CN103897574B - Photochromic composition coating, photochromic composition coating product and preparation method of photochromic composition coating product - Google Patents
Photochromic composition coating, photochromic composition coating product and preparation method of photochromic composition coating product Download PDFInfo
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Abstract
The invention discloses a photochromic composition coating, a photochromic composition coating product and a preparation method of the photochromic composition coating product. The coating comprises at least one photochromic factor in a photochromic amount, polymeric polylol of which the number-average molecular weight is 200-2,000, at least one isocyanate group-containing substance of which the number-average molecular weight is 150-300, at least one vinyl-containing substance and auxiliary materials, wherein main chains of the polymeric polylol, isocyanate group-containing substance and vinyl-containing substance contain at least one of carbonic ester, aromatic series or aliphatic series. The coating product comprises a white sheet, dyed sheet or polarized sheet serving as a substrate. The preparation method of the coating product comprises the following steps: coating the substrate with the photochromic composition coating; fixing the coating by adopting thermocuring and photocuring. The photochromic composition coating has the advantages that air bubbles are not produced when the substrate is coated with the coating, and the coating is high in hardness and wear-resistant.
Description
Technical field
The present invention relates to a kind of optical material, particularly relate to the preparation method of a kind of photochromic composition coating and photochromic composition coated products and these goods.
Background technology
Existing Photochromic plastic articles is in Photochromic plastic articles, add the photochromic factor (photochromic dyes), or adds the photochromic factor by Surface absorption plavini.Under sunlight (there is ultraviolet), the easy variable color of this kind of Photochromic plastic articles (being colored), after keeping out of the sun, this kind of Photochromic plastic articles recovers original color (fading).But current Photochromic plastic articles exists following shortcoming: Photochromic plastic articles surface easily produces bubble or sends out mist, or Photochromic plastic articles surface hardness is high, easy to wear etc.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide one and does not produce the higher and anti abrasive photochromic composition coating of bubble, hardness;
The second object of the present invention is to provide a kind of photochromic composition coated products;
The third object of the present invention is to provide the preparation method of this photochromic composition coated products.
Technical scheme: photochromic composition coating of the present invention, it is characterized in that comprising following component: the material containing isocyanate group that the polymerized polyalcohol that the photochromic factor of at least one photochromic amount, number-average molecular weight (Mn) are 200-2000, at least one number-average molecular weight (Mn) are 150-300, at least one contain material and the auxiliary material of vinyl, wherein, containing at least one in carbonic ether, aromatic series or aliphatics on the main chain of described polymerized polyalcohol, the material containing isocyanate group and the material containing vinyl.
Wherein, described polymerized polyalcohol is at least one in PAO and PO, PCDO; The described material containing isocyanate group is at least one in IPDI, HDI, H12MDI, TDI, MDI; The described material containing vinyl is polymethylmethacrylate; Described auxiliary material is solvent, initiator, catalyzer, ultra-violet stabilizer and tensio-active agent.
Said components is made by following weight proportion:
Described PAO is formed by the monomer polymerization with following general formula:
Wherein, R1 is H, CH3, OH or SH, and R2 is H, CH3, OH or SH, and R3 is H, CH3, C2H5, OH or SH, and R4 is C5H9, OH or SH.
Described PAO obtains particular by following reaction:
Wherein, temperature of reaction 90-110 DEG C, the reaction times is 3.8-4.2h, and uses initiator in reaction process.
Above-mentioned reactant is made by following weight proportion:
Photochromic composition coated products of the present invention, comprises matrix and is coated in the photochromic composition coating on matrix.
Wherein, described matrix is white tiles, staining section or polaroid.
The preparation method of photochromic composition coated products of the present invention, is first coated on matrix by photochromic composition coating, then adopts the mode of thermofixation and photocuring to fix coating simultaneously.
Wherein, described cure times is more than 1h, and described thermal curing time is 1min.
Beneficial effect: compared with prior art, its remarkable advantage is in the present invention: do not produce bubble after 1, photochromic composition coating of the present invention is coated on matrix, and coating hardness is higher, not easy to wear; 2, coating of the present invention can be used for specific refractory power 1.499, the common eyeglass of 1.56,1.60,1.67,1.74 grades, and variable color sheet and polaroid; 3, photochromic composition coated products long service life of the present invention, uses more than 1 year almost without damage; 4, the preparation method of coated products of the present invention adopts thermofixation and photocuring to carry out simultaneously, and solidification effect is excellent.
Embodiment:
Below technical scheme of the present invention is described further.
Photochromic composition coating (hereinafter referred to as coating) the photochromic factor is joined preparation in corresponding lysate and obtains, the main component of this lysate is urethane or the material (being preferably acrylic) containing vinyl (band vinyl group), and in prior art, the two selects one.These two kinds of lysates respectively have quality, and wherein, urethane easily regulates physical property, but synthesis condition is comparatively harsh, and such as the reaction times is longer; Acrylic is compared with urethane, and its synthesis is easily carried out, and the reaction times is short, but is difficult to control its physical property.These two kinds of lysates (urethane and acrylic) are mixed to get the composition of required physical property by the present invention, and reaction easily carry out, consuming time shorter.
Urethane of the present invention is by polymerized polyalcohol (band OH group) and synthesizes containing the material (band NCO group) of isocyanate group.Wherein, polymerized polyalcohol number-average molecular weight (Mn) through test of many times the present invention screening is 200-2000, preferred Mn is 200-1000, does not send out mist and hardness and transparency are better after can ensureing coating coating, and this number-average molecular weight measures (lower with) by polystyrene chromatography method; Meanwhile, the heterogeneity index of this polymerized polyalcohol, below 2.0, can ensure that coatingsurface is comparatively even.Polymerized polyalcohol is at least one in PAO and PO, PCDO, and obtained coating solution hardness is better, is beneficial to the dissolving of the photochromic factor.
PO is polyvalent alcohol, the carbonate polyol (carbonate polyol) of such as available from Aldrich Co, and its number-average molecular weight (Mn) is 1000;
PCDO(polycarbonatediol) be polycarbonate diol, also can available from Aldrich Co, its number-average molecular weight (Mn) is 800;
PAO（Polyacrylol）
Structural formula:
Molecular formula: C14H24O5; Its number-average molecular weight (Mn): 273.
PAO of the present invention is formed by following monomer polymerization:
r1:H, CH3, OH or SH,
R2:H, CH3, OH or SH,
R3:H, CH3, C2H5, OH or SH,
R4:C5H9, OH or SH.
PAO obtains particular by following reaction:
Wherein, temperature of reaction 90-110 DEG C, preferable temperature is 100 DEG C; Reaction times is 3.8-4.2h, and the preferred time is 4h, and uses initiator V-65(2,2'-Azobis(2,4-dimethylvaleronitrile) in reaction process).
Reactant ratio and reaction conditions table specific as follows:
Table 1
The present invention is 150-300 containing the number-average molecular weight (Mn) of the material of isocyanate group, is specially at least one in IPDI, HDI, H12MDI, TDI, MDI.
Wherein,
IPDI(isophorone diisocyante), isophorone diisocyanate, C12H18N2O2, number-average molecular weight (Mn) is 222.3, available from Aldrich Co.
Its molecular formula is
HDI(1,6-hexamethylene diisocyanate), hexamethylene diisocyanate, C8H12N2O2, number-average molecular weight (Mn) is 168.19, available from Aldrich Co.
Its molecular formula is
TDI(toluene diisocyante), tolylene diisocyanate, C9H6N2O2, number-average molecular weight (Mn) is 174.2, available from Aldrich Co.
Its molecular formula is
In addition, H12MDI and MDI Ye Shi available from Aldrich Co.
The present invention, containing the material of vinyl (band vinyl group), is preferably acrylic (polymethylmethacrylate).
The present invention use solvent have NMP(n-Methylene-pyrrolidone), Toluene(toluene), methanol(methyl alcohol) or cyclohexanone(pimelinketone) etc., all can available from Aldrich Co.Wherein, we find NMP(Chinese name n-methylene pyrrolidine ketone through test of many times, C5H9NCO5H, and number-average molecular weight (Mn) is 99.13) solvability best, urethane and acrylic are organically combined.
Other auxiliary material that the present invention uses:
Initiator, V-65(2,2'-Azobis(2,4-dimethylvaleronitrile)), purchased from Wakco chemicals(Wakco chemical);
Catalyzer, purchased from sankyo organic chemicals-Stann BDC (Dibuthyltin dichloride);
Ultra-violet stabilizer (UV stablizer), purchased from seesorb709;
Tensio-active agent, purchased from BYK company-BYK301.
The photochromic factor (or being called photochromic dyes) that the present invention uses, purchased from vivimed company,
Can be such as:
1, Spirooxazine(spirooxazine), its chemical formula is
2, Spiropyrans(spiro-pyrans), its chemical formula is
3, Chromenes(chromene), its chemical formula is
Each raw material weight proportioning that the present invention prepares coating sees the following form 2:
Table 2
Coating of the present invention adopts conventional technique means obtained, all pours glass reaction machine into by all raw materials in table 2, and mixing, stirring, control various parameter, react.
Above-mentioned obtained coating, its number-average molecular weight, between 500-50000, preferably between 800-15000, has the second-order transition temperature of more than 5 DEG C simultaneously.
Obtained coating is coated on matrix, be specially: the coating solution (or being called photochromic hardening solution) dripping about 1-2g on the lens surface that the speed of 400-500rpm rotates, carry out the photocuring that the thermofixation (being preferably 1min) of 0.5-1.5min and more than 1h are no more than 2h after rotating 10-20 second with the speed of 800-2000rpm again after dripping upper 5-10 second, finally obtain photochromic composition coated products (hereinafter referred to as coated products).
Thermofixation is the method evaporating solvent by physical heating, makes coating hardens; Photocuring utilizes UV-light cause the material generation crosslinking reaction in coating thus form new chemical bond to realize coating hardens, and therefore these two kinds of methods respectively have quality.And existing coating system can only adopt above-mentioned a kind of curing mode; And the present invention can adopt above-mentioned two kinds of curing modes simultaneously, be coated on matrix with making coating uniform, and after coating curing, hardness is better, partially not soft hard only, lower, the curing speed of simultaneously consuming energy comparatively fast, easily realizes.
Above-mentioned matrix is white tiles, staining section or polaroid, and its specific refractory power is between 1.499-1.74; Also organic or inorganic aggretion type substrate can be chosen from through thermoset and thermoplastic material.
Detected as follows by the coated products that 12 groups of embodiments in table 1 obtain, detected result is in table 3:
1, the transmitance before coated products variable color and after variable color is detected
Equipment: Simitsu UV spectrometer;
Colour-change light source: 350nm, temperature 24 DEG C, 15 seconds time, transmitance measures wavelength: 490nm.
2, the bubble of coated products and blue mist situation is detected
In table 3, X represents not to be had, and 0 indicates, △ indicates a bit.
The obtained coating of embodiment 5,6,7,9,10,11,12 does not produce bubble and blue mist, and this is because lysate adds the cause of urethane and acryl.
3, surface hardness measures
Equipment: the Fisherscope HCV of Fisher Technology Inc. company, model H-100
Method: lens surface is at 10N/mm
2pressure under adhere to 15 seconds after, make measurement of hardness in its 2 μm of degree of depth, get each eyeglass do measure for 2 ~ 5 times after the statistical average that obtains.
As shown in Table 3, the coated products surface hardness that embodiment 6,9,10,11,12 obtains is very high, and the coated products surface hardness that embodiment 7 obtains is higher.
Table 3
Claims (7)
1. a photochromic composition coating, it is characterized in that, comprise following component: the material containing isocyanate group, polymethylmethacrylate and auxiliary material that the polymerized polyalcohol that the photochromic factor of at least one photochromic amount, number-average molecular weight are 200-1000, at least one number-average molecular weight are 150-300;
Wherein, described polymerized polyalcohol is at least one in PAO and polyvalent alcohol, polycarbonate diol, the described material containing isocyanate group is at least one in IPDI, HDI, TDI, and described auxiliary material is solvent, initiator, catalyzer, ultra-violet stabilizer and tensio-active agent;
Described PAO is formed by the monomer polymerization with following general formula:
Wherein, R1 is H, CH
3, OH or SH, R2 be H, CH
3, OH or SH, R3 be H, CH
3, C
2h
5, OH or SH, R4 be C
5h
9, OH or SH;
The weight proportion of each component is as follows:
2. photochromic composition coating according to claim 1, is characterized in that, described PAO is obtained by following reaction:
Wherein, temperature of reaction 90-110 DEG C, the reaction times is 3.8-4.2h, and uses initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) in reaction process.
3. photochromic composition coating according to claim 2, is characterized in that, the weight proportion of described reactant is as follows:
4. a photochromic composition coated products, is characterized in that: comprise matrix and be coated in the photochromic composition coating according to any one of claim 1-3 on matrix.
5. photochromic composition coated products according to claim 4, is characterized in that: described matrix is white tiles, staining section or polaroid.
6. a preparation method for photochromic composition coated products, is characterized in that: be first coated on matrix by the photochromic composition coating such as according to any one of claim 1-3, then adopts the mode of thermofixation and photocuring to fix coating simultaneously.
7. the preparation method of photochromic composition coated products according to claim 6, is characterized in that: the time of described photocuring is 1-2h, and the time of described thermofixation is 0.5-1.5min.
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| CN106634533B (en) * | 2016-12-26 | 2019-04-16 | 北京东方雨虹防水技术股份有限公司 | A kind of thermochromism polyurethane water-proof paint |
| CN109535888A (en) * | 2018-10-25 | 2019-03-29 | 广州市科涵实业有限责任公司 | A kind of one pack system photochromic coating and preparation method thereof |
| CN110323263A (en) * | 2019-07-10 | 2019-10-11 | 京东方科技集团股份有限公司 | Polaroid, display device |
| CN112708344B (en) * | 2021-01-06 | 2022-01-11 | 光易科技(无锡)有限公司 | Photochromic composition of hyperbranched polyurethane vinyl ether, product and preparation method |
| CN114335894A (en) * | 2021-12-21 | 2022-04-12 | 惠州锂威新能源科技有限公司 | Diaphragm with photochromic coating, preparation method thereof and secondary battery |
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| CN1251116A (en) * | 1997-02-21 | 2000-04-19 | Pp工业俄亥俄公司 | Photochromic polyurethane coating and articles having such coating |
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| US8318890B2 (en) * | 2005-02-18 | 2012-11-27 | Asahi Kasei Chemicals Corporation | Polycarbonate diol |
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