CN101586017A - Storage light-emitting silicone sealant - Google Patents

Storage light-emitting silicone sealant Download PDF

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Publication number
CN101586017A
CN101586017A CN 200910145373 CN200910145373A CN101586017A CN 101586017 A CN101586017 A CN 101586017A CN 200910145373 CN200910145373 CN 200910145373 CN 200910145373 A CN200910145373 A CN 200910145373A CN 101586017 A CN101586017 A CN 101586017A
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silicone sealant
parts
emitting
storage light
light
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CN101586017B (en
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陈炳耀
张秋明
陈亮
刘国贞
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Guangdong Sanhe Holding Co ltd
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Guangdong Sanhe Chemical Industry Technology Co Ltd
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Abstract

The invention a storage light-emitting silicone sealant, wherein the weight ratio of the formula is: Alpha, Omega-85-100 parts of polysiloxanediol, 10-25 parts of silicon dioxide, 3-15 parts of a crosslinker, 0.2-2 parts of a catalyzer, 1-5 parts of a coupling agent, 3-10 parts of a multicolour long afterglow storage radiant agent, 0.1-2 parts of a light stabilizer and 1-20 parts of a superfine alkali free glass fibre powder. The advantages of the invention are as follows: 1, using is safe, and radioactivity of the added the multicolour long afterglow storage radiant agent is low; 2, luminescence time is long, and the superfine alkali free glass fibre powder is added to improve transmission of light, fully absorb optical energy by the sealant and prolong afterglow time; 3, emitting colour is pentiful, and the storage light-emitting silicone sealant with different emitting colours can be blended by adding the multicolour long afterglow storage radiant agent, with good decoration and indication function; 4, good matching with luminous products or non-luminous products, the sealant can be widely applied to bonding and sealing of fire-fighting indication products, interior decoration and mounting of handcrafts; 5, weather ability and cracking resistance are improved by adding the light stabilizer and the superfine alkali free glass fibre powder, and service life is also prolonged.

Description

Storage light-emitting silicone sealant
Technical field
The present invention relates to a kind of silicone sealant, particularly a kind of luminous energy that sunlight or source of artificial light produce and storage light-emitting silicone sealant that luminous energy can be slowly released of absorbing.
Technical background
Along with the transformation of people's aesthetic standards, how existing practicality has the product emerge in multitude of sight again, and noctilucent material is wherein all used in many products to some extent.Traditional noctilucent material is sulfide-based fluorescent material, as ZnS:Cu, Er, and CaSrS:Bi, CaS:Bi etc., this class material noctilucence time is short, and low lightness has been added radioelement for improving its luminosity and noctilucence time, certainly will cause human body harm and environmental pollution.Kai Fa steady persistence advanced luminescent material in recent years, as rare earth ion europium (Eu) activated aluminate type noctilucent material, this material is long time of persistence, by absorbing ultraviolet or visible light, after being transformed, luminous energy is stored in the lattice, energy slowly can be converted into luminous energy again and luminous, open up novel noctilucent material field.Typical noctilucence product has noctilucence glass, noctilucence glass Mosaic, noctilucence Glass Craft, Noctilucent ceramics, luminescent coating, noctilucence ceramic tile, luminous plastics, luminescent screen or the like on the market.For example well-known: the precious wound science and technology in Taiwan is developed the glassy product-PolyGlow noctilucence glass of innovation recently, has after enough illumination, continues emitting characteristics in the dark, can build the atmosphere of hazy and illusionary romance at night.Be a kind ofly can satisfy high-end decoration and the functional glass market requirement and performance Designers, the required super new glass material of architect's intention; The disclosed patent CN101066856 of China relates to a kind of luminous GRP floor tile, has solved that the raw materials used cost of existing noctilucence floor tile is higher, manufacturing process is than complexity and the relatively poor problem of material capability, and the practicality of this material is strengthened greatly; The glad noctilucence glass Mosaic that reaches the production of noctilucence Science and Technology Ltd. in Foshan, the mosaic that seems ordinary under available light has colors such as oyster, white, and after the enough illumination, dark is sentenced colors such as jaundice green, blue-greenish colour, sky blue.The noctilucence glass Mosaic is used for local-style dwelling houses and public building, not only can beautify U.S. decorations and live and Working environment, simultaneously its absorb behind luminous energy in the dark or night self luminous characteristics brought very big convenience for people's live and work, saved the energy.The low emergency lighting effect of the luminous of Noctilucent ceramics, noctilucence glass Mosaic, its meaning is not only just energy-conservation, and its distinctive light penetration power can guide people in case of emergency to withdraw in order in dense smoke, reduces chaotic.
Yet the adhering and sealing of materials such as noctilucence glass, noctilucence glass Mosaic, noctilucence Glass Craft, Noctilucent ceramics, noctilucence ceramic tile all needs to use seal gum.Traditional neutral silicone seal gum is a single-component, and self cure has excellent cementability, and is easy to use, is widely used in the adhering and sealing of aluminum alloy doors and windows, glass and glasswork, pottery, masonry and most of plastics.But owing to lack illumination effect, when adhering and sealing noctilucence product or non-noctilucence product, integral body attractive in appearance there is considerable influence,, requires further to improve especially to the influence of whole luminous effect.
The objective of the invention is in conjunction with the performance characteristics of neutral silicone seal gum and the utilisation technology of luminescent material, prepare and a kind ofly absorb the luminous energy that sunlight or source of artificial light produce, and slowly discharge the luminous storage light-emitting silicone sealant of luminous energy.
Summary of the invention
The present inventor inquires into repeatedly for achieving the above object, found that and in common neutral silicone seal gum, add colorful long-afterglow energy-accumulating luminous agent, photostabilizer and superfine alkali free glass fibre powder, has luminous effect, time of persistence is long, the use selectivity is good, the transparency is good, and has effectively improved the weathering resistance and the resistance to cracking of neutral silicone seal gum.Can with noctilucence product or the supporting uses of non-noctilucence product such as noctilucence glass, noctilucence glass Mosaic, noctilucence Glass Craft, Noctilucent ceramics, noctilucence ceramic tile, thereby finished the present invention.
Storage light-emitting silicone sealant of the present invention is achieved in that prescription is by weight ratio:
α, 85~100 parts of alpha, omega-dihydroxy polysiloxane
0~25 part of silica 1
3~15 parts of linking agents
0.2~2 part of catalyzer
1~5 part of coupling agent
3~10 parts of colorful long-afterglow energy-accumulating luminous agents
0.1~2 part of photostabilizer
1~20 part of superfine alkali free glass fibre powder
Aforesaid α, alpha, omega-dihydroxy polysiloxane contain the poly organo siloxane compound that intramolecularly has the functional group shown in the following chemical formula (1) at least,
Figure A20091014537300051
(n=50 in the formula~2000, R is CH 3-or CH 3CH 2-or phenyl, can be identical or different);
Aforesaid α, in the alpha, omega-dihydroxy polysiloxane structure formula, R is CH 3-;
Aforesaid linking agent is at least a in methyl tri acetylacetonate oximino silane, methyl tributanoximo silane, the vinyl tributanoximo silane;
Aforesaid catalyzer is at least a in stannous octoate, dibutyl tin acetate or the dibutyl tin laurate;
Aforesaid coupling agent is at least a in N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-chloropropyl triethoxysilane, the γ-An Bingjisanyiyangjiguiwan;
Aforesaid photostabilizer is to contain the hindered amine compound that intramolecularly has the functional group shown in the following chemical formula (2) at least,
Figure A20091014537300061
(R1~R10 represents that hydrogen atom or carbonatoms are that 1~10 alkyl or carbonatoms are 1~10 substituted alkyl in the formula, can be identical or different);
Aforesaid photostabilizer is Succinic acid dimethylester-1-(2-hydroxyethyl)-4-hydroxyl-2,2,6,6-tetramethyl piperidine polycondensate, sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) ester, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, 2-(3,5-tertiary butyl-4-hydroxy benzyl)-2-n-butylmalonic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester, 1,2,3,4-BTCA 1,2,2,6,6-pentamethyl--4-piperidyl/tridecyl ester, N, N '-two-(3-aminopropyl) quadrol-2,4-is two, and [N-butyl-N-(1,2,2,6,6-pentamethyl--4-pyridyl) amino]-at least a in the 6-chloro-1,3,5-triazines condenses;
Aforesaid colorful long-afterglow energy-accumulating luminous agent is energy-accumulating luminous dose an of aluminates system of the prior art, the employing aluminate is a matrix, rare earth ion is main activator, has also added Vanadium Pentoxide in FLAKES, magnesium oxide or boron trioxide in addition as the twilight sunset toughener, makes its fluorescent lifetime longer;
Aforesaid colorful long-afterglow energy-accumulating luminous agent, the chemical expression of its main component is:
MO·NO·Al 2O 3·R:Eu、Ln
Wherein M is at least a among Sr, Ca, Ba, the Zn;
N is at least a among Mg, Cd, the Be;
R is P 2O 5, MgO, B 2O 3In at least a;
Ln is at least a among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Si, Sn, the Sb;
By changing element kind and the proportioning of M in the chemical expression, can obtain the colorful long-afterglow energy-accumulating luminous agent of different glow colors.
The manufacture method of storage light-emitting silicone sealant of the present invention:
With α, alpha, omega-dihydroxy polysiloxane, silicon-dioxide add in the planetary mixer, after stirring 30~120 minutes under vacuum tightness 0.07~0.12Mpa, the rotating speed 20~60rpm, add linking agent, catalyzer, silane coupling agent, colorful long-afterglow energy-accumulating luminous agent, photostabilizer, superfine alkali free glass fibre powder, under vacuum tightness 0.07~0.12Mpa, rotating speed 15~60rpm, reacted 45~120 minutes, make storage light-emitting silicone sealant.
The present invention compared with prior art has following characteristics:
1. safe in utilization, the colorful long-afterglow energy-accumulating luminous agent radioactivity of interpolation is low.
2. luminescence time is long, adds superfine alkali free glass fibre powder, improves light transmission, helps colloid and fully absorbs luminous energy, prolongs time of persistence.
3. glow color is abundant, adds the adjustable storage light-emitting silicone sealant of allotting different glow colors of colorful long-afterglow energy-accumulating luminous agent, and good decorative property views and admires superior with indicative function.
4. matching capacity is strong, can with noctilucence product or the supporting use of non-noctilucence product, be widely used in the adhering and sealing of fire-fighting indication product, indoor finishing, the aspects such as mounting of artwork.
5. weather resistance is good, adds photostabilizer and superfine alkali free glass fibre powder and has improved weathering resistance and resistance to cracking, has prolonged work-ing life.
Embodiment
Embodiment 1
With α, 85 kilograms of alpha, omega-dihydroxy polydimethyl siloxanes, silicon-dioxide adds in the planetary mixer for 20 kilograms, at vacuum tightness 0.09Mpa, rotating speed 25rpm stirs after 80 minutes down, add 8 kilograms of methyl tri acetylacetonate oximino silanes, 0.5 kilogram of stannous octoate, 1 kilogram of γ-chloropropyl triethoxysilane, 2 kilograms of the colorful long-afterglow energy-accumulating luminous agents of yellow green light, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester is 0.2 kilogram, 2 kilograms of superfine alkali free glass fibre powder are at vacuum tightness 0.08Mpa, rotating speed 55rpm reacted 90 minutes down, made storage light-emitting silicone sealant.
Embodiment 2
With α, 90 kilograms of alpha, omega-dihydroxy polydimethyl siloxanes, silicon-dioxide adds in the planetary mixer for 22 kilograms, at vacuum tightness 0.10Mpa, rotating speed 35rpm stirs after 70 minutes down, add 3 kilograms of methyl tributanoximo silanes, 0.8 kilogram of dibutyl tin laurate, 2 kilograms of γ-An Bingjisanyiyangjiguiwans, 8 kilograms of the colorful long-afterglow energy-accumulating luminous agents of ruddiness, 2-(3,5-tertiary butyl-4-hydroxy benzyl)-2-n-butylmalonic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester is 1 kilogram, 10 kilograms of superfine alkali free glass fibre powder are at vacuum tightness 0.09Mpa, rotating speed 45rpm reacted 100 minutes down, made storage light-emitting silicone sealant.
Embodiment 3
With α, 100 kilograms of alpha, omega-dihydroxy polydimethyl siloxanes, silicon-dioxide adds in the planetary mixer for 25 kilograms, at vacuum tightness 0.12Mpa, rotating speed 45rpm stirs after 60 minutes down, add 13 kilograms of vinyl tributanoximo silanes, 1.2 kilograms of dibutyl tin acetates, 5 kilograms of N-β-aminoethyls-γ-An Bingjisanjiayangjiguiwan, 10 kilograms of the colorful long-afterglow energy-accumulating luminous agents of purple light, sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) ester is 1.5 kilograms, 8 kilograms of superfine alkali free glass fibre powder are at vacuum tightness 0.10Mpa, rotating speed 35rpm reacted 110 minutes down, made storage light-emitting silicone sealant.
Main raw material(s) title, technical indicator:
1. α, alpha, omega-dihydroxy polydimethyl siloxane
Outward appearance: the water white transparency thick liquid, do not have mechanical impurity
Viscosity (25 ℃, mPas): 2000~300000
2. silicon-dioxide
Specific surface area (m 2/ g): 150~200
Dioxide-containing silica is (based on firing product, %): 〉=99.8
Apparent density (g/L): 25~60
3. methyl tri acetylacetonate oximino silane
Outward appearance: light yellow transparent liquid
Chromatographic purity (%): 〉=95
PH value: 6.5~7.5
4. methyl tributanoximo silane
Outward appearance: colourless transparent liquid
Chromatographic purity (%): 〉=95
PH value: 6.5~7.5
5. vinyl tributanoximo silane
Outward appearance: colourless transparent liquid
Chromatographic purity (%): 〉=95
PH value: 6.5~7.5
6. stannous octoate
Outward appearance: pale yellow oily liquid body
Density (25 ℃, g/cm 3): 1.230~1.270
Inferior tin content (%):>26
7. dibutyl tin acetate
Outward appearance: colourless transparent liquid
Density (25 ℃, g/cm 3): 1.249~1.255
Tin content (%): 30 ± 0.5
8. dibutyl tin laurate
Outward appearance: light yellow transparent liquid
Density (25 ℃, g/cm 3): 1.025~1.065
Tin content (%): 17~19
9.N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan
Outward appearance: colourless or little yellow transparent liquid
Chromatographic purity (%): 〉=98
Density (25 ℃, g/cm 3): 1.010~1.030
10. γ-chloropropyl triethoxysilane
Outward appearance: colourless transparent liquid
Chromatographic purity (%): 〉=98
Density (25 ℃, g/cm 3): 1.004~1.006
11. γ-An Bingjisanyiyangjiguiwan
Outward appearance: colourless transparent liquid
Chromatographic purity (%): 〉=98
Density (25 ℃, g/cm 3): 0.940~0.950
12. colorful long-afterglow energy-accumulating luminous agent
Particle diameter (order): 200~300
After-glow brightness (mcd/m 2): initial brightness>2000,120min brightness>20
Time of persistence (min):>600
Specific radioactivity (Bqkg -1): I Ra≤ 1.0, I γ≤ 1.3
13. hindered amine light stabilizer
Outward appearance: white or light yellow crystalline powder
Purity (%): 〉=99
14. superfine alkali free glass fibre powder
Specification: 50 orders~100 orders
The main project sampling inspection of reference standard " GB/T14683-2003 silicone building sealant ", " GB6566-2001 radioactive material nucleic is limited the quantity of ", its performance index such as following table:
Figure A20091014537300101

Claims (10)

1. storage light-emitting silicone sealant is characterized in that prescription is by weight ratio:
α, 85~100 parts of alpha, omega-dihydroxy polysiloxane
0~25 part of silica 1
3~15 parts of linking agents
0.2~2 part of catalyzer
1~5 part of coupling agent
3~10 parts of colorful long-afterglow energy-accumulating luminous agents
0.1~2 part of photostabilizer
1~20 part of superfine alkali free glass fibre powder.
2. storage light-emitting silicone sealant as claimed in claim 1 is characterized in that α, and the alpha, omega-dihydroxy polysiloxane is to contain the poly organo siloxane compound that intramolecularly has the functional group shown in the following chemical formula (1) at least,
Figure A2009101453730002C1
(n=5 α~2000 in the formula, R is CH 3-or CH 3CH 2-or phenyl, can be identical or different).
3. storage light-emitting silicone sealant as claimed in claim 2 is characterized in that α, and in the alpha, omega-dihydroxy polysiloxane structure formula, R is CH 3-.
4. storage light-emitting silicone sealant as claimed in claim 1 is characterized in that linking agent is at least a in methyl tri acetylacetonate oximino silane, methyl tributanoximo silane, the vinyl tributanoximo silane.
5. storage light-emitting silicone sealant as claimed in claim 1 is characterized in that catalyzer is at least a in stannous octoate, dibutyl tin acetate or the dibutyl tin laurate.
6. storage light-emitting silicone sealant as claimed in claim 1 is characterized in that coupling agent is at least a in N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-chloropropyl triethoxysilane, the γ-An Bingjisanyiyangjiguiwan.
7. storage light-emitting silicone sealant as claimed in claim 1 is characterized in that photostabilizer is to contain the hindered amine compound that intramolecularly has the functional group shown in the following chemical formula (2) at least,
Figure A2009101453730003C1
(R1~R10 represents that hydrogen atom or carbonatoms are that 1~10 alkyl or carbonatoms are 1~10 substituted alkyl in the formula, can be identical or different).
8. storage light-emitting silicone sealant as claimed in claim 7 is characterized in that photostabilizer is Succinic acid dimethylester-1-(2-hydroxyethyl)-4-hydroxyl-2,2,6,6-tetramethyl piperidine polycondensate, two (the 1-octyloxies-2,2 of sebacic acid, 6,6-tetramethyl--4-piperidyl) ester, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, 2-(3,5-tertiary butyl-4-hydroxy benzyl)-2-n-butylmalonic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester, 1,2,3,4-BTCA 1,2,2,6,6-pentamethyl--4-piperidyl/tridecyl ester, N, N '-two-(3-aminopropyl) quadrol-2, the two [N-butyl-N-(1 of 4-, 2,2,6,6-pentamethyl--4-pyridyl) amino]-6-chloro-1,3, at least a in the 5-triazine condenses.
9. storage light-emitting silicone sealant as claimed in claim 1, it is characterized in that colorful long-afterglow energy-accumulating luminous agent is energy-accumulating luminous dose an of aluminates system of the prior art, the employing aluminate is a matrix, rare earth ion is main activator, also added Vanadium Pentoxide in FLAKES, magnesium oxide or boron trioxide in addition as the twilight sunset toughener, made its fluorescent lifetime longer.
10. storage light-emitting silicone sealant as claimed in claim 9 is characterized in that the chemical expression of colorful long-afterglow energy-accumulating luminous agent main component is: MONOAl 2O 3R:Eu, Ln
Wherein M is at least a among Sr, Ca, Ba, the Zn;
N is at least a among Mg, Cd, the Be;
R is P 2O 5, MgO, B 2O 3In at least a;
Ln is at least a among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Si, Sn, the Sb; By changing element kind and the proportioning of M in the chemical expression, can obtain the colorful long-afterglow energy-accumulating luminous agent of different glow colors.
CN 200910145373 2009-05-18 2009-05-18 Storage light-emitting silicone sealant Active CN101586017B (en)

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Cited By (4)

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CN102712841A (en) * 2010-01-07 2012-10-03 夏普株式会社 Fluorescent material and process for production of fluorescent material
CN105713551A (en) * 2016-05-06 2016-06-29 烟台图文马克化工科技有限公司 Silicone sealant for plastic-steel doors and windows
CN107892897A (en) * 2017-12-12 2018-04-10 苏州铂邦胶业有限公司 A kind of strong cohesion silicone sealant and preparation method thereof
CN108893091A (en) * 2018-05-18 2018-11-27 江苏中南建设装饰有限公司 A kind of curtain wall fluorescence sealant and preparation method thereof

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CN100560688C (en) * 2005-09-23 2009-11-18 大连路明发光科技股份有限公司 Long after glow luminous material and manufacture method thereof
CN101250391A (en) * 2008-04-12 2008-08-27 中山市三和气雾有限公司 One-component thermostable silicone sealant

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Publication number Priority date Publication date Assignee Title
CN102712841A (en) * 2010-01-07 2012-10-03 夏普株式会社 Fluorescent material and process for production of fluorescent material
CN105713551A (en) * 2016-05-06 2016-06-29 烟台图文马克化工科技有限公司 Silicone sealant for plastic-steel doors and windows
CN107892897A (en) * 2017-12-12 2018-04-10 苏州铂邦胶业有限公司 A kind of strong cohesion silicone sealant and preparation method thereof
CN107892897B (en) * 2017-12-12 2020-11-10 苏州铂邦胶业有限公司 Silicone sealant with strong adhesive force and preparation method thereof
CN108893091A (en) * 2018-05-18 2018-11-27 江苏中南建设装饰有限公司 A kind of curtain wall fluorescence sealant and preparation method thereof
CN108893091B (en) * 2018-05-18 2020-12-25 江苏中南建设装饰有限公司 Fluorescent sealant for curtain wall and preparation method thereof

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