Classifications

• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
  • C03C17/23—Oxides
  • C03C17/25—Oxides by deposition from the liquid phase
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen

Definitions

• the present invention relates to glass components used for flexible glass, coating films, and the like.
• inorganic materials have high dimensional stability, but are heavy and have low flexibility.
• organic materials have advantages such as lightness and good workability, but there is concern about insufficient strength. Therefore, for example, an organic-inorganic hybrid material having properties of both an inorganic material and an organic material is known (see Patent Document 1).
• glycerin is attracting attention as a biomass raw material that considers the environment and safety, and is expected to be widely used not only for cosmetics, foods, and pharmaceuticals, but also for industrial purposes.
• the applicant of the present application has been researching and developing glycerin for a long time, and has developed glass components for substrates using polyglycerin compounds.
• An object of the present invention is to provide a glass component that exhibits excellent flexibility when used for flexible glass, coating films, and the like.
• the present invention is a compound having a (poly)glycerin skeleton with an average degree of polymerization of 1 to 100, and a glass component containing a (poly)glycerin-based alkoxysilane having an alkoxysilyl group.
• the cured product obtained by curing the above glass component had excellent flexibility without breaking or cracking when bent. Therefore, the glass component of the present invention can be applied to flexible glass and coating materials.
• the present invention is a compound having a (poly)glycerin skeleton with an average degree of polymerization of 1 to 100, and is a glass component containing a (poly)glycerin-based alkoxysilane having an alkoxysilyl group.
• the present invention is a glass component containing a (poly)glycerin-based alkoxysilane having a plurality of alkoxysilyl groups at the terminals of the (poly)glycerin skeleton.
• (Poly)glycerin represents glycerin or polyglycerin.
• the (poly)glycerin according to the present invention has an average degree of polymerization of 1 to 100, preferably has a lower limit of 2 or more, more preferably 4 or more, and a preferred upper limit of 70 or less, more preferably 20 or less, and most preferably 15. It is below.
• the average degree of polymerization is calculated from the following formula (2) and the following formula (3) from the hydroxyl value obtained by the terminal analysis method.
• the hydroxyl value in formula (3) is a numerical value that is an index of the number of hydroxyl groups contained in (poly)glycerin, and the amount of acetic acid required to acetylate the free hydroxyl groups contained in 1 g of (poly)glycerin.
• the (poly)glycerin-based alkoxysilane according to the present invention is preferably a reaction product obtained by reacting (poly)glycerin or a (poly)glycerin derivative with a compound having an alkoxysilyl group.
• the (poly)glycerin or (poly)glycerin derivative is preferably a compound represented by the structure of the following formula (1).
• AO is an alkylene having 1 to 4 carbon atoms
• Oxide is represented by R1, which is the same or different functional group and includes any reactive functional group selected from the group consisting of hydrogen, a thiol group, a (meth)acryloyl group, an epoxy group, and an allyl group. is a substituent.
• AO includes, for example, ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO), preferably ethylene oxide (EO).
• EO ethylene oxide
• p, q, and r described in formula (1) represents the average number of additions of alkylene oxide to one hydroxyl group of polyglycerol, and each is preferably 0-50, more preferably 1-20.
• the sum of p, q, and r (p+q+r) is preferably 1-130, more preferably 5-120.
• (poly)glycerin or (poly)glycerin derivatives include (poly)glycerin, (poly)glycerin alkylene oxide adduct, (poly)glycerin (alkylene oxide) thioglycolate, (poly)glycerin (alkylene oxide) ) 3-mercaptopropionate, (poly) glycerin (alkylene oxide) (meth) acrylate, (poly) glycerin (alkylene oxide) (poly) glycidyl ether, (poly) glycerin (alkylene oxide) (poly) allyl ether, etc. mentioned.
• a compound having an alkoxysilyl group is, for example, an alkoxysilane having a vinyl group, an allyl group, an isocyanate group, a thiol group, a (meth)acryloyl group, an epoxy group, a hydroxyl group, an amino group, a hydrosilyl group, or the like.
• the (poly)glycerin-based alkoxysilane according to the present invention is obtained by reacting a reactive functional group contained in (poly)glycerin or a (poly)glycerin derivative with a reactive functional group contained in the alkoxysilane. is preferred.
• the resulting reaction product it is preferable that 20 to 100% of the reactive functional groups of the (poly)glycerin or (poly)glycerin derivative are reacted and bonded, More preferably, 50-100% of the reactive functional groups are reacted and attached.
• the glass component of the present invention is a compound having a (poly)glycerin skeleton with an average degree of polymerization of 1 to 100, and contains a (poly)glycerin-based alkoxysilane having an alkoxysilyl group.
• the glass component of the present invention includes those containing organic/inorganic compounds within a range that does not impair the effects of the present invention.
• the glass component of the present invention can be used to prepare a cured coating film by applying it to various substrates and curing it.
• the method of curing the coating film is not particularly limited, but curing by a sol-gel reaction is preferred, for example.
• the glass component of the present invention When the glass component of the present invention is cured by a sol-gel reaction, water necessary for hydrolyzing the metal alkoxide is added.
• a catalyst to promote the hydrolysis and polycondensation reaction of the metal alkoxide, and examples of the catalyst include acid catalysts and alkali catalysts used in conventional sol-gel methods.
• Acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, formic acid, organic acids, photoacid generators and the like.
• alkali catalysts include inorganic base compounds such as metal hydroxides and ammonia, organic base compounds such as amines and phosphines, and photobase generators.
• a coating method for producing a coating film using the glass component of the present invention is not particularly limited, but examples include cast coating, spin coating, blade coating, dip coating, roll coating, A bar coat method, a die coat method, and the like can be mentioned.
• the film thickness of the coating film can be appropriately changed from 0.1 to 100 ⁇ m depending on the application.
• the glass component of the present invention since the (poly)glycerin-based alkoxysilane has a flexible skeleton structure, it is possible to form a thick film of 30 ⁇ m or more.
• additives When curing the present invention, other additives may be added to the extent that the effects of the present invention are not impaired.
• additives include ultraviolet absorbers, colorants, pigments, antioxidants, anti-yellowing agents, bluing agents, antifoaming agents, thickeners, anti-settling agents, antistatic agents, surfactants, Examples include adhesion promoters, infrared absorbers, light stabilizers, and the like.
• an organic solvent may be mixed.
• alcohols include methanol, ethanol, butanol, isobutanol, isopropyl alcohol, propanol, t-butanol, sec-butanol, benzyl alcohol
• ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, Cyclohexanone, diacetone alcohol, esters such as ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate, ethers is isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, glycols are ethylene glycol, diethylene glycol,
• silicate monomers such as TMOS and TEOS
• silicate oligomers such as methyl silicate and ethyl silicate
• polysilsesquioxane can be blended.
• substrates for applying the glass component of the present invention include glass, polyethylene terephthalate, polycarbonate, plastics such as acrylic, metals, stone rocks, and the like.
• the coating film produced from the glass component of the present invention is used for coating automobile windshields, lamp covers, camera lenses, goggles, etc., for example. Moreover, since the coating film has bending resistance, it can be used for touch panel displays, electronic paper, organic EL lighting, substrate glass for solar cells, members of flexible devices, and the like.
• Example 1 1.20 g of alkoxysilane compound (A1), 1.44 g of propylene glycol monomethyl ether, 0.33 g of water, and 0.12 g of 1 wt % nitric acid aqueous solution were uniformly stirred and mixed to obtain a coating liquid. Then, the prepared mixture was applied to a 100 ⁇ m-thick PET film (Cosmo Shine A4300, manufactured by Toyobo) using an applicator (250 ⁇ m, Coating Tester Kogyo). After application, the coating film was air-dried at room temperature for 1 hour or longer, and then allowed to stand in a dryer (SPHH-101, manufactured by Espec) set at 80° C. for 30 minutes to obtain a cured coating film.
• SPHH-101 manufactured by Espec
• Examples 2 to 21 A coating liquid and a cured coating film were prepared in the same manner as in Example 1 except that the alkoxysilane compound (A1) used in Example 1 was changed to the alkoxysilane compounds (A2) to (A21).
• Example 22 0.5 g of alkoxysilane compound (A1), 0.5 g of methyl silicate (MS-51, manufactured by Colcoat), 1.00 g of propylene glycol monomethyl ether, 0.56 g of water, and 0.20 g of 1 wt% nitric acid aqueous solution were uniformly mixed. The mixture was stirred and mixed to obtain a coating liquid. Then, the prepared mixture was applied to a 100 ⁇ m-thick PET film (Cosmoshine A4300, manufactured by Toyobo) using an applicator (250 ⁇ m, Coating Tester Kogyo). The applied coating film was air-dried at room temperature for 1 hour or longer, and then allowed to stand in a dryer (SPHH-101, manufactured by Espec) set at 80° C. for 30 minutes to obtain a cured coating film.
• SPHH-101 manufactured by Espec
• ⁇ Comparative Example 1> 1.0 g of methyl silicate (MS-51, manufactured by Colcoat), 0.20 g of propylene glycol monomethyl ether, 1.43 g of water, and 0.10 g of 1 wt % nitric acid aqueous solution were uniformly stirred and mixed to obtain a coating liquid. Then, the prepared mixture was applied to a 100 ⁇ m-thick PET film (Cosmo Shine A4300, manufactured by Toyobo) using an applicator (250 ⁇ m, Coating Tester Kogyo). The applied coating film was air-dried at room temperature for 1 hour or longer, and then allowed to stand in a dryer (SPHH-101, manufactured by Espec) set at 80° C. for 30 minutes to obtain a cured coating film.
• SPHH-101 manufactured by Espec
• the flexibility of the cured coating films of Examples 1 to 22 and Comparative Example 1 was evaluated by the following flex resistance and flex durability.
• (Flexibility) Evaluated using a mandrel rod according to JIS K5600-5-1 (cylindrical mandrel method). Place the coated surface of the cured coating on the inside or outside along the mandrel rod and bend it until the opposing surfaces are parallel. (mm) was recorded.
• (bending durability) Affix the cured coating with tape to a clamshell type bending tester (DMLHP-CS, manufactured by Yuasa System Equipment Co., Ltd.), and perform a continuous inward or outward bending test under the conditions of a bending diameter of 10 mm and a test speed of 30 rpm. Carried out.
• DMLHP-CS clamshell type bending tester
• Table 1 shows the composition of Examples 1 to 22 and Comparative Example 1.
• Table 2 shows the evaluation results of bending resistance
• Table 3 shows the evaluation results of bending durability.
• the bending durability shown in Table 3 was tested by extracting some examples.
• Example 1 using the cured coating film obtained from the (poly)glycerin-based alkoxysilane of the present invention, no cracks or cracks occurred in the bending resistance test even when the outer diameter of the mandrel rod was 2 mm. Compared with Comparative Example 1 using a cured coating film obtained from a specific alkoxysilane, the flex resistance was excellent. Further, as in Example 22, by blending the (poly)glycerin-based alkoxysilane of the present invention with the low-flexibility alkoxysilane shown in Comparative Example 1, the flex resistance was greatly improved.

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• 2022
  • 2022-05-20 JP JP2023522731A patent/JPWO2022244859A1/ja active Pending
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