Embodiment
The employed base material of otpical leaf of the present invention can be the known person of any persond having ordinary knowledge in the technical field of the present invention, for example is glass or plastics.Above-mentioned plastic basis material there is no particular restriction, and it is such as but not limited to polyacrylate resin (polyacrylate resin), as polymethylmethacrylate (polymethyl methacrylate, PMMA); Polycarbonate resin (polycarbonate resin); Polystyrene resin; Poly-cyclic olefin resins (polycycloolefin resin); Polyolefin resin (polyolefin resin) is as tygon (PE) or polypropylene (PP); Poly-cellulose acetate resin; Polyimide resin (polyimide resin); Vibrin (polyester resin), as polyethylene terephthalate (polyethylene terephthalate, PET); Or its potpourri.The thickness of base material depends on the demand of the optical articles of wishing to get usually, and it is preferable less than 1 millimeter, is more preferred from 0.1~0.6 millimeter.
For strengthening the toughness of base material; form a protective seam at least one surface of base material; this protective seam can form by any prior art method, its such as but not limited to by apply, paste, modes such as evaporation or sputter form this protective seam on the surface of this base material, be preferably coating method.
For keeping the original penetrability of base material, the refractive index of this protective seam is preferable suitable with refractive index base material, for example between 1.4 to 1.6.Simultaneously, identical or be similar to base material by shrinkage factor (shrinkagerate) essence of suitable this organic layer of control, can prevent that base material from producing warpage.Moreover for reducing cost and control the quality of otpical leaf, the thickness of its organic layer should be between 1 micron to 20 microns, and is preferable between 5 microns to 15 microns, better between 8 microns to 12 microns.
Otpical leaf of the present invention comprises one deck organic layer at least, and this organic layer comprises (a) thermoset resin and (b) rigidizer.Organic layer used in the present invention comprises thermoset resin (thermal setting resin), it is preferably fluorocarbon resin or polyacrylate resin such as but not limited to polystyrene resin, vibrin, epoxy resin, fluorocarbon resin, polyacrylate resin, polycarbonate or its potpourri.The present invention uses thermoset resin can avoid resin too fast because of setting rate, produce very big internal stress, cause the problem of institute's substrates coated buckling deformation, and has high strength and good toughness, and good thermotolerance, and have high solids content (high solids content), contain less solvent, so can shorten stoving time and reduce baking temperature, reduce the volumetric contraction phenomenon that is caused because of a large amount of solvent evaporates.Generally speaking, under about 25 ℃ to 150 ℃ temperature, reaction can be cured, therefore, running cost can be further reduced.Can be used for thermoset resin of the present invention, its mean molecular weight is generally between about 10
4To about 2 * 10
6Between, preferable between about 2 * 10
4To about 3 * 10
5Between, better for about 3 * 10
4To about 10
5Between.In specific words, thermoset resin of the present invention is derived from the monomer mixture that comprises following monomer:
(a1) monomer, its have at least a not with the thermal curable functional group of rigidizer reaction, this sense base system is selected from the group that is made up of hydroxyl, vinyl, amide group, amido formate base, epoxy radicals, carbonyl and composition thereof,
(a2) monomer, its have at least a can with the functional group of (b) rigidizer reaction, this sense base system is selected from the group that is made up of hydroxyl, carboxyl, amido, epoxy radicals and composition thereof.
The main chain system of thermoset resin of the present invention is made of at least a (a1) monomer, and different thermoset resin systems use different (a1) monomers.The for example preferred embodiment according to the present invention, the thermoset resin of selecting for use are polyacrylate resin, and its (a1) monomer comprises at least a acrylic monomer with following general formula:
R wherein
1Be hydrogen atom or methyl; R
2Be hydrogen atom, C
6~C
18Aromatic series base (aromatic group), C
1~C
18Fatty group (aliphatic group) or C
2~C
4Epoxy radicals.Acrylic monomer used in the present invention is preferably (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) cyclohexyl acrylate, (methyl) glycidyl acrylate or its potpourri.
Another specific embodiment according to the present invention, thermoset resin used in the present invention are fluorocarbon resin, and this resinoid has good thermotolerance, comprise at least a fluorochemical monomer in order to (a1) monomer that forms this fluorocarbon resin.This fluorochemical monomer is a personage institute well known of being familiar with this technology, and it is preferably chlorotrifluoroethylene such as but not limited to tetrafluoroethene, hexafluoropropylene, chlorotrifluoroethylene, vinylidene, fluorothene, difluoroethylene or its potpourri.
(a2) used in the present invention monomer, must have at least a can with the functional group of (b) rigidizer reaction, produce backbone molecule and form interlinkage (Crosslinking) with intermolecular netted the combination, this sense base system is selected from by hydroxyl (OH), carboxyl (COOH), amido (NH
2), the group that formed of epoxy radicals and composition thereof, be preferably hydroxyl (OH).(a2) of the present invention monomer is such as but not limited to (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, hydroxybutyl vinethene, methacrylic acid-2-hydroxy methacrylate or its potpourri.
For plasticity, reduction in the adherence between increase stress buffer ability, raising protective seam and the base material, the enhancing are worked as the warpage defective of use base material (especially to glass baseplate; particularly less than 1 millimeter glass baseplate); optionally; the present invention also can comprise (a3) monomer in order to the monomer mixture that forms thermoset resin, and it is to be selected from three grades of carboxylic acid ester monomers, vinyl ether monomers, Vinyl Acetate Monomer, styrene monomer or its potpourri.
Be applicable to vinyl ether monomers of the present invention, there is no particular restriction, it is such as but not limited to having C
2~C
11The alkyl vinyl ether monomer of carbon number, its optional free straight chain shape alkyl vinyl ether monomer, branched-chain alkyl vinyl ether monomers, cyclic alkyl vinyl ether monomers and composition thereof constitute group, vinyl ether monomers used in the present invention is preferably cyclohexyl vinethene, ethyl vinyl ether and combination thereof.
Be applicable to three grades of carboxylates of the present invention, the following general formula of cording:
R wherein
3, R
4And R
5System represents the alkyl chain of straight chain or tool side chain: C
mH
2m+1, the integer of m=1 to 7 wherein; The preferably, R
3, R
4And R
5The carbon number summation be 9-11; And
R
6System is selected from the group that is made of following group:
Preferable is CH=CH
2Or
The example that is applicable to three grades of carboxylates of the present invention comprise three grades the last of the ten Heavenly stems vinyl carboxylates, three grades the ninth of the ten Heavenly Stems vinyl carboxylates and three grades the last of the ten Heavenly stems carboxylic acid epoxy propyl ester.
(a3) the general use of monomer there is no particular restriction, but if effect is preferable, then the particular thermal thermosetting resin can be arranged in pairs or groups and be used specific (a3) monomer, says it for example, polyacrylate resin can arrange in pairs or groups three grades of carboxylic acid ester monomers or Vinyl Acetate Monomer or its potpourri are more preferred from three grades of carboxylic acid ester monomers of collocation; The fluorocarbon resin vinyl ether monomers of then arranging in pairs or groups.
(b) used in the present invention rigidizer is a persond having ordinary knowledge in the technical field of the present invention institute well known; it has and at least aly can produce molecule and intermolecular chemical bond with (a2) monomer in the protective seam and form the functional group of interlinkage (Crosslinking), and this sense base system is selected from by isocyanate group (NCO), hydroxyl, carboxyl, ester group, acid anhydride base, amido (NH
2Or NHR) and composition thereof the group that is formed is preferably isocyanate group.By any known method in the prior art, can prepare polyisocyanate (polyisocyanate) with at least one free isocyanate groups.For example use monoisocyanates, diisocyanate or triisocyanate with functional group.The suitable diisocyanate and the example of triisocyanate include, but is not limited to: 1, hexamethylene-diisocyanate (Hexamethylene diisocyanate, HDI), 1,4-cyclohexane diisocyanate (1,4-Cyclohexane diisocyanate, CHDI), toluene diisocyanate (Toluene diisocyanate, TDI), 4,4 '-benzhydryl vulcabond (4,4 '-diphenylmethane diisocyanate, MDI), isophorone diisocyanate (Isophorone diisocyanate, IPDI), hexamethylene diisocyanate trimer or isophorone diisocyanate trimer.
According to a preferred embodiment of the present invention, the otpical leaf system that the present invention has reinforced structure comprises: a thickness is less than 1 millimeter glass baseplate; And the protective seam that is coated on a surface of this base material, these protection series of strata are made of organic layer, this organic layer has 5 microns to 15 microns thickness, and the preferable refractive index that has between 1.4 to 1.6, and this organic layer comprises (a) polyacrylate resin and (b) has isocyanate group functional group's rigidizer, is preferably diisocyanate; Wherein this otpical leaf measures according to the JISK7136 standard method, has the light penetration degree more than 90%; This polyacrylate resin is derived from the monomer mixture that comprises following monomer:
(a1) monomer, it is to be selected from the group that is made of (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate and composition thereof; And
(a2) monomer, its have can with the hydroxyl of (b) rigidizer reaction, preferably system is selected from the group that is made of (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, methacrylic acid-2-hydroxy methacrylate and composition thereof,
Above-mentioned monomer mixture can further comprise (a3) monomer, as the defined three grades of carboxylic acid ester monomers of preamble.
Protective seam of the present invention can optionally add any persond having ordinary knowledge in the technical field of the present invention's known additives, and it is such as but not limited to antistatic agent, fluorescer, ultraviolet light absorber, leveling agent, initiating agent, promoter, solvent, wetting agent, stabilization agent and spreading agent etc.
Can be used in antistatic agent of the present invention and there is no particular restriction, be that the persond having ordinary knowledge in the technical field of the present invention knows, for example ethoxy fatty acid glyceride class, quaternary ammonium compound compound, fatty amine analog derivative, epoxy resin (as polyethylene oxide), siloxane (siloxane) or other alcohol derivatives are as poly-ethanol ester, polyglycol ether etc.According to a specific embodiment of the present invention, the surface resistivity of otpical leaf of the present invention is between about 10
8To about 10
12Ω/ (square).
Can make an addition to the ultraviolet light absorber in the protective seam of otpical leaf of the present invention; the personage institute well known of this technology is had the knack of by system; it for example is benzotriazole (benzotriazoles), phentriazine class (benzotriazines), Benzophenone class (benzophenones) or salicyclic acid derivatives (salicylicacid derivatives) etc.; or use and can absorb ultraviolet inorganic particles, it is such as but not limited to zinc paste, silicon dioxide, titania, aluminium oxide, calcium sulphate, barium sulphate, lime carbonate or its potpourri.The particle size of above-mentioned inorganic particles is generally 1~100 nanometer (nano meter), is preferably 20~50 nanometers.
Can make an addition to the fluorescer in the otpical leaf protective seam of the present invention, there is no particular restriction, be to be familiar with known to the people of this skill, and it can be organism, such as but not limited to benzo
The two triazines (diphenylethylenebistriazines) of azole (benzoxazoles), benzimidazole (benzimidazoles) or talan.
One specific embodiment according to the present invention; lie in substrate surface and apply organic layer as protective seam; the organic series of strata that are used among the present invention comprise a kind of two-part thermocurable resin; it can be coated on the base material according to the known any way of persond having ordinary knowledge in the technical field of the present invention, and for example makes otpical leaf of the present invention via the method that comprises following steps:
(I) with (a1) monomer, (a2) monomer and (a3) monomer optionally, and optionally mix with known adjuvant (as solvent, initiating agent etc.), stoichiometric number hour under suitable temperature forms a multipolymer;
(II) this multipolymer is added rigidizer, optionally mix with known adjuvant (as solvent, promoter etc.), form a coating, it is coated on substrate surface, to form a protective seam;
(III) will be somebody's turn to do through the base material that applies and send dryer to, evaporating solvent is warming up to the required solidification temperature of thermoset resin, heats several minutes, carries out the heat curing polyreaction.
If need, can repeat above steps, to obtain the protective seam of plural layer.
Can make an addition to the initiating agent of above-mentioned steps (I), the personage institute well known of this technology is had the knack of by system, it for example is peroxidating benzene, cumyl peroxide, butylhydroperoxide, hydrogen phosphide cumene, tert-butyl peroxide maleic acid, the potpourri of potpourri, superoxide and the cobalt compound of tert-butyl hydroperoxide, acetyl pexoxide, lauroyl peroxide, azoisobutyronitrile (AIBN), ABVN, superoxide and amino acid or sulfonic acid or they's potpourri are preferably azoisobutyronitrile.
The promoter that can make an addition to above-mentioned steps (II) is at least a being selected from by methyl morpholine (methylmorpholine), ethyl morpholine (ethyl morpholine), triethylamine (triethyl amine), trimethylbenzene methyl amine (dimethyl benzyl amine), dimethylethanolamine (dimethyl ethanolamine), ethylenediamine (ethylene diamine), dimethyl lauryl amine (dimethyl laurylamine), lupetazin (dimethyl piperazine), hexane diamine (triethylene diamine), tetramethylethylenediamine (tetramethyl ethylene diamine), 4-methyl hexamethylene diamine (tetramethylhexamethylene diamine), 1,3,5-three or two aminomethyl phenol (1,3,5-tri diaminomethylphenol), 1,4-diaza-(2,2,2) bicyclooctane (1,4-diaza-(2,2,2) bicyclooctane), the own tetramine of hexamethyl (hexamethyl triethylene tetramine), lead octoate (lead octoate), dibutyl tin dilaurate (dibutyl tin dilaurirate), the group that thylhexoic acid tin (tin ethylhexanoate) and zirconium caprylate (zirconium octoate) are formed is preferably dibutyl tin dilaurate.
Can be used for solvent of the present invention and there is no particular restriction, it for example can be benzene class, ester class or ketone or its potpourri.The limiting examples of benzene kind solvent comprises: benzene,toluene,xylene (xylene), trimethylbenzene or styrene or its potpourri.The limiting examples of esters solvent comprises: ethyl acetate, butyl acetate, diethyl carbonate, ethyl formate, methyl acetate, acetic acid ethoxy ethyl ester, acetic acid ethoxy propyl ester or monomethyl ether propylene glycol ester or its potpourri.The limiting examples of ketones solvent comprises acetone, butanone, methyl ethyl ketone, cyclohexanone (cyclohexanone) or methyl isobutyl ketone or its potpourri.
In the above-mentioned steps (II), thermoset resin can directly be coated on the base material, and base material does not need to do extra surface treatment to increase adherence.The method system that applies in addition is familiar with this operator and knows, for example can use slit coating (slit coating), nick version printing coating (micro gravure coating), roller coating (roller coating) etc., or the combination of said method.
The protective seam that otpical leaf of the present invention had has high strength and good toughness, and good adherence is arranged between protective seam and the base material, does not therefore need to add in addition inorganics to gain in strength and adherence.Therefore, otpical leaf of the present invention can have preferable light penetration degree.Otpical leaf of the present invention measures according to JIS K7136 standard method, has the light penetration degree more than 90%, the preferable light penetration degree that has between 90% to 99%.Blooming of the present invention can be used in the light source device; for example: advertising lamp box and flat-panel screens etc.; especially can be used in the face equipment or backlight module of LCD (LCD); otpical leaf of the present invention forms protective seam at substrate surface; can strengthen the toughness of this base material effectively; and surfacing does not have warpage, therefore can avoid optical property to be affected.
Following examples will the present invention is described further, only non-in order to limiting the scope of the invention, and anyly is familiar with the technology of the present invention field person, without prejudice to spirit of the present invention following modification of being reached and variation, all belongs to scope of the present invention.
In the example, employed abbreviation is defined as follows:
MMA: methyl methacrylate
BA: butyl acrylate
2-HEMA: methacrylic acid-2-hydroxy methacrylate (2-hydroxyethyl methacrylate)
MAA: methacrylic acid
Cardura E10: three grades of carboxylate trade names, (Singapore's Hexion (Hexion) company)
AIBN: azoisobutyronitrile
CTFE: chlorotrifluoroethylene
EVE: ethyl vinyl ether
CHVE: cyclohexyl vinethene
HBVE: hydroxyl-butyl vinyl ether
TEA: triethylamine
N-3390: polyisocyanate trade name, Bayer company
N-75: polyisocyanate trade name, Bayer company
BAC: butyl acetate
DBTL: dibutyl tin dilaurate
Preparation example 1
Monomer, solvent and the suitable initiating agent of getting different proportion prepare the polyacrylate resin of embodiment 1, and preparation condition is as shown in table 1:
Table 1
Potpourri |
Monomeric species |
Consumption (gram) |
MMA |
29.0 |
BA |
11.0 |
2-HEMA |
7.0 |
MAA |
0.5 |
Cardura?E10 |
2.5 |
Solvent (dimethylbenzene) |
25.0 |
Solvent (BAC) |
25.0 |
Initiator (AIBN) |
1.0 |
Temperature of reaction (℃) |
110℃ |
Time (hour) |
8 hours |
Gu composition (weight %) |
50% |
Embodiment 1
With above-mentioned prepared polyacrylate resin and rigidizer and other solvent reaction, make the thermoset resin of protective seam of the present invention, preparation condition is as shown in table 2:
Table 2
Raw material |
Embodiment 1 |
Polyacrylate resin |
46.0 gram |
Polyisocyanate N-75 |
8.0 gram |
Toluene |
23.0 gram |
Butanone |
23.0 gram |
DBTL(1%) |
0.05 gram |
Condition of cure |
80~90 ℃, 2~3 minutes |
Preparation example 2-3
Monomer, solvent and the suitable initiating agent of getting different proportion prepare the fluorocarbon resin of embodiment 2, and preparation condition is as shown in table 3:
Table 3
|
Preparation example 2 |
Preparation example 3 |
Monomeric species and consumption (gram) |
CTFE |
420 |
325 |
EVE |
136 |
80.8 |
CHVE |
106 |
143.6 |
HBVE |
79 |
76.7 |
Solvent (toluene) |
462 |
394 |
Initiating agent (AIBN) |
2.2 |
1.6 |
TEA |
1.2 |
1.8 |
Temperature of reaction (℃) |
65℃ |
65℃ |
Reaction time (hour) |
22 hours |
22 hours |
Solid content (weight %) |
60.3 weight % |
59.6 weight % |
Embodiment 2-3
With above-mentioned prepared fluorocarbon resin and rigidizer and other solvent reaction, reaction conditions is as shown in table 4:
Table 4
|
Embodiment 2 |
Embodiment 3 |
Fluorocarbon resin |
10 grams |
10 grams |
Polyisocyanate N-3390 |
1.4 gram |
1.4 gram |
BAC |
20 grams |
20 grams |
DBTL(1%) |
0.05 gram |
0.05 gram |
Condition of cure |
60 ℃, 2 hours |
60 ℃, 2 hours |
Comparative example 1[does not contain rigidizer]
Commercially available thermoplasticity acryl resin: eterac 7109-X-50 (Eternal company)
Comparative example 2[does not contain three grades of carboxylic acid ester monomers and Vinyl Acetate Monomer]
But commercially available heat solidity acryl resin: eterac 7302-XC-60 (Eternal company)
Comparative example 3[does not contain vinyl ether monomers]
But commercially available heat solidity fluorocarbon resin: eterflon 4261A (Eternal company)
Method of testing:
Thickness test: utilize film thickness gauge [PIM-100, TESA company], press down the thickness that the way of contact measures embodiment 1 to 3 and comparative example diaphragm with 1N.
Film forming: coating is after solidifying, and hardens in surface bone dry, and whether look it has after-tackiness, and no after-tackiness then film forming is good.
Light penetration degree: utilize NDH 5000W haze meter (Japanese electric look company),, record full light penetration degree (Tt) according to JIS K7136 standard method.
The adherence test: hundred lattice scrapers are scraped in film coated surface, and after the back sticked tightly with adhesive tape, 90 ° tore up, and judge to peel off the lattice number.
Chemical proofing: 10%NaOH soaked 7 days, and 7 days backsights are filmed to have or not and peeled off.
Weatherability: QUV condition (ultraviolet 313nm, 60 ℃ * 4 hours+40 ℃ * 4 hours) is through shining more than 1000 hours, loss of gloss rate<60% of filming.
Camber test: testing sample is cut into the smooth diaphragm of length and width 100mm * 100mm, place 120 ℃ of baking ovens after 10 minutes, take out and be statically placed in room temperature, rise again to room temperature up to diaphragm, with the warpage degree of four jiaos on clearance gauge measurement diaphragm, use the heat-resisting and anti-warpage performance of assessment testing sample.
Test result:
Embodiment 1-3 is coated on 1 millimeter the glass baseplate, test result is as shown in table 5.
Table 5
|
Embodiment 1 |
Embodiment 2 |
Embodiment 3 |
Comparative example 1 |
Comparative example 2 |
Comparative example 3 |
Thickness (μ m) |
10±2μm |
10±2μm |
?10±2μm |
10±2μm |
10±2μm |
10±2μm |
Film forming |
Good |
Good |
Good |
Good |
Good |
Good |
The light penetration degree |
95 |
92 |
?91 |
88 |
93 |
90 |
Adherence |
100/100 |
100/100 |
?100/100 |
0/100 |
30/100 |
20/100 |
Chemical proofing |
Good |
Good |
Good |
Good |
Good |
Good |
Weatherability |
Good |
Good |
Good |
Can |
Good |
Good |
Camber test |
Good |
Good |
Good |
Difference |
Difference |
Difference |