ratio of diol to diisocyanate of 1 : 1.05 favors formation of isocyanate terminated silicone-organic hybrid polymer and gives the highest chain extension and viscosity relative to the 1 : 1.5 ratio of the same reactants. On the other hand, a ratio of diol to diisocyanate of 1.05 : 1 would favor hydroxy terminated silicone-organic hybrid polymer with the highest chain extension and viscosity relative to when the ratio is 1.5: 1 of the same reactants.
  • dihydoxy functional silicone-organic hybrid polymers finding use in the present disclosure include: from Shin Etsu KF-6000, KF-6001, KF-6002, KF- 6003, X-22-4952, X-22-4272, KF-6123, X-21-5841 and KF-9701; or from Siltech Corporation Silmer OHT A0, Silmer OH Di-10, or Silmer OH Di-50.
  • the structure of Silmer OHT AO is:
  • the dihydroxy functional silicone-organic hybrid polymers can either be linear as is shown below in Structure II or branched chain with pendant groups having hydroxyl functional groups as in Silmer OHT AO.
  • Each R is independently a covalent bond, a hydrocarbylene having 1 to 30 carbon atoms or a heterocarbylene having 1 to 30 carbon atoms and one or more of nitrogen, oxygen or sulfur atoms in the backbone.
  • R is an alkylene or cycloalkylene segment containing 1- 30 carbon atoms and m is 1 to 10,000 and more preferably 1 to 1,000.
  • Organic diisocyanates or polyisocyanates that find use in the present disclosure either for reaction with the dihydroxy functional silicone-organic hybrid polymers or for addition to the LOCA formulation include, but are not limited to: isophorone diisocyanate (IPDI), IPDI trimer, polymeric IPDI, naphthalene 1,5 -diisocyanate (NDI), methylene bis-cyclohexylisocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), isocyanurate of TDI, TDI-trimethylolpropane adduct, polymeric TDI, hexamethylene diisocyanate (HD I), HDI isocyanurate, HDI biurate, polymeric HDI, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate
  • Preferred aliphatic diisocyanates include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), pentamethylenediisocyanate, TAKENATETM 600 (1,3, Bis(isocyanatemethyl)cyclohexane), TAKENATETM D-120N (an aliphatic polyisocyanate adduct based on hydrogenated xylylene diisocyanate), both available from Mitsui Chemicals, and 4,4’ -methylene dicyclohexyl diisocyanate (H12-MDI).
  • Aliphatic and cycloaliphatic diisocyanates and polyisocyanates are preferred. In some embodiments aromatic diisocyanates are not used as they contribute to color and higher viscosity of the resulting copolymers, which is not desirable.
  • These polymers find use in the present disclosure in a reaction with organic
  • R and R’ are each independently hydrocarbylene having 1 to 30 carbon atoms or heterocarbylene having 1 to 30 carbon atoms and one or more of nitrogen, oxygen or sulfur atoms in the backbone.
  • R and R’ are each independently organic segments selected from the group consisting of alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
  • tricycloalkylarylenes bisphenylenes, cycloalkylarylenes, polyoxyalkylenes, heterocycloalkylene, heterocycloarylenes and mixtures thereof; optionally, the alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
  • R and R’ are each independently selected from an alkylene having 4 to 20 carbon atoms, cycloalkylene having 4 to 20 carbon atoms, an alkylene ether having 4 to 20 carbon atoms or a cycloalkylene ether having 4 to 20 carbon atoms and one or more oxygen atoms.
  • n and m are each independently 1 to 10000 Preferably, n is 1 to 1,000 and m is 1 to 20
  • Silicone polyaspartic esters according to the present disclosure are made by reaction of polyamine functional silicone-organic hybrid polymers with maleate esters. Because of steric effects and electronic effects coming from the ester groups around the secondary amine
  • polyaspartic esters react slowly with isocyanate compounds as compared to the reaction rate of simple primary and secondary amines with isocyanates, which takes place instantaneously.
  • This relatively lower reactivity of polyaspartic esters with multifunctional isocyanates gives sufficient open time in the reaction for use in the shadow reaction of a 2K LOCA formulation.
  • the presence of succinate ester units in the silicone polyaspartic esters adds additional organic portions to the silicone-organic hybrid polymers.
  • Polyfunctional silicone polyaspartic esters according to the present disclosure were made by the reaction of the corresponding polyfunctional amine silicone-organic hybrid polymers with dibutyl maleate ester.
  • polyamine functional silicone-organic hybrid polymers that can be used for the synthesis of silicone polyaspartic esters according to the present disclosure include, but are not limited to: polyamine functional silicone-organic hybrid polymers such as KF-868, KF-865, KF- 864, KF-859, KF-393, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867, KF-8021, KF-869, KF-861, KF-877, KF-889, KF-8010, KF-8008, KF-8012, X-22-3939A, X-22-161A, X-22-161B, X- 22-9409, X-22-1660B-3 and P
  • polyamine functional silicone-organic hybrid polymers that find use in the present disclosure include those available from Genesee Polymers such as GP-4, GP-6, GP-581, GP-988-1, GP-344, GP-997, GP-342, GP-316, GP- 967, GP-965, GP-654 and GP-966.
  • the Genesee Polymers exhibit the following suitable structures.
  • the polyamine functional silicone-organic hybrid polymers used to form the silicone polyaspartic esters can be based off any of structures GP I, GP II and GP III wherein the amine functionality is at least 2 to 20 and the values for x, the organic functional portion, can range from 0 to 2000.
  • the photoinitiator component of the LOCA formulations is used in an amount sufficient to effectuate cure.
  • photoinitiators include, one or more selected from the group consisting of benzyl ketals, hydroxyl ketones, amine ketones and acylphosphine oxides, such as 2-hy droxy -2-methyl- 1 -phenyl- 1 -acetone, diphenyl (2,4,6- triphenylbenzoyl)-phosphine oxide, 2-benzyl-dimethylamino-l-(4-morpholinophenyl)-butan-l-one, benzoin dimethyl ketal dimethoxy acetophenone, a-hy droxy benzyl phenyl ketone, 1 -hydroxy- 1- methyl ethyl phenyl ketone, oligo-2-hydoxy-2-methyl-l-(4-(l-methyvinyl
  • photoinitiators may be used individually or in combination which each other. Photoinitiators may be used in non-limiting amounts of about 0.01% by wt. to about 3.0% by wt. of the total composition, and desirably in about 0.05% by wt. to about 1.0% by wt. of the total composition.
  • the photoinitiator is Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (TPO) or Irgacure 819.
  • the catalyst finding use in the present disclosure can be any catalyst for isocyanate reaction with hydroxyl groups.
  • Some examples include amine catalysts such as 2,2’- dimorpholinodiethylether and triethylenediamine and organometallic catalysts such as dibutyltin dilaurate, dibutyltin dioctoate, Bismuth carboxylate catalysts that are available with the tradename K Kcat XK640, Zr based catalysts such as K Kat A 209 which is available from King industries.
  • the catalyst is preferably present in an amount of from 0.002 to 3.5 wt.%, more preferably 0.005 to 0.2 wt.% based on the total composition weight.
  • the optional diluent useful for the present disclosure preferably is a low viscosity, reactive diluent, monomer or reactive diluent polymer.
  • the organic diluent can be a liquid having a viscosity of 5 cPs to 3,000 cPs at 25 °C.
  • the organic diluent is desirably compatible with the silicone-organic hybrid polymer and the silicone-organic hybrid (meth)acrylate polymer at about 25 °C.
  • the organic diluent may comprise mono-functional (meth)acrylates, (meth)acrylamides, (meth)acrylic acid and combinations thereof.
  • Illustrative examples of useful mono-functional (meth)acrylates include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, alkenyl (meth)acrylates, heterocycloalkyl (meth)acrylates, heteroalkyl methacrylates, alkoxy polyether mono(meth)acrylates.
  • the diluent is used in an amount of from 0 to 10 wt.%, more preferably from 1 to 6wt.% based on the total composition weight.
  • the alkyl group on the (meth)acrylate diluents may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, desirably 1 to 10 carbon atoms, optionally having at least one substituent selected from an alkyl group having 1 to 10 carbon atoms, substituted or
  • unsubstituted cycloalkyl group having 1 to 20 carbon atoms desirably 1 to 10 carbon atoms
  • substituted or unsubstituted bicyclo or tyricycloalkyl group having 1 to 20 carbon atoms desirably 1 to 15 carbon atoms
  • an alkoxy group having 1 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms.
  • alkenyl group on the (meth)acrylate diluents may be a substituted or
  • unsubstituted alkenyl group having 2 to 20 carbon atoms desirably 2 to 10 carbon atoms, optionally having at least one substituent selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an epoxy group having 2 to 10 carbon atoms, or a hydroxyl.
  • the heterocyclo group on the (meth)acrylate diluents may be a substituted or unsubstituted heterocyclo group having 2 to 20 carbon atoms, desirably 2 to 10 carbon atoms, containing at least one hetero atom selected from N and O, and optionally having at least one substituent selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an epoxy group having 2 to 10 carbon atoms.
  • Alkoxy polyether mono(meth)acrylate diluents can be substituted with an alkoxy group having 1 to 10 carbons and the poly ether can have 1 to 10 repeat units.
  • mono-functional (meth)acrylate reactive diluents include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, lauryl acrylate, isooctyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, octadecyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-methoxyethyl acrylate, 2-phenoxyethyl acrylate, dicyclopentadienyl (meth)acrylate,
  • a few especially preferred diluents include 2-(2-ethoxyethoxy)ethyl acrylate and 2-methoxyethyl acrylate.
  • Useful (meth)acrylamides may be unsubstituted (meth)acrylamides, N-alkyl substituted (meth)acrylamides or N,N-dialkyl substituted (meth)acrylamides.
  • the alkyl substituent desirably has 1 to 8 carbon atoms, such as N- ethyl acrylamide, N-octyl acrylamide and the like.
  • the alkyl substituent desirably has 1 to 4 carbon atoms, such as N,N-dimethyl acrylamide and N,N-di ethyl acrylamide.
  • the dual cure LOCA formulations according to the present disclosure will have a viscosity of 500 cPs to 100,000 cPs, more preferably 1000 cPs to about 50,000 cPs at 25 °C.
  • a LOCA formulation prepared according to the present disclosure and cured has a refractive index of from 1.3 to 1.6, most preferably from 1.35 to 1.55.
  • the LOCA composition according to the present disclosure can optionally comprise isocyanate stabilizers, UV stabilizers and color stabilizers. Some useful UV stabilizers are the hindered amine light stabilizers (HALS). A UV stabilizer which carries a silyl group allowing it to be incorporated into the end product during crosslinking or curing can also be used. Furthermore, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus and/or sulfur can also be useful.
  • the LOCA composition can optionally include isocyanate stabilizer such as p-toluenesulfonyl isocyanate (PTSI), benzoyl chloride or ppm levels of phosphoric acid.
  • isocyanate stabilizer such as p-toluenesulfonyl isocyanate (PTSI), benzoyl chloride or ppm levels of phosphoric acid.
  • Example 1 preparation of a silicone-organic hybrid (meth)acrylate polymer having a single acrylate terminal end.
  • a 500 mL pre-dried 3 necked round bottom flask was equipped with a mechanical stirrer and a dry nitrogen inlet. Then 100 g (18.7 mmol) of the dihydroxy functional silicone-organic hybrid polymer KF-6003 was added to the flask. The material in the flask was dried at 70 °C under vacuum for 1 hour to remove any traces of moisture.
  • (meth)acrylate polymer is based on Structure I and has the general structure shown below.
  • Example 2 preparation of a partially acrylate end-capped silicone-organic hybrid (meth)acrylate polymer having a single acrylate terminal end.
  • a 1L pre-dried 3 necked round bottom flask was equipped with a mechanical stirrer and dry nitrogen inlet. Then 504 g (0.158 mol) of the dihydroxy functional silicone-organic hybrid polymer KF-6002 was added to the flask. The material in the flask was dried at 80 °C under vacuum for 1 hour to remove any traces of moisture.
  • Example 3 preparation of a partially acrylate end-capped silicone-organic hybrid (meth)acrylate polymer having a single acrylate terminal end.
  • a 1L pre-dried 3 necked round bottom flask was equipped with a mechanical stirrer and dry nitrogen inlet. Then 504 g (0.158 mol) of the dihydroxy functional silicone-organic hybrid polymer KF-6002 was added to the flask. The material in the flask was dried at 80°C under vacuum for 1 hour to remove any traces of moisture. After cooling to 65°C, 26 mg of BHT and 26 mg of Irganox 1010 were added to the flask followed by 0.13 g of an acetone solution of K cat XK-640 bismuth carboxylate catalyst.
  • the flask was put under nitrogen atmosphere and then 19.11 g of HD I (0.113mol) was added. After the addition was over, the reaction was further stirred for 2 hours at the same temperature. Then 5.13 g of AOI (36 mmol) was added and the mixture further stirred for 1 hour to give a partially acrylate end-capped silicone-organic hybrid (meth)acrylate polymer according to the present disclosure in quantitative yield.
  • the partially acrylate end-capped silicone-organic hybrid (meth)acrylate polymer is based on Structure I and has the general structure shown below.
  • Example 4 preparation of an isocyanate terminated silicone-organic hybrid polymer.
  • a 500 mL pre-dried 3 necked round bottom flask was equipped with a mechanical stirrer and dry nitrogen inlet. Then 286.8 g (91 mmol) of the dihydroxy functional silicone-organic hybrid polymer KF-6002 was added to the flask. The material in the flask was dried at 80 °C under vacuum for 1 hour to remove any traces of moisture. After cooling to 65 °C, 20 mg of BHT and 20 mg of Irganox 1010 were added to the flask followed by 5 drops of an acetone solution of K cat XK-640 bismuth carboxylate catalyst.
  • the isocyanate terminated silicone-organic hybrid polymer in accordance with the present disclosure was transferred to an air tight syringe under nitrogen atmosphere. Isocyanate titration was performed on this polymer to measure the % of isocyanate content.
  • the isocyanate terminated silicone-organic hybrid polymer is based on Structure III and has a general structure as shown below.
  • Example 5 preparation of an isocyanate terminated silicone-organic hybrid polymer.
  • a 1L pre-dried 3 necked round bottom flask was equipped with a mechanical stirrer and dry nitrogen inlet. Then 500 g, OH# 24 213 mmol, of the dihydroxy functional silicone-organic hybrid polymer KF-6003 was added to the flask. The material in the flask was dried at 80 °C under vacuum for 1 hour to remove any traces of moisture. After cooling to 65 °C, 20 mg of BHT and 20 mg of Irganox 1010 were added followed by 24.39 g (145 mmoles), of hexamethylene diisocyanate.
  • Example 6 preparation of a silicone polyaspartic ester.
  • a 250mL round bottomed flask was equipped with a mechanical stirrer and thermocouple. Then 90.62 g (EW 1474, 61 mmol) of a bis(3-aminopropyl) terminated polydimethylsiloxane polymer and 14.03 g (61 mmol) of dibutyl maleate were added to the flask. The mixture was stirred at 65 °C for about 4 hours by which time 80% of reaction was complete. The resulting mixture was stored at 25 °C for 3 weeks to drive the reaction to about 95% conversion.
  • the resulting silicone polyaspartic ester is a low viscosity colorless liquid based on structure IV and having the general structure shown below.
  • the silicone polyaspartic esters finding use in the present disclosure have Structure IV wherein n ranges from 0 to 500.
  • Example 7 preparation of a silicone polyaspartic ester.
  • a 250mL round bottomed flask was equipped with a mechanical stirrer and thermocouple. Then 116.2 g (EW 3710, 31 mmol) of a polydimethylsiloxane polymer (KF-864 from Shin-Etsu) and 7.15 g (31 mmol) of dibutyl maleate were added to the flask. The mixture was stirred at 65 °C for about 4 hours by which time 80% of reaction was complete. The resulting mixture was stored at 25 °C for 3 weeks to drive the reaction to about 95% conversion. This gave silicone polyaspartic ester as a colorless liquid based on structure V and having the general structure shown below.
  • the silicone polyaspartic esters finding use in the present disclosure have Structure V wherein m ranges from 10 to 2000 and n ranges from 4 to 20.
  • Adhesive Formulation 1 In Formulation 1, the silicone-organic hybrid
  • (meth)acrylate polymer of Example 1 was used as the UV cure component.
  • the isocyanate terminated silicone-organic hybrid polymer of Example 4 and the silicone polyaspartic ester of Example 6 were used for the shadow cure components. Since Example 1 also has some residual hydroxyl groups, this silicone-organic hybrid (meth)acrylate polymer is also expected to contribute to some shadow cure reaction with isocyanates. Therefore, the stoichiometry was carefully balanced to maintain a 1 : 1 ratio between isocyanate functionality to amine functionality of the silicone polyaspartic ester of Example 6 and the hydroxyl functionality of Example 1.
  • the composition of Adhesive Formulation 1 is shown below in Table 3.
  • Adhesive Formulation 1 can be split into a 2K formulation by combining compatible components such as the silicone-organic hybrid (meth)acrylate polymer, silicone polyaspartic ester and the tin catalyst in one part while the isocyanate terminated silicone-organic hybrid polymer, photoinitiator and acrylate diluent can be in another part.
  • An exemplary two-part formulation, Adhesive Formulation 2 is as shown below in Table 4.
  • Adhesive Formulation 1 Optical aging results for the dual UV and shadow cured Adhesive Formulation 1 are shown below in Table 5.
  • Adhesive Formulation 1 was applied and cured between two Gorilla glass plates with 250 micron spacers. Cured reaction products of Adhesive Formulation 1 showed acceptable optical aging results after accelerated weathering testing using a QUV accelerated weathering tester, available from Q-Lab Corporation, with 1,000 hours of alternating UV exposure at 90 °C and 85°C/85% relative humidity exposure. This is an accelerated weathering test that reproduces the damage caused by sunlight, rain and dew.
  • Adhesive Formulation 3 Another dual cure formulation, Adhesive Formulation 3, was developed including a silicone polyaspartic ester for the shadow cure reaction with an organic polyisocyanate, IPDI.
  • the components of Adhesive Formulation 3 are shown below in Table 6.
  • other organic polyisocyanates can be used in the formulation in place of the IPDI.
  • Adhesive Formulation 3 evidence for a shadow cure reaction in Adhesive Formulation 3 between the silicone polyaspartic ester and the organic polyisocyanate comes from the increase in Shore 00 hardness for Adhesive Formulation 3 that occurred after the initial UV cure.
  • the Shore 00 hardness was 7 after the initial UV cure and increased to about 25 after 2 days standing at 25 °C.
  • Adhesive Formulation 3 can also be split into a 2K system by one skilled in the art.
  • the above formulation can be designed into a 10: 1 two-part formulation as shown below.
  • Adhesive Formulation 3 also showed good optical properties after 1000 hours of QUV, 90°C, 85°C/85% Relative Humidity aging. Adhesive Formulation 3 was applied and cured between two Gorilla glass plates with 250 micron spacers. The results are shown below in Table 7.
  • Adhesive Formulation 4 Another dual cure formulation, Adhesive Formulation 4, was developed including the silicone polyaspartic ester of Example 7 for shadow cure reaction with isocyanate terminated silicone-organic hybrid polymer of Example 4. The components of Adhesive Formulation 4 are shown below in Table 8.
  • Adhesive Formulation 4 Since a trifunctional crosslinkable silicone polyaspartic ester is used in Adhesive Formulation 4 the shadow cure was very fast. After mixing and with no exposure to UV radiation the shadow cured only formulation became a gel in 30 minutes after mixing indicating a very fast shadow cure. Further evidence for shadow cure after UV cure came from a Shore 00 hardness increase after the initial UV cure, which increased from 2 to about 42 after 4 days standing at 25 °C Adhesive Formulation 4 can also be split into a 2K system by one skilled in the art by separating incompatible components. For example, by the isocyanate, diluent and photoinitiator will be one part and the rest of components will be another part.
  • Adhesive Formulation 4 was subjected to optical aging after placing between two Gorilla glass plates and curing. Good optical properties were obtained with this formulation after over 1000 hours of QUV, 90°C, 85°C/85% RH aging. The results are shown below in Table 9.
  • Adhesive Formulation 4 can be lowered by replacing some of the trifunctional silicone polyaspartic ester crosslinker with a difunctional diol as shown in Adhesive Formulation 5 in Table 10 below.
  • Adhesive Formulation 5 also showed a very fast shadow cure, about 30 minutes at 25 °C, but the Shore 00 hardness after dual cure was 36 after 4 days, which is lower than that observed for Adhesive Formulation 4, which showed a Shore 00 hardness of 42 after 4 days.
  • Adhesive Formulation 5 was subjected to optical aging after being placed between two Gorilla glass plates with spacers. Good optical properties were obtained with this formulation after 1000 hours of QUV, 90°C, 85°C/85% RH aging. The results are shown below in table 11.
  • Adhesive Formulation 6 A two-part dual cure formulation was developed including the isocyanate terminated silicone-organic hybrid of Example 5, the silicone-organic hybrid
  • This formulation was a 1 : 1 2K formulation since the amounts used in both parts was identical.
  • the formulation components are shown below in Table 12. After mixing and with no exposure to UV radiation the shadow cured only formulation became a gel in about 20 minutes indicating a very fast shadow cure.
  • premix 1 and premix 2 were made prior to Adhesive Formulation 6 preparation.
  • the components used in premix 1 and premix 2 are shown in the Tables below.
  • Adhesive Formulation 6 was subjected to optical aging study both as a 2K and IK formulation to compare the optical aging results.
  • the optical aging results were similar for both IK and 2K versions of Adhesive Formulation 6, as shown in table 15 below.
  • the formulations were place between two Gorilla glass plates with spacers and cured.
  • Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough

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Abstract

La présente invention concerne des adhésifs optiquement clairs liquides à double durcissement, qui comprennent un polymère (méth)acrylate hybride silicone-organique durcissable aux UV et une portion durcissable à l'ombre. La portion durcissable à l'ombre comprend un ester polyaspartique de silicone et soit un polyisocyanate organique soit un polymère hybride silicone-organique terminé par un groupe isocyanate. Les composés peuvent être utilisés comme adhésifs dans un système à deux composants. L'utilisation des adhésifs selon l'invention est particulièrement préférée pour le remplissage de composants électro-optiques spécialement pour les applications d'adhésifs d'affichage automobile.
PCT/US2020/034825 2019-06-05 2020-05-28 Résines hybrides de silicone-organiques à double durcissement WO2020247226A1 (fr)

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CN115976877A (zh) * 2022-12-27 2023-04-18 广东利宏达包装有限公司 一种包装盒的表面处理工艺

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CN113462163A (zh) * 2021-06-30 2021-10-01 成都硅宝科技股份有限公司 一种脱醇型高强度透明流淌硅橡胶及制备方法
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CN115976877B (zh) * 2022-12-27 2023-10-13 广东利宏达包装有限公司 一种包装盒的表面处理工艺

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