WO2016106939A1 - Glass shatter-proof glue composition and glass product and use - Google Patents

Glass shatter-proof glue composition and glass product and use Download PDF

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Publication number
WO2016106939A1
WO2016106939A1 PCT/CN2015/072108 CN2015072108W WO2016106939A1 WO 2016106939 A1 WO2016106939 A1 WO 2016106939A1 CN 2015072108 W CN2015072108 W CN 2015072108W WO 2016106939 A1 WO2016106939 A1 WO 2016106939A1
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Prior art keywords
glass
sio
component
amount
adhesive composition
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PCT/CN2015/072108
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French (fr)
Chinese (zh)
Inventor
郑海庭
李碧霞
何海
朱经纬
黄光燕
Original Assignee
广州慧谷化学有限公司
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Publication of WO2016106939A1 publication Critical patent/WO2016106939A1/en

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Classifications

    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • 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
    • 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

Definitions

  • the present invention relates to a silicone composition, and more particularly to a glass shatterproof adhesive composition and use thereof, and a glass article coated with the composition.
  • Increasing the impact strength of glass products generally has the following methods: one is to improve the strength of the glass product itself by improving the glass formulation or the process method; the second is to apply a layer of explosion-proof reinforced film to the glass product, such as an automobile glass explosion-proof film; The third is to achieve the impact resistance of the glass product by applying a layer of paint to the surface of the glass article and curing it.
  • CN100569685C discloses a production process of a glass shatterproof adhesive, which is a silicone resin, a silicone rubber, a butyl acetate, a silicone resin curing agent or a silicone rubber curing agent.
  • the weight is mixed, stirred, ground and filtered at room temperature to obtain a milky white glass coating, and then the coating is sprayed on the glass, and then dried at a low temperature of 80-100 ° C and dried at a high temperature of 180-220 ° C.
  • CN101724340A also discloses a method for producing a glass anti-crushing coating and a method for applying the same, which comprises a calcium halophosphate powder or a silicon micro powder, a silicone resin, a silica matting agent, a silicone resin cured product, an inorganic pigment, The solvent is evenly dispersed, and the impurities are filtered through a filter, and left to stand for 10-36 hours to obtain a white gel-like shatterproof coating, and the coating is sprayed on the glass, and then dried at a high temperature of 180-250 °C.
  • the technical problem to be solved by the present invention is to overcome the above-mentioned drawbacks of the prior art, and to provide a glass shatterproof adhesive composition which is simple in production process and requires only low-temperature baking and high production efficiency.
  • the invention provides a glass shatterproof glue composition, comprising:
  • the component (C) is used in an amount of 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the composition, and the component (D) fumed silica is used in an amount of 3 to 10 parts by weight.
  • the present invention also provides a glass article comprising a glass body, wherein the glass body is coated with a cured product of the glass shatterproof adhesive composition of the present invention.
  • the present invention also provides a glass shatterproof adhesive composition for use in a glass article, characterized in that it comprises the following steps:
  • Dilution the composition of any one of claims 1-8 is diluted with an organic solvent
  • Coating coating the diluted composition on a glass article
  • Curing curing the glass article coated with the composition at a temperature of 80-150 ° C;
  • Cooling Cool to room temperature.
  • the invention has the beneficial effects that the glass shatterproof adhesive composition of the invention has simple production process and only needs low temperature baking, the coating maintains good appearance and light extraction efficiency, and the surface level is good and solidified.
  • the appearance is colorless and transparent, and has excellent shatterproof properties.
  • Vi denotes a vinyl group
  • Me denotes a methyl group
  • MQ configuration means a three-dimensional structure having SiO 4/2 units
  • MD configuration means a linear structure having SiO 2/2 units.
  • the invention provides a glass shatterproof glue composition, comprising:
  • the organopolysiloxane has a viscosity of 3000-9000 mPa ⁇ s;
  • the component (C) is used in an amount of 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the composition, and the component (D) fumed silica is used in an amount of 3 to 10 parts by weight.
  • component (A) is a main component of the composition of the present invention, and alkenyl groups in components (A) and (C) are mutually reacted with silicon-bonded hydrogen atoms in component (B). Form a crosslink bond and cure.
  • the molecular structure of the component (A) is a linear molecular chain structure having at least two silicon-bonded alkenyl groups per molecule.
  • the component (A) is preferably a liquid linear structure organopolysiloxane comprising R 1 3 SiO 1/2 units and R 2 2 SiO 2/2 units, wherein R 1 and R 2 are selected Monovalent substituted or unsubstituted hydrocarbyl groups from the same or different alkenyl groups, containing no aromatic hydrocarbons, and no aliphatic unsaturated bonds.
  • the alkenyl group in common reacts with the silicon-bonded hydrogen atom in the component (B) to form a cross-linking bond. And curing.
  • the alkenyl group in the component (A) may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, and most preferably a vinyl group.
  • the monovalent substituted or unsubstituted hydrocarbon group in the component (A) which does not contain an aromatic hydrocarbon and does not contain an aliphatic unsaturated bond may include the following groups: methyl group, ethyl group, propyl group, butyl group, pentyl group. A hexyl, heptyl or similar alkyl group, a chloromethyl group, a 3-chloropropyl group or a similar haloalkyl group, most preferably a methyl group.
  • the content of the alkenyl group is preferably 0.001 to 0.05 mol/100 g; the viscosity of the component (A) in the present invention is limited to 3,000. -9000mPa ⁇ s, when the viscosity of the component (A) is less than 3000 mPa ⁇ s, the glass shatterproof performance is poor; when the viscosity of the component (A) is more than 9000 mPa ⁇ s, the paint film flow is adjusted, specifically It is manifested that the leveling time becomes longer, or the film thickness is difficult to achieve uniformity.
  • the (A) has the following average unit molecular formula
  • R 5 is selected from the same or different alkenyl groups
  • R 6 is selected from the same or different monovalent substituted or unsubstituted alkyl groups, 65 ⁇ a3 ⁇ 900.
  • the alkenyl group in R 5 may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, and most preferably a vinyl group.
  • the monovalent substituted or unsubstituted alkyl group in R 6 may include a group: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or the like, most preferably methyl.
  • the component (A) may include the following molecular formula as a representative:
  • the component (B) is one of the main components of the composition of the present invention, and the silicon-bonded hydrogen atom in this component reacts with the alkenyl group in the component (A) and the component (C). Form a crosslink bond and cure.
  • the molecular structure of the component (B) is a linear molecular chain structure having at least two silicon-bonded hydrogen atoms per molecule.
  • the component (B) is preferably a liquid linear structure polyorganohydridosiloxane comprising R 3 3 SiO 1/2 units and R 4 2 SiO 2/2 units, R 3 and R 4 selected Monovalent substituted or unsubstituted hydrocarbyl and hydrogen atoms which are the same or different from aromatic hydrocarbon-free and free of aliphatic unsaturated bonds.
  • the monovalent substituted or unsubstituted hydrocarbon group which does not contain an aromatic hydrocarbon and does not contain an aliphatic unsaturated bond in the component (B) may include the following groups: methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. , heptyl or similar alkyl, chloromethyl, 3-chloropropyl or similar haloalkyl, most preferably methyl.
  • the present invention defines a molar ratio of hydrogen bonded to silicon in the component (B) to be 0.7 to 1.6 mol/100 g.
  • the hydrogen content of the component (B) is less than 0.7 mol/100 g, the elongation at break of the cured product is relatively low, which affects the glass shatterproof property; when the hydrogen content of the component (B) is more than 1.6 mol At /100g, it also shows that the elongation at break of the cured product is relatively low, which affects the glass shatterproof performance.
  • the ratio of the silicon-bonded hydrogen atom in the component (B) to the molar amount of the alkenyl groups in the components (A) and (C) is from 0.9 to 3.0.
  • the (B) has the following average unit molecular formula
  • the R 8 may include a group: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or the like alkyl, chloromethyl, 3-chloropropyl or similar alkyl halide The group is most preferably a methyl group.
  • the component (B) may include the following molecular formula as a representative:
  • the amounts of the component (A) and the component (B) are not particularly limited and may be used in a conventional amount in the art, for example, the component (B) of the component (A) is used in a weight ratio of 1:99- 99:1. More preferably, component (A) is used in an amount of 20 to 75 parts by weight, based on 100 parts by weight of the total amount of the composition, component (B) The amount used is 1 to 30 parts by weight.
  • the molecular structure of the component (C) is a solid three-dimensional structure molecular chain structure, and should contain R 1 3 SiO 1/2 units and SiO 4/2 units in one molecule.
  • the alkenyl group in component (C) may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, and most preferably a vinyl group.
  • the monovalent substituted or unsubstituted hydrocarbon group in the component (C) which does not contain an aromatic hydrocarbon and does not contain an aliphatic unsaturated bond may include the following groups: methyl group, ethyl group, propyl group, butyl group, pentyl group.
  • the alkenyl group is contained in an amount of from 0.01 to 0.30 mol / 100 g, preferably from 0.02 to 0.25 mol / 100 g.
  • the component (C) is used in an amount of 20 to 40 parts by weight based on 100 parts by weight of the total amount of the composition, and when the amount of the component (C) is less than 20 parts by weight, the cured product is used.
  • the hardness is low, the tensile strength and the elongation at break are both low, which is characterized by softening of the cured product and poor shatterproof property; when the amount of the component (C) is more than 40 parts by weight, the hardness is high and stretching High strength but low elongation at break, showing brittleness and poor shatterproof performance.
  • the (C) has the following average unit molecular formula
  • R 7 is selected from the same or different alkenyl groups
  • the alkenyl group in R 7 may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, most preferably a vinyl group
  • a monovalent substituted or unsubstituted alkyl group is a methyl group, an ethyl group, or a propyl group.
  • the monovalent substituted or unsubstituted alkyl group in R 6 may include a group: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or the like, most preferably methyl.
  • component (C) may include the following formula as a representative:
  • component (D) serves as one of the main components and functions as a toughening and reinforcing agent in the composition.
  • Component (D) is fumed silica, and its mesh number is limited to 200-4000 mesh. When it is less than 200 mesh, it shows that the paint film is turbid after curing, which affects the light output of the bulb; when it is larger than 4000 mesh, the cost is too high.
  • the component (D) is used in an amount of 3 to 10 parts by weight, based on 100 parts by weight of the total amount of the composition, and when the amount of the component (D) is less than 3 parts by weight, it is expressed as glass. The crushing performance is poor; when the amount of the component (D) is more than 10 parts by weight, the paint film flow is uneven.
  • the invention adopts a linear structure organopolysiloxane with a viscosity of 3000-9000 mPa ⁇ s.
  • This design enables the agglomerated fumed silica to be uniformly dispersed into agglomerated during the process of mixing and dispersing the resin and the fumed silica.
  • the body forms a three-dimensional network structure, which can improve the strength and improve the toughness, so that when the glass product falls from a high place, the coating plays a buffering protection function, thereby preventing the glass from being broken.
  • the component (E) is a catalyst which causes a hydrosilylation reaction between an alkenyl group in the components (A) and (C) and a silicon-bonded hydrogen atom in the component (B).
  • component (E) is a catalyst that promotes curing of the composition.
  • the type of the catalyst in the present invention is not particularly limited, and a catalyst conventionally used in the art may be, for example, a platinum catalyst, a rhodium catalyst or a palladium catalyst, and the present invention is preferably a platinum catalyst.
  • the amount of the component (E) to be used is not particularly limited, and it is preferably used in an amount sufficient to promote the curing reaction of the composition.
  • the present invention employs an octanol solution of chloroplatinic acid (platinum concentration: 5 wt%) as a catalyst.
  • the curable glass shatterproof adhesive composition of the present invention may further comprise a component (F) addition reaction inhibitor for the purpose of prolonging the storage period of the curable glass shatterproof adhesive composition of the present invention.
  • the reaction inhibitor is a temperature-dependent substance which, when heated to a certain extent, rapidly loses its inhibition, causing the composition to undergo a curing reaction.
  • the kind weight and the addition amount of the addition reaction inhibitor of the component (F) are not particularly limited, and a conventional inhibitor in the art may be used, and the amount added may be added as needed.
  • the component (F) in the present invention is 2-benzene.
  • the base 3-butyn-2-ol is added in an amount of 0.1% by weight based on the total weight of the composition.
  • the glass shatterproof adhesive composition of the present invention may further comprise a component (G) adhesion promoter, the function of which is to increase the bonding force between the shatterproof glue and the glass, and prevent the lamp from being used after long-term lighting.
  • the shatterproof glue caused by high temperature deteriorates and falls off.
  • the type weight and the addition amount of the component (G) adhesion promoter are not particularly limited, and a conventional adhesion promoter in the art may be used, and the amount of addition may be added as needed, for example, the component (G) adhesion promoter of the present invention is ⁇ -glycidoxypropyltrimethoxysilane, manufactured by Chengdu Chenguang Chemical Research Institute under the trade name KH560, is added in an amount of 1% by weight based on the total weight of the composition.
  • the preparation method of the components (A) to (G) is not particularly limited, and it can be obtained by a conventional method in the art, or is commercially available.
  • the preparation method of the glass shatterproof glue composition of the invention firstly mixes the components (A), (D) and silazane in an internal mixer for 2 hours, and then vacuums at 170 ° C for 2 hours, and then discharges the mixture into other materials.
  • Component each component is divided by mass
  • components (F) and (G) and other additives such as inorganic fillers, pigments, flame retardants and heat-resistant agents are added to prepare curable glass.
  • a glass article comprising a glass body, the glass body being coated with the present A cured product of the glass shatterproof adhesive composition of the invention.
  • the use of the glass shatterproof adhesive composition of the present invention in a glass product comprises: first diluting the mixed composition in an organic solvent, and the type of the organic solvent is not limited, and may be a conventional organic solvent in the technical field.
  • the type of the organic solvent is not limited, and may be a conventional organic solvent in the technical field.
  • butyl acetate is used in the specific embodiment of the invention.
  • the dilution concentration is preferably diluted to a viscosity of 10 to 100 mPa ⁇ s; then the diluted composition is coated on the glass body, and the thickness of the coating layer may be selected to have different thicknesses as needed, for example, preferably 20 to 200 ⁇ m;
  • the glass article coated with the composition was placed in an oven, cured at a temperature of 80-150 ° C, and cooled to room temperature.
  • the glass shatterproof adhesive composition of the invention is kept at 100 ° C for 1 h, and then maintained at 150 ° C for 3 h, and then formed to have a tensile strength of 8.0 MPa or more at a temperature of 25 ° C and a humidity of 60% RH.
  • the hardness values of the three points were measured using a Shore A hardness tester and the hardness was equal to or greater than A70. It has the advantages of good surface leveling and excellent shatterproof properties.
  • This component is an organosilicon compound having a viscosity of 1500 mPa ⁇ s at 25 ° C and a vinyl molar content of 0.005 mol/100 g.
  • This component is an organosilicon compound having a viscosity of 3000 mPa ⁇ s at 25 ° C and a vinyl molar content of 0.003 mol/100 g.
  • This component is an organosilicon compound having a viscosity of 5000 mPa ⁇ s at 25 ° C and a vinyl molar content of 0.002 mol/100 g.
  • This component is an organosilicon compound having a viscosity of 9000 mPa ⁇ s at 25 ° C and a vinyl molar content of 0.0015 mol/100 g.
  • This component is an organosilicon compound having a viscosity of 12000 mPa ⁇ s at 25 ° C and a vinyl molar content of 0.001 mol/100 g.
  • This component is an organosilicon compound having a viscosity of 25 mPa ⁇ s at 25 ° C and a hydrogen molar content of 0.5 mol/100 g.
  • This component was an organosilicon compound having a viscosity of 34 mPa ⁇ s at 25 ° C and a hydrogen molar content of 0.7 mol/100 g.
  • This component is an organosilicon compound having a viscosity of 30 mPa ⁇ s at 25 ° C and a hydrogen molar content of 1.0 mol/100 g.
  • This component is an organosilicon compound having a viscosity of 30 mPa ⁇ s at 25 ° C and a hydrogen molar content of 1.5 mol / 100 g.
  • This component is an organosilicon compound having a viscosity of 10 mPa ⁇ s at 25 ° C and a hydrogen molar content of 1.7 mol/100 g.
  • the component was solid at 25 ° C, had a number average molecular weight of 3,400 and a vinyl content of 0.10 mol / 100 g.
  • D1 is 150 mesh
  • D2 is 200 mesh
  • D3 is 400 mesh
  • D4 is 4000 mesh
  • Adhesion Promoter Chengdu Chenguang Chemical Research Institute KH560
  • the resin (A), (D) and silazane prepared in the synthesis example were mixed for 2 hours in an internal mixer, and then evacuated at 170 ° C for 2 hours, and then discharged, and other components were mixed according to the combination shown in Table 1 ( The components are in parts by mass to give the composition of the present invention.
  • the obtained composition was poured into a mold, and heat-cured to form a film.
  • the baking conditions were: curing at 100 ° C for 1 hour, and curing at 150 ° C for 3 hours. And measuring the hardness, tensile strength, elongation at break of the obtained film Rate, test results are shown in Table 1.
  • a sheet having a thickness of about 2 mm was prepared, kept at 100 ° C for 1 h, and then cured at 150 ° C for 3 h, and then the sheet was processed into a dumbbell shape and utilized at 25 ° C and 60% RH.
  • the universal material testing machine tests its tensile strength and elongation at break.
  • the obtained composition was diluted with butyl acetate to a viscosity of 40 mPa ⁇ s, sprayed on the surface of a 40 W glass bulb lamp, coated with 100 ⁇ m, and cured in an oven at 80 ° C for 15 minutes. After cooling, the bulb was placed on the wooden floor. Above, 1.5m from the ground, the lamp holder is facing up, the bulb is facing down, and it is free to land three times to see if the glass is broken.
  • the viscosity of the vinyl resin was between 3,000 and 9000, and the composition was excellent in performance.
  • the amount of fumed silica was between 3 and 10 parts, and the composition was excellent in performance.
  • the mesh of fumed silica was between 200 and 4000 mesh, and the composition was excellent in performance.
  • the amount of the MQ resin was between 20 and 40 parts, and the composition was excellent in performance.
  • the hydrogen content was between 0.7 and 1.6, and the composition was excellent in performance.
  • the amount of the MQ resin was less than 20 parts or more, the cured product was too soft or too brittle, and the glass shatterproof property was poor.
  • the invention has the beneficial effects that the glass shatterproof adhesive composition of the invention has simple production process and only needs low temperature baking, the coating maintains good appearance and light extraction efficiency, and the surface level is good and solidified.
  • the appearance is colorless and transparent, and has excellent shatterproof properties.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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Abstract

Provided is a glass shatter-proof glue composition, comprising: (A) an organopolysiloxane having a straight chain structure and having at least two alkenyl groups bonded with silicon per molecule; (B) a polyorganohydrogensiloxane having a straight chain structure and having at least two hydrogen atoms bonded with silicon per molecule; (C) an organopolysiloxane having a solid three-dimensional structure and comprising a R 1 3SiO 1/2 unit and an SiO 4/2 unit; (D) a fumed silica with a mesh number of 200-4000 mesh; and (E) a hydrosilylation catalyst in an amount sufficient to accelerate the curing of the composition. Also provided are a glass product and the application method of the glass shatter-proof glue combination on the glass product. The production process of the composition is simple, only requiring low-temperature baking, and has a high production efficiency.

Description

玻璃防碎胶组合物及玻璃制品及应用Glass shatterproof adhesive composition and glass product and application 技术领域Technical field
本发明涉及一种有机硅组合物，特别涉及一种玻璃防碎胶组合物及其应用，以及涂覆有所述组合物的玻璃制品。The present invention relates to a silicone composition, and more particularly to a glass shatterproof adhesive composition and use thereof, and a glass article coated with the composition.
背景技术Background technique
随着清洁能源的发展，特别是LED灯及光伏产业的发展，对相关玻璃制品的性能要求也越来越高。除了美观，高透光性等要求之外，对玻璃制品的抗冲击强度要求也具有很高的要求。With the development of clean energy, especially the development of LED lamps and photovoltaic industry, the performance requirements of related glass products are also getting higher and higher. In addition to aesthetics, high light transmission and other requirements, the impact strength requirements of glass products are also very high.
提高玻璃制品的抗冲击强度通常具有如下方式，一是通过改进玻璃配方或工艺方法等手段来提高玻璃制品本身的强度；二是给玻璃制品上贴一层防爆强化膜，例如汽车玻璃防爆膜；三是通过给玻璃制品表面涂覆一层涂料并加以固化，实现玻璃制品的抗冲击性能。Increasing the impact strength of glass products generally has the following methods: one is to improve the strength of the glass product itself by improving the glass formulation or the process method; the second is to apply a layer of explosion-proof reinforced film to the glass product, such as an automobile glass explosion-proof film; The third is to achieve the impact resistance of the glass product by applying a layer of paint to the surface of the glass article and curing it.
现有技术中，对于第三种方式，CN100569685C公开了一种玻璃防碎胶的生产工艺，是将有机硅树脂、有机硅橡胶、醋酸丁酯、有机硅树脂固化剂或有机硅橡胶固化剂按重量比常温下混合、搅拌、研磨、过滤，得到乳白色玻璃涂料，再将涂料喷涂在玻璃上，再经80-100℃低温烘干和180-220℃高温烘干。此外，CN101724340A也公开了一种玻璃防碎胶用涂料的生产方法及其应用方法，将卤磷酸钙粉或硅微粉、有机硅树脂、二氧化硅消光剂、有机硅树脂固化物、无机颜料、溶剂分散均匀，通过过滤机滤除杂质，静置10-36小时，得白色胶状的防碎涂料，将涂料喷涂在玻璃上，再经180-250℃高温烘干。In the prior art, for the third mode, CN100569685C discloses a production process of a glass shatterproof adhesive, which is a silicone resin, a silicone rubber, a butyl acetate, a silicone resin curing agent or a silicone rubber curing agent. The weight is mixed, stirred, ground and filtered at room temperature to obtain a milky white glass coating, and then the coating is sprayed on the glass, and then dried at a low temperature of 80-100 ° C and dried at a high temperature of 180-220 ° C. In addition, CN101724340A also discloses a method for producing a glass anti-crushing coating and a method for applying the same, which comprises a calcium halophosphate powder or a silicon micro powder, a silicone resin, a silica matting agent, a silicone resin cured product, an inorganic pigment, The solvent is evenly dispersed, and the impurities are filtered through a filter, and left to stand for 10-36 hours to obtain a white gel-like shatterproof coating, and the coating is sprayed on the glass, and then dried at a high temperature of 180-250 °C.
上述现有技术的不足之处在于玻璃涂料的生产工艺及其应用步骤较复杂，且均需要高温烘烤，不利于提高生产效率。The shortcoming of the above prior art is that the production process of the glass coating and the application steps thereof are complicated, and both require high temperature baking, which is not conducive to improving production efficiency.
发明内容Summary of the invention
本发明所要解决的技术问题是克服现有技术的上述缺陷，提供一种生产工艺简单，只需要低温烘烤，生产效率高的玻璃防碎胶组合物。The technical problem to be solved by the present invention is to overcome the above-mentioned drawbacks of the prior art, and to provide a glass shatterproof adhesive composition which is simple in production process and requires only low-temperature baking and high production efficiency.
本发明提供的一种玻璃防碎胶组合物，包括： The invention provides a glass shatterproof glue composition, comprising:
(A)每一分子具有至少两个与硅键合的链烯基的直链结构有机聚硅氧烷，所述有机聚硅氧烷的粘度为3000-9000mPa·s；(A) a linear structure organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule, the organopolysiloxane having a viscosity of from 3,000 to 9000 mPa·s;
(B)每一分子具有至少两个与硅键合的氢原子的直链结构聚有机氢化硅氧烷，所述聚有机氢化硅氧烷的氢摩尔含量为0.7-1.6摩尔/100g；(B) a linear structure polyorganohydridosiloxane having at least two silicon-bonded hydrogen atoms per molecule, the polyorganohydridosiloxane having a hydrogen molar content of from 0.7 to 1.6 mol/100 g;
(C)包括R1 3SiO1/2单元和SiO4/2单元的固态三维结构有机聚硅氧烷，R1选自相同或不相同的链烯基、不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基；(C) a solid three-dimensional organopolysiloxane comprising R 1 3 SiO 1/2 units and SiO 4/2 units, R 1 being selected from the same or different alkenyl groups, containing no aromatic hydrocarbons and not containing aliphatic a monovalent substituted or unsubstituted hydrocarbon group of a saturated bond;
(D)目数为200-4000目的气相二氧化硅；(D) fumed silica having a mesh number of 200-4000 mesh;
相对于100重量份的组合物总量，所述组分(C)的用量为20-40重量份，所述组分(D)气相二氧化硅的用量为3-10重量份。The component (C) is used in an amount of 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the composition, and the component (D) fumed silica is used in an amount of 3 to 10 parts by weight.
(E)用量足以促进该组合物固化的氢化硅烷化催化剂。(E) a hydrosilylation catalyst in an amount sufficient to promote solidification of the composition.
为解决上述技术问题，本发明还提供了一种玻璃制品，包括玻璃本体，其中，所述玻璃本体上涂布有本发明所述的玻璃防碎胶组合物的固化物。In order to solve the above technical problems, the present invention also provides a glass article comprising a glass body, wherein the glass body is coated with a cured product of the glass shatterproof adhesive composition of the present invention.
为解决上述技术问题，本发明还提供了一种玻璃防碎胶组合物在玻璃制品上的应用，其特征在于，包括如下步骤：In order to solve the above technical problems, the present invention also provides a glass shatterproof adhesive composition for use in a glass article, characterized in that it comprises the following steps:
稀释：将权利要求1-8任一项所述的组合物用有机溶剂进行稀释；Dilution: the composition of any one of claims 1-8 is diluted with an organic solvent;
涂覆：将所述稀释后的组合物涂覆在玻璃制品上；Coating: coating the diluted composition on a glass article;
固化：将涂覆有所述组合物的玻璃制品在80-150℃温度下固化；Curing: curing the glass article coated with the composition at a temperature of 80-150 ° C;
冷却：冷却至室温。Cooling: Cool to room temperature.
本发明的有益效果：与现有技术相比，本发明的玻璃防碎胶组合物，生产工艺简单，只需要低温烘烤，涂层保持着良好的外观和出光效率，表面流平好、固化后外观无色透明，具有优异的防碎性能。The invention has the beneficial effects that the glass shatterproof adhesive composition of the invention has simple production process and only needs low temperature baking, the coating maintains good appearance and light extraction efficiency, and the surface level is good and solidified. The appearance is colorless and transparent, and has excellent shatterproof properties.
具体实施方式detailed description
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步的详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects of the present invention more clear, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
以下描述中，Vi指代为乙烯基，Me指代为甲基，MQ构型指具有SiO4/2单元的三维结构，MD构型指具有SiO2/2单元的直链结构。In the following description, Vi denotes a vinyl group, Me denotes a methyl group, MQ configuration means a three-dimensional structure having SiO 4/2 units, and MD configuration means a linear structure having SiO 2/2 units.
本发明提供的一种玻璃防碎胶组合物，包括：The invention provides a glass shatterproof glue composition, comprising:
(A)每一分子具有至少两个与硅键合的链烯基的直链结构有机聚硅氧烷， 所述有机聚硅氧烷的粘度为3000-9000mPa·s；(A) a linear structure organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule, The organopolysiloxane has a viscosity of 3000-9000 mPa·s;
(B)每一分子具有至少两个与硅键合的氢原子的直链结构聚有机氢化硅氧烷，所述聚有机氢化硅氧烷的氢摩尔含量为0.7-1.6摩尔/100g；(B) a linear structure polyorganohydridosiloxane having at least two silicon-bonded hydrogen atoms per molecule, the polyorganohydridosiloxane having a hydrogen molar content of from 0.7 to 1.6 mol/100 g;
(C)包括R1 3SiO1/2单元和SiO4/2单元的固态三维结构有机聚硅氧烷，R1选自相同或不相同的链烯基、不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基；(C) a solid three-dimensional organopolysiloxane comprising R 1 3 SiO 1/2 units and SiO 4/2 units, R 1 being selected from the same or different alkenyl groups, containing no aromatic hydrocarbons and not containing aliphatic a monovalent substituted or unsubstituted hydrocarbon group of a saturated bond;
(D)目数为200-4000目的气相二氧化硅；(D) fumed silica having a mesh number of 200-4000 mesh;
相对于100重量份的组合物总量，所述组分(C)的用量为20-40重量份，所述组分(D)气相二氧化硅的用量为3-10重量份。The component (C) is used in an amount of 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the composition, and the component (D) fumed silica is used in an amount of 3 to 10 parts by weight.
(E)用量足以促进该组合物固化的氢化硅烷化催化剂。(E) a hydrosilylation catalyst in an amount sufficient to promote solidification of the composition.
其中，所述组分(A)是本发明组合物的主要成分，组分(A)和(C)中的链烯基共同与组分(B)中的与硅键合的氢原子相互反应，形成交联键，并进行固化。组分(A)的分子结构是每一分子具有至少两个与硅键合的链烯基的直链分子链结构。作为优选实施方式，所述组分(A)优选为包括R1 3SiO1/2单元和R2 2SiO2/2单元的液态直链结构有机聚硅氧烷，其中R1和R2选自相同或不相同的链烯基、不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基。Wherein component (A) is a main component of the composition of the present invention, and alkenyl groups in components (A) and (C) are mutually reacted with silicon-bonded hydrogen atoms in component (B). Form a crosslink bond and cure. The molecular structure of the component (A) is a linear molecular chain structure having at least two silicon-bonded alkenyl groups per molecule. As a preferred embodiment, the component (A) is preferably a liquid linear structure organopolysiloxane comprising R 1 3 SiO 1/2 units and R 2 2 SiO 2/2 units, wherein R 1 and R 2 are selected Monovalent substituted or unsubstituted hydrocarbyl groups from the same or different alkenyl groups, containing no aromatic hydrocarbons, and no aliphatic unsaturated bonds.
直链结构的组分(A)和三维结构的组分(C)共混后，其中的链烯基共同与组分(B)中的与硅键合的氢原子相互反应，形成交联键，并进行固化。组分(A)中的链烯基可用乙烯基、丙烯基、丁烯基、戊烯基和己烯基为代表，最优选为乙烯基。所述组分(A)中的不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基，可包括下述基团：甲基、乙基、丙基、丁基、戊基、己基、庚基或类似的烷基，氯代甲基、3-氯丙基或类似的卤代烷基，最优选为甲基。为了进一步提高所述组分(A)和组分(B)的反应性，所述链烯基的含量优选为0.001-0.05mol/100g；本发明对在组分(A)的粘度限定为3000-9000mPa·s，当组分(A)的粘度小于3000mPa·s时，则表现为玻璃防碎性能差；当组分(A)的粘度大于9000mPa·s时，则漆膜流平差，具体表现为流平时间变长，或者是漆膜厚度难以达到均一。After the component (A) of the linear structure and the component (C) of the three-dimensional structure are blended, the alkenyl group in common reacts with the silicon-bonded hydrogen atom in the component (B) to form a cross-linking bond. And curing. The alkenyl group in the component (A) may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, and most preferably a vinyl group. The monovalent substituted or unsubstituted hydrocarbon group in the component (A) which does not contain an aromatic hydrocarbon and does not contain an aliphatic unsaturated bond may include the following groups: methyl group, ethyl group, propyl group, butyl group, pentyl group. A hexyl, heptyl or similar alkyl group, a chloromethyl group, a 3-chloropropyl group or a similar haloalkyl group, most preferably a methyl group. In order to further increase the reactivity of the component (A) and the component (B), the content of the alkenyl group is preferably 0.001 to 0.05 mol/100 g; the viscosity of the component (A) in the present invention is limited to 3,000. -9000mPa·s, when the viscosity of the component (A) is less than 3000 mPa·s, the glass shatterproof performance is poor; when the viscosity of the component (A) is more than 9000 mPa·s, the paint film flow is adjusted, specifically It is manifested that the leveling time becomes longer, or the film thickness is difficult to achieve uniformity.
作为本发明的优选实施方式之一，所述(A)具有下述平均单元分子式，As one of preferred embodiments of the present invention, the (A) has the following average unit molecular formula,
R5R6 2SiO(R6 2SiO)a3SiR6 2R5，R 5 R 6 2 SiO(R 6 2 SiO) a3 SiR 6 2 R 5 ,
其中R5选自相同或不相同的链烯基，R6选自相同或不相同的单价取代或未取代的烷基，65<a3<900。其中R5中的链烯基可用乙烯基、丙烯基、丁烯基、 戊烯基和己烯基为代表，最优选为乙烯基。所述R6中的单价取代或未取代的烷基，可包括下述基团：甲基、乙基、丙基、丁基、戊基、己基、庚基或类似的烷基，最优选为甲基。Wherein R 5 is selected from the same or different alkenyl groups, and R 6 is selected from the same or different monovalent substituted or unsubstituted alkyl groups, 65 < a3 < 900. The alkenyl group in R 5 may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, and most preferably a vinyl group. The monovalent substituted or unsubstituted alkyl group in R 6 may include a group: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or the like, most preferably methyl.
例如，所述组分(A)可包括如下分子式作为代表：For example, the component (A) may include the following molecular formula as a representative:
(CH2＝CH)(CH3)2SiO[(CH3)2SiO]a3Si(CH3)2(CH2＝CH)。(CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] a3 Si(CH 3 ) 2 (CH 2 =CH).
所述组分(B)是本发明组合物的主要成分之一，这一组分中的与硅键合的氢原子与组分(A)和组分(C)中的链烯基相互反应，形成交联键，并进行固化。组分(B)的分子结构是每一分子具有至少两个与硅键合的氢原子的直链分子链结构。作为优选实施方式，所述组分(B)优选为包括R3 3SiO1/2单元和R4 2SiO2/2单元的液态直链结构聚有机氢化硅氧烷，R3和R4选自相同或不相同的不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基和氢原子。组分(B)中的不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基，可包括下述基团：甲基、乙基、丙基、丁基、戊基、己基、庚基或类似的烷基，氯代甲基、3-氯丙基或类似的卤代烷基，最优选为甲基。本发明对在组分(B)中与硅键合的氢摩尔含量限定为0.7-1.6mol/100g。当组分(B)的氢摩尔含量小于0.7mol/100g时，则表现为固化物的断裂伸长率比较低，影响了玻璃防碎性能；当组分(B)的氢摩尔含量大于1.6mol/100g时，也表现为固化物的断裂伸长率比较低，影响了玻璃防碎性能。The component (B) is one of the main components of the composition of the present invention, and the silicon-bonded hydrogen atom in this component reacts with the alkenyl group in the component (A) and the component (C). Form a crosslink bond and cure. The molecular structure of the component (B) is a linear molecular chain structure having at least two silicon-bonded hydrogen atoms per molecule. As a preferred embodiment, the component (B) is preferably a liquid linear structure polyorganohydridosiloxane comprising R 3 3 SiO 1/2 units and R 4 2 SiO 2/2 units, R 3 and R 4 selected Monovalent substituted or unsubstituted hydrocarbyl and hydrogen atoms which are the same or different from aromatic hydrocarbon-free and free of aliphatic unsaturated bonds. The monovalent substituted or unsubstituted hydrocarbon group which does not contain an aromatic hydrocarbon and does not contain an aliphatic unsaturated bond in the component (B) may include the following groups: methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. , heptyl or similar alkyl, chloromethyl, 3-chloropropyl or similar haloalkyl, most preferably methyl. The present invention defines a molar ratio of hydrogen bonded to silicon in the component (B) to be 0.7 to 1.6 mol/100 g. When the hydrogen content of the component (B) is less than 0.7 mol/100 g, the elongation at break of the cured product is relatively low, which affects the glass shatterproof property; when the hydrogen content of the component (B) is more than 1.6 mol At /100g, it also shows that the elongation at break of the cured product is relatively low, which affects the glass shatterproof performance.
进一步，所述组分(B)中的与硅键合的氢原子与组分(A)和(C)中的链烯基的摩尔量之比为0.9-3.0。Further, the ratio of the silicon-bonded hydrogen atom in the component (B) to the molar amount of the alkenyl groups in the components (A) and (C) is from 0.9 to 3.0.
作为本发明的优选实施方式之一，所述(B)具有下述平均单元分子式，As one of preferred embodiments of the present invention, the (B) has the following average unit molecular formula,
R8 3SiO(R8 2SiO)b1(R8HSiO)b2Si R8 3，R 8 3 SiO(R 8 2 SiO) b1 (R 8 HSiO) b2 Si R 8 3 ,
其中R8选自相同或不相同的单价取代或未取代的烷基，0.2<b1<0.8，0.2<b2<0.8，且b1+b2＝1。所述R8可包括下述基团：甲基、乙基、丙基、丁基、戊基、己基、庚基或类似的烷基，氯代甲基、3-氯丙基或类似的卤代烷基，最优选为甲基。Wherein R 8 is selected from the same or different monovalent substituted or unsubstituted alkyl groups, 0.2 < b1 < 0.8, 0.2 < b2 < 0.8, and b1 + b2 = 1. The R 8 may include a group: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or the like alkyl, chloromethyl, 3-chloropropyl or similar alkyl halide The group is most preferably a methyl group.
例如，所述组分(B)可包括如下分子式作为代表：For example, the component (B) may include the following molecular formula as a representative:
(CH3)3SiO((CH3)2SiO)b1(CH3HSiO)b2Si(CH3)3。(CH 3 ) 3 SiO((CH 3 ) 2 SiO) b1 (CH 3 HSiO) b2 Si(CH 3 ) 3 .
本发明中，对组分(A)和组分(B)的用量没有特别限定，可以作为本领域常规用量使用，例如组分(A)的组分(B)重量用量比为1:99-99:1。更优选为相对于100重量份的组合物总量，组分(A)的用量为20-75重量份，组分(B) 的用量为1-30重量份。In the present invention, the amounts of the component (A) and the component (B) are not particularly limited and may be used in a conventional amount in the art, for example, the component (B) of the component (A) is used in a weight ratio of 1:99- 99:1. More preferably, component (A) is used in an amount of 20 to 75 parts by weight, based on 100 parts by weight of the total amount of the composition, component (B) The amount used is 1 to 30 parts by weight.
组分(C)的分子结构是固态三维结构分子链结构，且在一个分子中应当含有R1 3SiO1/2单元和SiO4/2单元。组分(C)中的链烯基可用乙烯基、丙烯基、丁烯基、戊烯基和己烯基为代表，最优选为乙烯基。所述组分(C)中的不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基，可包括下述基团：甲基、乙基、丙基、丁基、戊基、己基、庚基或类似的烷基，氯代甲基、3-氯丙基或类似的卤代烷基，最优选为甲基。为了进一步提高所述组分(C)和组分(B)的反应性，所述链烯基的含量为0.01-0.30mol/100g，优选为0.02-0.25mol/100g。The molecular structure of the component (C) is a solid three-dimensional structure molecular chain structure, and should contain R 1 3 SiO 1/2 units and SiO 4/2 units in one molecule. The alkenyl group in component (C) may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, and most preferably a vinyl group. The monovalent substituted or unsubstituted hydrocarbon group in the component (C) which does not contain an aromatic hydrocarbon and does not contain an aliphatic unsaturated bond may include the following groups: methyl group, ethyl group, propyl group, butyl group, pentyl group. A hexyl, heptyl or similar alkyl group, a chloromethyl group, a 3-chloropropyl group or a similar haloalkyl group, most preferably a methyl group. In order to further increase the reactivity of the component (C) and the component (B), the alkenyl group is contained in an amount of from 0.01 to 0.30 mol / 100 g, preferably from 0.02 to 0.25 mol / 100 g.
本发明中，相对于100重量份的组合物总量，所述组分(C)的用量限定为20-40重量份，当组分(C)的用量小于20重量份时，则固化物的硬度偏低，拉伸强度和断裂伸长率均偏低，具体表现为固化物偏软，防碎性能差；当组分(C)的用量大于40重量份时，则硬度偏高，拉伸强度高但断裂伸长率偏低，表现为偏脆，防碎性能也差。In the present invention, the component (C) is used in an amount of 20 to 40 parts by weight based on 100 parts by weight of the total amount of the composition, and when the amount of the component (C) is less than 20 parts by weight, the cured product is used. The hardness is low, the tensile strength and the elongation at break are both low, which is characterized by softening of the cured product and poor shatterproof property; when the amount of the component (C) is more than 40 parts by weight, the hardness is high and stretching High strength but low elongation at break, showing brittleness and poor shatterproof performance.
作为本发明的优选实施方式之一，所述(C)具有下述平均单元分子式，As one of preferred embodiments of the present invention, the (C) has the following average unit molecular formula,
(SiO4/2)a1(R7R6 2SiO1/2)a2，(SiO 4/2 ) a1 (R 7 R 6 2 SiO 1/2 ) a2 ,
其中R7选自相同或不相同的链烯基，R6选自相同或不相同的单价取代或未取代的烷基，0.5<a1<0.99，0.01<a2<0.5，且a1+a2＝1。其中R7中的链烯基可用乙烯基、丙烯基、丁烯基、戊烯基和己烯基为代表，最优选为乙烯基，单价取代或未取代的烷基以甲基、乙基、丙基、丁基、戊基、己基、庚基或类似的烷基，最优选为甲基。所述R6中的单价取代或未取代的烷基，可包括下述基团：甲基、乙基、丙基、丁基、戊基、己基、庚基或类似的烷基，最优选为甲基。Wherein R 7 is selected from the same or different alkenyl groups, and R 6 is selected from the same or different monovalent substituted or unsubstituted alkyl groups, 0.5 < a1 < 0.99, 0.01 < a2 < 0.5, and a1 + a2 = 1 . Wherein the alkenyl group in R 7 may be represented by a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group, most preferably a vinyl group, and a monovalent substituted or unsubstituted alkyl group is a methyl group, an ethyl group, or a propyl group. Alkyl, butyl, pentyl, hexyl, heptyl or a similar alkyl group, most preferably a methyl group. The monovalent substituted or unsubstituted alkyl group in R 6 may include a group: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or the like, most preferably methyl.
例如，所述组分(C)可包括如下分子式作为代表：For example, the component (C) may include the following formula as a representative:
(SiO4/2)a1(CH2＝CH(CH3)2SiO1/2)a2；(SiO 4/2 ) a1 (CH 2 =CH(CH 3 ) 2 SiO 1/2 ) a2 ;
(SiO4/2)a1((CH2＝CH)2CH3SiO1/2)a2；(SiO 4/2 ) a1 ((CH 2 =CH) 2 CH 3 SiO 1/2 ) a2 ;
(SiO4/2)a1(CH2＝CH(CH3)2SiO1/2)a2((CH2＝CH)2CH3SiO1/2)a2’。(SiO 4/2 ) a1 (CH 2 =CH(CH 3 ) 2 SiO 1/2 ) a2 ((CH 2 =CH) 2 CH 3 SiO 1/2 ) a2' .
本发明中，组分(D)作为主要成分之一，在组合物中起增韧补强的作用。组分(D)为气相二氧化硅，其目数限定为200-4000目，当小于200目时，表现为固化后漆膜浑浊，影响灯泡出光；大于4000目时，成本太高。本发明中，相对于100重量份的组合物总量，所述组分(D)的用量限定为3-10重量份，当组分(D)的用量小于3重量份时，表现为玻璃防碎性能差；当组分(D)的用量大于10重量份时，表现为漆膜流平差。 In the present invention, component (D) serves as one of the main components and functions as a toughening and reinforcing agent in the composition. Component (D) is fumed silica, and its mesh number is limited to 200-4000 mesh. When it is less than 200 mesh, it shows that the paint film is turbid after curing, which affects the light output of the bulb; when it is larger than 4000 mesh, the cost is too high. In the present invention, the component (D) is used in an amount of 3 to 10 parts by weight, based on 100 parts by weight of the total amount of the composition, and when the amount of the component (D) is less than 3 parts by weight, it is expressed as glass. The crushing performance is poor; when the amount of the component (D) is more than 10 parts by weight, the paint film flow is uneven.
本发明采用粘度3000-9000mPa·s的直链结构有机聚硅氧烷，这种设计使得树脂与气相二氧化硅密炼分散的过程中，能均匀的将附聚体气相二氧化硅分散成聚集体，形成三维网络结构，该三维网络结构即能提高强度、又提高了韧性，使玻璃制品从高处落下时，涂层起到缓冲保护作用，进而防止玻璃破碎。The invention adopts a linear structure organopolysiloxane with a viscosity of 3000-9000 mPa·s. This design enables the agglomerated fumed silica to be uniformly dispersed into agglomerated during the process of mixing and dispersing the resin and the fumed silica. The body forms a three-dimensional network structure, which can improve the strength and improve the toughness, so that when the glass product falls from a high place, the coating plays a buffering protection function, thereby preventing the glass from being broken.
本发明中，组分(E)是促使组分(A)和(C)中的链烯基与组分(B)中的硅键合的氢原子发生氢化硅烷化反应的催化剂。换句话说，组分(E)是促进组合物固化的触媒。其中，本发明对催化剂种类没有特别限定，本领域的常用催化剂均可，例如铂类催化剂、铑类催化剂或钯类催化剂，本发明优选为铂类催化剂。具体实例包括：铂黑、氯铂酸、氯铂酸的醇溶液、铂-链烯基硅氧烷络合物、铂-烯烃络合物等，优选为铂-链烯基硅氧烷络合物，对组分(E)的用量没有特别限制，其用量需足以促进该组合物固化反应即可。本发明采用氯铂酸的辛醇溶液(铂浓度为5wt％)作为催化剂。In the present invention, the component (E) is a catalyst which causes a hydrosilylation reaction between an alkenyl group in the components (A) and (C) and a silicon-bonded hydrogen atom in the component (B). In other words, component (E) is a catalyst that promotes curing of the composition. Here, the type of the catalyst in the present invention is not particularly limited, and a catalyst conventionally used in the art may be, for example, a platinum catalyst, a rhodium catalyst or a palladium catalyst, and the present invention is preferably a platinum catalyst. Specific examples include: platinum black, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, etc., preferably a platinum-alkenylsiloxane complex The amount of the component (E) to be used is not particularly limited, and it is preferably used in an amount sufficient to promote the curing reaction of the composition. The present invention employs an octanol solution of chloroplatinic acid (platinum concentration: 5 wt%) as a catalyst.
本发明的可固化的玻璃防碎胶组合物中，还可包括组分(F)加成反应抑制剂，其作用是为了延长本发明的可固化的玻璃防碎胶组合物的储存期，加成反应抑制剂是一种带有温度依赖性的物质，加热到一定程度时迅速失去其抑制性，而使得组合物发生固化反应。组分(F)的加成反应抑制剂的种类重量和添加量没有特别限制，可使用本领域常规抑制剂，添加量可视需要添加，例如，本发明中组分(F)为2-苯基-3-丁炔-2-醇，添加量为组合物总重量的0.1％。The curable glass shatterproof adhesive composition of the present invention may further comprise a component (F) addition reaction inhibitor for the purpose of prolonging the storage period of the curable glass shatterproof adhesive composition of the present invention. The reaction inhibitor is a temperature-dependent substance which, when heated to a certain extent, rapidly loses its inhibition, causing the composition to undergo a curing reaction. The kind weight and the addition amount of the addition reaction inhibitor of the component (F) are not particularly limited, and a conventional inhibitor in the art may be used, and the amount added may be added as needed. For example, the component (F) in the present invention is 2-benzene. The base 3-butyn-2-ol is added in an amount of 0.1% by weight based on the total weight of the composition.
此外，本发明的玻璃防碎胶组合物中，还可包括组分(G)附着力促进剂，其作用是增加防碎胶和玻璃之间的的结合力，防止灯具在长期点亮使用后高温带来的防碎胶劣化脱落。组分(G)附着力促进剂的种类重量和添加量没有特别限制，可使用本领域常规附着力促进剂，添加量可视需要添加，例如，本发明组分(G)附着力促进剂为成都晨光化工研究院生产的牌号为KH560的γ-缩水甘油醚氧丙基三甲氧基硅烷，添加量为组合物总重量的1％。In addition, the glass shatterproof adhesive composition of the present invention may further comprise a component (G) adhesion promoter, the function of which is to increase the bonding force between the shatterproof glue and the glass, and prevent the lamp from being used after long-term lighting. The shatterproof glue caused by high temperature deteriorates and falls off. The type weight and the addition amount of the component (G) adhesion promoter are not particularly limited, and a conventional adhesion promoter in the art may be used, and the amount of addition may be added as needed, for example, the component (G) adhesion promoter of the present invention is Γ-glycidoxypropyltrimethoxysilane, manufactured by Chengdu Chenguang Chemical Research Institute under the trade name KH560, is added in an amount of 1% by weight based on the total weight of the composition.
本发明中，对组分(A)-(G)的制备方法没有特别限定，可采用本领域常规方式制备获得，或商购获得。In the present invention, the preparation method of the components (A) to (G) is not particularly limited, and it can be obtained by a conventional method in the art, or is commercially available.
本发明所述玻璃防碎胶组合物的制备方法，先将组分(A)、(D)、硅氮烷在密炼机混合2小时后，在170℃抽真空2h后出料，混入其他组分(各组分按质量份数计)，并视需要添加组分(F)和(G)以及其他添加剂如无机填料、颜料、阻燃剂和耐热剂等，从而制备可固化的玻璃防碎胶组合物。The preparation method of the glass shatterproof glue composition of the invention firstly mixes the components (A), (D) and silazane in an internal mixer for 2 hours, and then vacuums at 170 ° C for 2 hours, and then discharges the mixture into other materials. Component (each component is divided by mass), and if necessary, components (F) and (G) and other additives such as inorganic fillers, pigments, flame retardants and heat-resistant agents are added to prepare curable glass. A shatterproof glue composition.
本发明中，提供一种玻璃制品，包括玻璃本体，所述玻璃本体上涂布有本 发明所述的玻璃防碎胶组合物的固化物。In the present invention, there is provided a glass article comprising a glass body, the glass body being coated with the present A cured product of the glass shatterproof adhesive composition of the invention.
本发明所述玻璃防碎胶组合物在玻璃制品上的应用，包括：先将上述混合后的组合物在有机溶剂中进行稀释，所述有机溶剂种类没有限定，可以为本技术领域常规有机溶剂，例如，本发明具体实施例中采用醋酸丁酯。稀释浓度优选为稀释至粘度为10-100mPa·s；然后将稀释后的组合物涂布在所述玻璃本体上，涂层厚度可以视需要而选择不同的厚度，例如优选为20-200μm；然后将涂覆有所述组合物的玻璃制品放入烘箱，在80-150℃温度下固化，冷却至室温。The use of the glass shatterproof adhesive composition of the present invention in a glass product comprises: first diluting the mixed composition in an organic solvent, and the type of the organic solvent is not limited, and may be a conventional organic solvent in the technical field. For example, butyl acetate is used in the specific embodiment of the invention. The dilution concentration is preferably diluted to a viscosity of 10 to 100 mPa·s; then the diluted composition is coated on the glass body, and the thickness of the coating layer may be selected to have different thicknesses as needed, for example, preferably 20 to 200 μm; The glass article coated with the composition was placed in an oven, cured at a temperature of 80-150 ° C, and cooled to room temperature.
本发明所述的玻璃防碎胶组合物，在100℃下保持1h，然后150℃下保持3h固化后，形成在温度25℃，湿度60％RH条件下的拉伸强度大于等于8.0Mpa，断裂伸长率大于等于105％的固化体。使用邵氏A型硬度计取三个点测量硬度值取平均值，硬度为大于等于A70。具有良好的表面流平性和优异的防碎性能的优点。The glass shatterproof adhesive composition of the invention is kept at 100 ° C for 1 h, and then maintained at 150 ° C for 3 h, and then formed to have a tensile strength of 8.0 MPa or more at a temperature of 25 ° C and a humidity of 60% RH. A cured body having an elongation of 105% or more. The hardness values of the three points were measured using a Shore A hardness tester and the hardness was equal to or greater than A70. It has the advantages of good surface leveling and excellent shatterproof properties.
合成实施例1Synthesis Example 1
将八甲基环四硅烷50.9g，四甲基二乙烯基四甲基二硅氧烷8.3g加入烧瓶，搅拌均匀后加入四甲基氢氧化铵2.5g，升温到120℃反应18小时，然后继续升温到180℃反应2小时，然后升温到200℃抽真空脱去低沸点物质，得到以下结构树脂：50.9 g of octamethylcyclotetrasilane and 8.3 g of tetramethyldivinyltetramethyldisiloxane were added to the flask, and after stirring, 2.5 g of tetramethylammonium hydroxide was added, and the mixture was heated to 120 ° C for 18 hours, and then reacted for 18 hours. The temperature was further raised to 180 ° C for 2 hours, and then the temperature was raised to 200 ° C to evacuate the low-boiling substance to obtain the following structural resin:
(CH2＝CH)(CH3)2SiO[(CH3)2SiO]84Si(CH3)2(CH2＝CH)  (A1)(CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 84 Si(CH 3 ) 2 (CH 2 =CH) (A1)
该组分为在25℃下粘度为1500mPa·s的有机硅化合物，且乙烯基摩尔含量在0.005摩尔/100g。This component is an organosilicon compound having a viscosity of 1500 mPa·s at 25 ° C and a vinyl molar content of 0.005 mol/100 g.
合成实施例2Synthesis Example 2
将八甲基环四硅烷50.2g，四甲基二乙烯基四甲基二硅氧烷5.2g加入烧瓶，搅拌均匀后加入四甲基氢氧化铵2.5g，升温到120℃反应14小时，然后继续升温到180℃反应3小时，然后升温到200℃抽真空脱去低沸点物质，得到以下结构树脂：50.2 g of octamethylcyclotetrasilane and 5.2 g of tetramethyldivinyltetramethyldisiloxane were added to the flask, and after stirring, 2.5 g of tetramethylammonium hydroxide was added, and the mixture was heated to 120 ° C for 14 hours, and then reacted for 14 hours. The temperature was further raised to 180 ° C for 3 hours, and then the temperature was raised to 200 ° C to evacuate the low-boiling substance to obtain the following structural resin:
(CH2＝CH)(CH3)2SiO[(CH3)2SiO]130Si(CH3)2(CH2＝CH)  (A2)(CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 130 Si(CH 3 ) 2 (CH 2 =CH) (A2)
该组分为在25℃下粘度为3000mPa·s的有机硅化合物，且乙烯基摩尔含量在0.003摩尔/100g。 This component is an organosilicon compound having a viscosity of 3000 mPa·s at 25 ° C and a vinyl molar content of 0.003 mol/100 g.
合成实施例3Synthesis Example 3
将八甲基环四硅烷50.4g，四甲基二乙烯基四甲基二硅氧烷1.4g加入烧瓶，搅拌均匀后加入四甲基氢氧化铵2.5g，升温到120℃反应15小时，然后继续升温到180℃反应2小时，然后升温到200℃抽真空脱去低沸点物质，得到以下结构树脂：50.4 g of octamethylcyclotetrasilane and 1.4 g of tetramethyldivinyltetramethyldisiloxane were added to the flask, and after stirring, 2.5 g of tetramethylammonium hydroxide was added, and the mixture was heated to 120 ° C for 15 hours, and then reacted for 15 hours. The temperature was further raised to 180 ° C for 2 hours, and then the temperature was raised to 200 ° C to evacuate the low-boiling substance to obtain the following structural resin:
(CH2＝CH)(CH3)2SiO[(CH3)2SiO]280Si(CH3)2(CH2＝CH)  (A3)(CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 280 Si(CH 3 ) 2 (CH 2 =CH) (A3)
该组分为在25℃下粘度为5000mPa·s的有机硅化合物，且乙烯基摩尔含量在0.002摩尔/100g。This component is an organosilicon compound having a viscosity of 5000 mPa·s at 25 ° C and a vinyl molar content of 0.002 mol/100 g.
合成实施例4Synthesis Example 4
将八甲基环四硅烷50.2g，四甲基二乙烯基四甲基二硅氧烷1.1g加入烧瓶，搅拌均匀后加入四甲基氢氧化铵2.5g，升温到120℃反应12小时，然后继续升温到180℃反应4小时，然后升温到200℃抽真空脱去低沸点物质，得到以下结构树脂：50.2 g of octamethylcyclotetrasilane and 1.1 g of tetramethyldivinyltetramethyldisiloxane were added to the flask, and after stirring, 2.5 g of tetramethylammonium hydroxide was added, and the mixture was heated to 120 ° C for 12 hours, and then reacted for 12 hours. The temperature was further raised to 180 ° C for 4 hours, and then the temperature was raised to 200 ° C to evacuate the low-boiling substance to obtain the following structural resin:
(CH2＝CH)(CH3)2SiO[(CH3)2SiO]360Si(CH3)2(CH2＝CH)  (A4)(CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 360 Si(CH 3 ) 2 (CH 2 =CH) (A4)
该组分为在25℃下粘度为9000mPa·s的有机硅化合物，且乙烯基摩尔含量在0.0015摩尔/100gThis component is an organosilicon compound having a viscosity of 9000 mPa·s at 25 ° C and a vinyl molar content of 0.0015 mol/100 g.
合成实施例5Synthesis Example 5
将八甲基环四硅烷50.4g，四甲基二乙烯基四甲基二硅氧烷0.9g加入烧瓶，搅拌均匀后加入四甲基氢氧化铵2.5g，升温到120℃反应15小时，然后继续升温到180℃反应6小时，然后升温到200℃抽真空脱去低沸点物质，得到以下结构树脂：50.4 g of octamethylcyclotetrasilane and 0.9 g of tetramethyldivinyltetramethyldisiloxane were added to the flask, and after stirring, 2.5 g of tetramethylammonium hydroxide was added, and the mixture was heated to 120 ° C for 15 hours, and then reacted for 15 hours. The temperature was further raised to 180 ° C for 6 hours, and then the temperature was raised to 200 ° C to evacuate the low-boiling substance to obtain the following structural resin:
(CH2＝CH)(CH3)2SiO[(CH3)2SiO]450Si(CH3)2(CH2＝CH)(A5)(CH 2 =CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] 450 Si(CH 3 ) 2 (CH 2 =CH)(A5)
该组分为在25℃下粘度为12000mPa·s的有机硅化合物，且乙烯基摩尔含量在0.001摩尔/100g。This component is an organosilicon compound having a viscosity of 12000 mPa·s at 25 ° C and a vinyl molar content of 0.001 mol/100 g.
合成实施例6Synthesis Example 6
20.3g Me3SiOSiMe3，80.2g(Me2SiO)4以及50g Me3SiO(MeHSiO)mSiMe3(成都晨光化工研究院)混合，加入7g份质量百分比98％的浓硫酸作催化剂，在室温下平衡5h，静置分层，除去酸水层，油层用Na2CO3 中和30min，过滤后得到收率达95％(质量分数)的以下产物：20.3g Me 3 SiOSiMe 3 , 80.2g (Me 2 SiO) 4 and 50g Me 3 SiO(MeHSiO) m SiMe 3 (Chengdu Chenguang Research Institute) were mixed, adding 7g parts by weight of 98% concentrated sulfuric acid as catalyst, at room temperature After equilibration for 5 h, the mixture was allowed to stand for stratification, and the acid water layer was removed. The oil layer was neutralized with Na 2 CO 3 for 30 min, and filtered to obtain the following product with a yield of 95% (mass fraction):
Me3SiO(MeHSiO)5(Me2SiO)7SiMe3。  (B1)Me 3 SiO(MeHSiO) 5 (Me 2 SiO) 7 SiMe 3 . (B1)
该组分为在25℃下粘度为25mPa·s的有机硅化合物，且氢摩尔含量在0.5摩尔/100g。This component is an organosilicon compound having a viscosity of 25 mPa·s at 25 ° C and a hydrogen molar content of 0.5 mol/100 g.
合成实施例7Synthesis Example 7
20.3g Me3SiOSiMe3，70g(Me2SiO)4以及55.6g Me3SiO(MeHSiO)mSiMe3(成都晨光化工研究院)混合，加入7g份质量百分比98％的浓硫酸作催化剂，在室温下平衡5h，静置分层，除去酸水层，油层用Na2CO3中和30min，过滤后得到收率达95％(质量分数)的以下产物：20.3g Me 3 SiOSiMe 3 , 70g (Me 2 SiO) 4 and 55.6g Me 3 SiO(MeHSiO) m SiMe 3 (Chengdu Chenguang Research Institute) were mixed, adding 7g parts by weight of 98% concentrated sulfuric acid as catalyst, at room temperature After equilibration for 5 h, the mixture was allowed to stand for stratification, and the acid water layer was removed. The oil layer was neutralized with Na 2 CO 3 for 30 min, and filtered to obtain the following product with a yield of 95% (mass fraction):
Me3SiO(MeHSiO)6(Me2SiO)6SiMe3。  (B2)Me 3 SiO(MeHSiO) 6 (Me 2 SiO) 6 SiMe 3 . (B2)
该组分为在25℃下粘度为34mPa·s的有机硅化合物，且氢摩尔含量在0.7摩尔/100g。This component was an organosilicon compound having a viscosity of 34 mPa·s at 25 ° C and a hydrogen molar content of 0.7 mol/100 g.
合成实施例8Synthesis Example 8
20.3g Me3SiOSiMe3，40.5g(Me2SiO)4以及60g Me3SiO(MeHSiO)mSiMe3(成都晨光化工研究院)混合，加入7g份质量百分比98％的浓硫酸作催化剂，在室温下平衡5h，静置分层，除去酸水层，油层用Na2CO3中和30min，过滤后得到收率达95％(质量分数)的以下产物：20.3g Me 3 SiOSiMe 3 , 40.5g (Me 2 SiO) 4 and 60g Me 3 SiO(MeHSiO) m SiMe 3 (Chengdu Chenguang Research Institute) were mixed, adding 7g parts by weight of 98% concentrated sulfuric acid as catalyst, at room temperature After equilibration for 5 h, the mixture was allowed to stand for stratification, and the acid water layer was removed. The oil layer was neutralized with Na 2 CO 3 for 30 min, and filtered to obtain the following product with a yield of 95% (mass fraction):
Me3SiO(MeHSiO)6(Me2SiO)4SiMe3。  (B3)Me 3 SiO(MeHSiO) 6 (Me 2 SiO) 4 SiMe 3 . (B3)
该组分为在25℃下粘度为30mPa·s的有机硅化合物，且氢摩尔含量在1.0摩尔/100g。This component is an organosilicon compound having a viscosity of 30 mPa·s at 25 ° C and a hydrogen molar content of 1.0 mol/100 g.
合成实施例9Synthesis Example 9
20.3g Me3SiOSiMe3，10.2g(Me2SiO)4以及80g Me3SiO(MeHSiO)mSiMe3(成都晨光化工研究院)混合，加入7g份质量百分比98％的浓硫酸作催化剂，在室温下平衡5h，静置分层，除去酸水层，油层用Na2CO3中和30min，过滤后得到收率达95％(质量分数)的以下产物：20.3g Me 3 SiOSiMe 3 , 10.2g (Me 2 SiO) 4 and 80g Me 3 SiO(MeHSiO) m SiMe 3 (Chengdu Chenguang Chemical Research Institute) were mixed, adding 7g parts by weight of 98% concentrated sulfuric acid as catalyst, at room temperature After equilibration for 5 h, the mixture was allowed to stand for stratification, and the acid water layer was removed. The oil layer was neutralized with Na 2 CO 3 for 30 min, and filtered to obtain the following product with a yield of 95% (mass fraction):
Me3SiO(MeHSiO)9(Me2SiO)1SiMe3。  (B4)Me 3 SiO(MeHSiO) 9 (Me 2 SiO) 1 SiMe 3 . (B4)
该组分为在25℃下粘度为30mPa·s的有机硅化合物，且氢摩尔含量在1.5摩尔/100g。 This component is an organosilicon compound having a viscosity of 30 mPa·s at 25 ° C and a hydrogen molar content of 1.5 mol / 100 g.
组分【B5】Component [B5]
Me3SiO(MeHSiO)mSiMe3(成都晨光化工研究院)Me 3 SiO(MeHSiO) m SiMe 3 (Chengdu Chenguang Chemical Research Institute)
该组分为在25℃下粘度为10mPa·s的有机硅化合物，且氢摩尔含量在1.7摩尔/100g。This component is an organosilicon compound having a viscosity of 10 mPa·s at 25 ° C and a hydrogen molar content of 1.7 mol/100 g.
合成实施例10Synthesis Example 10
将正硅酸乙酯10.4g加入烧瓶，依次加入无水乙醇30g和浓度为质量百分比37％的浓盐酸15g，70℃反应5分钟，加入四甲基二乙烯基四甲基二硅氧烷1.8g继续70℃回流240分钟，倒入分液漏斗，分去酸水层，有机层水洗到中性pH，倒入烧瓶，加入去离子水1g，70℃回流60min，水泵减压，得到以下结构的MQ树脂：10.4 g of tetraethyl orthosilicate was added to the flask, and 30 g of absolute ethanol and 15 g of concentrated hydrochloric acid having a concentration of 37% by mass were sequentially added, and reacted at 70 ° C for 5 minutes, and tetramethyldivinyltetramethyldisiloxane 1.8 was added. g Continue to reflux at 70 ° C for 240 minutes, pour into the separatory funnel, separate the acid water layer, wash the organic layer to neutral pH, pour into the flask, add 1 g of deionized water, reflux at 60 ° C for 60 min, depressurize the pump to obtain the following structure MQ resin:
平均组成式(ViMe2SiO0.5)0.07(SiO2)0.93  (C)Average composition formula (ViMe 2 SiO 0.5 ) 0.07 (SiO 2 ) 0.93 (C)
该组分25℃下为固体，数均分子量3400，乙烯基含量0.10mol/100g。The component was solid at 25 ° C, had a number average molecular weight of 3,400 and a vinyl content of 0.10 mol / 100 g.
组分【D1-D4】Component [D1-D4]
德国瓦克H30气相二氧化硅：D1是150目，D2是200目，D3是400目，D4是4000目Germany Wacker H30 fumed silica: D1 is 150 mesh, D2 is 200 mesh, D3 is 400 mesh, D4 is 4000 mesh
组分【E】Component [E]
加成反应催化剂：氯铂酸的辛醇溶液(铂浓度为5wt％)Addition reaction catalyst: octanol solution of chloroplatinic acid (platinum concentration: 5 wt%)
组分【F】Component [F]
抑制剂：2-苯基-3-丁炔-2-醇Inhibitor: 2-phenyl-3-butyn-2-ol
组分【G】Component [G]
附着力促进剂：成都晨光化工研究院KH560Adhesion Promoter: Chengdu Chenguang Chemical Research Institute KH560
实践实施例1～7以及比较例1～9Practical Examples 1 to 7 and Comparative Examples 1 to 9
先将合成实施例制备的树脂(A)、(D)、硅氮烷在密炼机混合2小时后，在170℃抽真空2h后出料，按照表1所示的组合混入其他组分(各组分按质量份数计)，得到本发明组合物。The resin (A), (D) and silazane prepared in the synthesis example were mixed for 2 hours in an internal mixer, and then evacuated at 170 ° C for 2 hours, and then discharged, and other components were mixed according to the combination shown in Table 1 ( The components are in parts by mass to give the composition of the present invention.
通过下述方法来评测得到的组合物的各物化性能。将结果记录于表1。The physical and chemical properties of the obtained composition were evaluated by the following methods. The results are reported in Table 1.
将得到的组合物倒入模具中，加热固化成型制成胶片，烘烤条件：100℃固化1小时，150℃固化3小时。并测定获得的胶片的硬度、拉伸强度、断裂伸长 率，测试结果见表1。The obtained composition was poured into a mold, and heat-cured to form a film. The baking conditions were: curing at 100 ° C for 1 hour, and curing at 150 ° C for 3 hours. And measuring the hardness, tensile strength, elongation at break of the obtained film Rate, test results are shown in Table 1.
【硬度】【hardness】
将得到的组合物脱泡后，取10g在100℃下保持1h，然后150℃下保持3h固化后，在25℃，60％RH的条件下使用邵氏A型硬度计取三个点测量硬度值，并记录平均值。After the obtained composition was defoamed, 10 g was kept at 100 ° C for 1 h, and then cured at 150 ° C for 3 h, and then three points were measured using a Shore A hardness tester at 25 ° C and 60% RH. Value and record the average.
【拉伸强度和断裂伸长率】[Tensile Strength and Elongation at Break]
将得到的组合物脱泡后，制备2mm左右厚度的薄片，在100℃下保持1h，然后150℃下保持3h固化后，将片加工成哑铃状，在25℃，60％RH的条件下利用万能材料试验机测试其拉伸强度和断裂伸长率。After defoaming the obtained composition, a sheet having a thickness of about 2 mm was prepared, kept at 100 ° C for 1 h, and then cured at 150 ° C for 3 h, and then the sheet was processed into a dumbbell shape and utilized at 25 ° C and 60% RH. The universal material testing machine tests its tensile strength and elongation at break.
【防摔测试】[Anti-fall test]
将得到的组合物用醋酸丁酯开稀到粘度40mPa·s，在40W的玻璃球泡灯表面喷涂，涂层100um，在80℃烘箱固化15分钟，冷却后，将球泡灯放置在木地板上方，距离地面1.5m，灯座朝上，球泡朝下，自由落地三次，观察玻璃是否碎裂。The obtained composition was diluted with butyl acetate to a viscosity of 40 mPa·s, sprayed on the surface of a 40 W glass bulb lamp, coated with 100 μm, and cured in an oven at 80 ° C for 15 minutes. After cooling, the bulb was placed on the wooden floor. Above, 1.5m from the ground, the lamp holder is facing up, the bulb is facing down, and it is free to land three times to see if the glass is broken.
表1Table 1
Figure PCTCN2015072108-appb-000001
Figure PCTCN2015072108-appb-000001
Figure PCTCN2015072108-appb-000002
Figure PCTCN2015072108-appb-000002
表2Table 2
Figure PCTCN2015072108-appb-000003
Figure PCTCN2015072108-appb-000003
如表1所示，实施例1-7，防碎测试通过，表面流平好、固化后外观无色透明，具有优异的防碎功能。 As shown in Table 1, in Examples 1-7, the shatterproof test was passed, the surface was well leveled, the appearance after curing was colorless and transparent, and the powder was excellent in shatterproof function.
如表1所示，实施例1-7，乙烯基树脂的粘度在3000-9000之间，组合物性能优异。As shown in Table 1, in Examples 1 to 7, the viscosity of the vinyl resin was between 3,000 and 9000, and the composition was excellent in performance.
如表1所示，实施例1-7，气相二氧化硅的用量在3-10份之间，组合物性能优异。As shown in Table 1, in Examples 1-7, the amount of fumed silica was between 3 and 10 parts, and the composition was excellent in performance.
如表1所示，实施例1-7，气相二氧化硅的目数在200-4000目之间，组合物性能优异。As shown in Table 1, in Examples 1-7, the mesh of fumed silica was between 200 and 4000 mesh, and the composition was excellent in performance.
如表1所示，实施例1-7，MQ树脂的用量在20-40份之间，组合物性能优异。As shown in Table 1, in Examples 1 to 7, the amount of the MQ resin was between 20 and 40 parts, and the composition was excellent in performance.
如表1所示，实施例1-7，含氢量0.7-1.6之间，组合物性能优异。As shown in Table 1, in Examples 1 to 7, the hydrogen content was between 0.7 and 1.6, and the composition was excellent in performance.
如表2所示，比较例1-2，气相二氧化硅的用量小于3份，玻璃防碎性能差；气相二氧化硅的用量大于10份，漆膜流平差。As shown in Table 2, in Comparative Example 1-2, the amount of fumed silica was less than 3 parts, and the glass shatterproof property was poor; the amount of fumed silica was more than 10 parts, and the paint film was leveled.
如表2所示，比较例3-4，乙烯基树脂的粘度小于3000mPa·s，玻璃防碎性能差；乙烯基树脂的粘度大于9000mPa·s，漆膜流平差。As shown in Table 2, in Comparative Example 3-4, the viscosity of the vinyl resin was less than 3000 mPa·s, and the glass shatterproof property was poor; the viscosity of the vinyl resin was more than 9000 mPa·s, and the paint film flow was poorly adjusted.
如表2所示，比较例5-6，MQ树脂的用量小于20份或大于40份，固化物太软或太脆，玻璃防碎性能差。As shown in Table 2, in Comparative Example 5-6, the amount of the MQ resin was less than 20 parts or more, the cured product was too soft or too brittle, and the glass shatterproof property was poor.
如表2所示，比较例7，气相二氧化硅的目数小于200目，固化后漆膜浑浊，影响灯泡出光。As shown in Table 2, in Comparative Example 7, the number of vapor phase silica was less than 200 mesh, and the film was turbid after curing, which affected the light emission of the bulb.
如表2所示，比较例8-9，含氢量小于0.7或大于1.6，固化物的断裂伸长率比较低，影响了玻璃防碎性能。As shown in Table 2, in Comparative Examples 8-9, the hydrogen content was less than 0.7 or more than 1.6, and the elongation at break of the cured product was relatively low, which affected the glass shatterproof performance.
本发明的有益效果：与现有技术相比，本发明的玻璃防碎胶组合物，生产工艺简单，只需要低温烘烤，涂层保持着良好的外观和出光效率，表面流平好、固化后外观无色透明，具有优异的防碎性能。The invention has the beneficial effects that the glass shatterproof adhesive composition of the invention has simple production process and only needs low temperature baking, the coating maintains good appearance and light extraction efficiency, and the surface level is good and solidified. The appearance is colorless and transparent, and has excellent shatterproof properties.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。 The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (11)

  1. 一种玻璃防碎胶组合物，其特征在于，包括：A glass shatterproof adhesive composition, comprising:
    (A)每一分子具有至少两个与硅键合的链烯基的直链结构有机聚硅氧烷，所述有机聚硅氧烷的粘度为3000-9000mPa·s；(A) a linear structure organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule, the organopolysiloxane having a viscosity of from 3,000 to 9000 mPa·s;
    (B)每一分子具有至少两个与硅键合的氢原子的直链结构聚有机氢化硅氧烷，所述聚有机氢化硅氧烷的氢摩尔含量为0.7-1.6摩尔/100g；(B) a linear structure polyorganohydridosiloxane having at least two silicon-bonded hydrogen atoms per molecule, the polyorganohydridosiloxane having a hydrogen molar content of from 0.7 to 1.6 mol/100 g;
    (C)包括R1 3SiO1/2单元和SiO4/2单元的固态三维结构有机聚硅氧烷，R1选自相同或不相同的链烯基、不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基；(C) a solid three-dimensional organopolysiloxane comprising R 1 3 SiO 1/2 units and SiO 4/2 units, R 1 being selected from the same or different alkenyl groups, containing no aromatic hydrocarbons and not containing aliphatic a monovalent substituted or unsubstituted hydrocarbon group of a saturated bond;
    (D)目数为200-4000目的气相二氧化硅；(D) fumed silica having a mesh number of 200-4000 mesh;
    相对于100重量份的组合物总量，所述组分(C)的用量为20-40重量份，所述组分(D)气相二氧化硅的用量为3-10重量份。The component (C) is used in an amount of 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the composition, and the component (D) fumed silica is used in an amount of 3 to 10 parts by weight.
    (E)用量足以促进该组合物固化的氢化硅烷化催化剂。(E) a hydrosilylation catalyst in an amount sufficient to promote solidification of the composition.
  2. 根据权利要求1所述的玻璃防碎胶组合物，其特征在于，相对于100重量份的组合物总量，组分(A)的用量为20-75重量份，组分(B)的用量为1-30重量份。The glass shatterproof adhesive composition according to claim 1, wherein the component (A) is used in an amount of 20 to 75 parts by weight based on 100 parts by weight of the total amount of the composition, and the amount of the component (B) is used. It is 1 to 30 parts by weight.
  3. 根据权利要求1所述的玻璃防碎胶组合物，其特征在于，所述(A)组分为包括R1 3SiO1/2单元和R2 2SiO2/2单元的液态直链结构有机聚硅氧烷，R1和R2选自相同或不相同的链烯基、不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基。The glass shatterproof adhesive composition according to claim 1, wherein the (A) component is a liquid linear structure organic including R 1 3 SiO 1/2 unit and R 2 2 SiO 2/2 unit. The polysiloxane, R 1 and R 2 are selected from the same or different alkenyl groups, monovalent substituted or unsubstituted hydrocarbyl groups containing no aromatic hydrocarbons and no aliphatic unsaturated bonds.
  4. 根据权利要求1所述的玻璃防碎胶组合物，其特征在于，所述组分(B)为包括R3 3SiO1/2单元和R4 2SiO2/2单元的液态直链结构聚有机氢化硅氧烷，R3和R4选自相同或不相同的不含芳烃且不含脂肪族不饱和键的单价取代或未取代的烃基和氢原子。The glass shatterproof adhesive composition according to claim 1, wherein the component (B) is a liquid linear structure polymerization comprising R 3 3 SiO 1/2 units and R 4 2 SiO 2/2 units. The organohydridosiloxane, R 3 and R 4 are selected from the same or different monovalent substituted or unsubstituted hydrocarbyl groups and hydrogen atoms which are free of aromatic hydrocarbons and contain no aliphatic unsaturated bonds.
  5. 根据权利要求1所述的玻璃防碎胶组合物，其特征在于，所述组分(B)中的与硅键合的氢原子与组分(A)和(C)中的链烯基的总摩尔量之比为0.9-3.0。 The glass shatterproof adhesive composition according to claim 1, wherein the silicon-bonded hydrogen atom in the component (B) and the alkenyl group in the components (A) and (C) The ratio of the total molar amount is from 0.9 to 3.0.
  6. 根据权利要求1所述的玻璃防碎胶组合物，其特征在于，所述(C)具有下述平均单元分子式，The glass shatterproof adhesive composition according to claim 1, wherein said (C) has the following average unit molecular formula,
    (SiO4/2)a1(R7 R6 2SiO1/2)a2，(SiO 4/2 ) a1 (R 7 R 6 2 SiO 1/2 ) a2 ,
    其中R7选自相同或不相同的链烯基，所述链烯基的含量为0.01-0.30mol/100g，R6选自相同或不相同的单价取代或未取代的烷基，0.5<a1<0.99，0.01<a2<0.5，且a1+a2＝1。Wherein R 7 is selected from the same or different alkenyl groups, the alkenyl group is present in an amount of from 0.01 to 0.30 mol per 100 g, and R 6 is selected from the same or different monovalent substituted or unsubstituted alkyl groups, 0.5 < a1 <0.99, 0.01 < a2 < 0.5, and a1 + a2 = 1.
  7. 根据权利要求3所述的玻璃防碎胶组合物，其特征在于，所述(A)具有下述平均单元分子式，The glass shatterproof adhesive composition according to claim 3, wherein said (A) has the following average unit molecular formula,
    R5R6 2 SiO(R6 2SiO)a3 SiR6 2 R5，R 5 R 6 2 SiO(R 6 2 SiO) a3 SiR 6 2 R 5 ,
    其中R5选自相同或不相同的链烯基，所述链烯基的含量0.001-0.05mol/100g，R6选自相同或不相同的单价取代或未取代的烷基，65<a3<900。Wherein R 5 is selected from the same or different alkenyl groups, the alkenyl group is contained in an amount of 0.001 to 0.05 mol/100 g, and R 6 is selected from the same or different monovalent substituted or unsubstituted alkyl groups, 65 <a3< 900.
  8. 根据权利要求4所述的玻璃防碎胶组合物，其特征在于，所述(B)具有下述平均单元分子式，The glass shatterproof adhesive composition according to claim 4, wherein the (B) has the following average unit molecular formula,
    R8 3SiO(R8 2SiO)b1(R8HSiO)b2 Si R8 3，R 8 3 SiO(R 8 2 SiO) b1 (R 8 HSiO) b2 Si R 8 3 ,
    其中R8选自相同或不相同的单价取代或未取代的烷基，0.2<b1<0.8，0.2<b2<0.8，且b1+b2＝1。Wherein R 8 is selected from the same or different monovalent substituted or unsubstituted alkyl groups, 0.2 < b1 < 0.8, 0.2 < b2 < 0.8, and b1 + b2 = 1.
  9. 一种玻璃制品，包括玻璃本体，其特征在于，所述玻璃本体上涂布有权利要求1-10任一项所述的玻璃防碎胶组合物的固化物。A glass article comprising a glass body, characterized in that the glass body is coated with a cured product of the glass shatterproof adhesive composition according to any one of claims 1 to 10.
  10. 玻璃防碎胶组合物在玻璃制品上的应用，其特征在于，包括如下步骤：The use of a glass shatterproof adhesive composition on a glass article is characterized in that it comprises the following steps:
    稀释：将权利要求1-10任一项所述的组合物用有机溶剂进行稀释；Dilution: the composition according to any one of claims 1 to 10 is diluted with an organic solvent;
    涂覆：将所述稀释后的组合物涂覆在玻璃制品上；Coating: coating the diluted composition on a glass article;
    固化：将涂覆有所述组合物的玻璃制品在80-150℃温度下固化；Curing: curing the glass article coated with the composition at a temperature of 80-150 ° C;
    冷却：冷却至室温。Cooling: Cool to room temperature.
  11. 根据权利要求10所述的玻璃防碎胶组合物在玻璃制品上的应用，其特征在于，所述稀释步骤中，对所述组合物稀释至粘度10-100mPa·s；涂覆步骤中，涂覆在玻璃制品上的组合物涂层厚度为20-200μm。 The use of the glass shatterproof adhesive composition according to claim 10 for a glass article, characterized in that in the diluting step, the composition is diluted to a viscosity of 10 to 100 mPa·s; in the coating step, the coating is carried out. The composition coating on the glass article has a coating thickness of 20-200 μm.
PCT/CN2015/072108 2014-12-29 2015-02-02 Glass shatter-proof glue composition and glass product and use WO2016106939A1 (en)

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