CN104284913B - Resin-coated dose - Google Patents
Resin-coated dose Download PDFInfo
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- CN104284913B CN104284913B CN201380023942.5A CN201380023942A CN104284913B CN 104284913 B CN104284913 B CN 104284913B CN 201380023942 A CN201380023942 A CN 201380023942A CN 104284913 B CN104284913 B CN 104284913B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
Abstract
The present invention provides following resin, i.e., this resin does not use the inorganic oxide particle comprising the dispersion stabilizer as foreign body, and the heavy atom such as the bromine of the electrode corrosion etc. without the variable color and circuit being susceptible to resin self and sulfur, transparent and there is the high refraction of refractive index more than 1.6, and the xanthochromia of film is few.A kind of resin solution, it contains and uses polymer obtained by the compound represented with formula [1].(in formula, R1And R2Being separately hydrogen atom or methyl, n is the integer of 2～10).
Description
Technical field
The present invention relates to containing there is the polymerizable monomer of 1,3,5-triazine ring and being polymerized or obtained by copolymerization
The resin solution of polymer is as new resin-coated dose that can form epithelium that is transparent and that have high refraction of main component.
Background technology
(methyl) acrylic resin such as polymethyl methacrylate and transparent epoxy resin, transparent organic silicon resin etc.
Transparent resins compared with glass, light weight and excellent in workability, be gradually widely used in the resin that keeps out the wind of airborne vehicle etc., transparent appearance
Device, transparent smears etc..
In recent years, in the field of the optics of glasses etc., use the resin-made of transparent resinous lens etc. the most in a large number
Product.
In the field of electronic material, the most gradually it is largely used to the antireflection smears of liquid crystal display, used for solar batteries
In the purposes of the optical electron material of the light accepting part etc. of transparent smears, light emitting diode, CCD and cmos sensor.
In the purposes of such optical electron material, in order to improve the transparency, light extraction efficiency and collection photosensitiveness, most cases
Under also require high refractive index and light resistance.
But, current transparent resin is capable of mechanical properties is carried out a certain degree of control by the method for crosslinking etc.
System, but for the raising of optical characteristics, particularly refractive index, need special technology.That is, as the refraction that can improve resin
The method of rate, it is proposed that be combined with the organic resin (with reference to patent documentation 1 and 2) of the heavy atom such as bromine and sulfur in a large number.
Additionally, propose the method for the inorganic oxide particle of dispersion height refraction in organic resin in recent years, (reference is specially
Profit document 3 and 4).
As for obtain the method for above-mentioned high refraction resin and propose be combined with the heavy atom such as bromine and sulfur in a large number
In the case of organic resin, it is commonly angled relative to light and heat unstable, during life-time service, is susceptible to the deterioration of variable color etc..Additionally,
When electronic material parts use, the problem being susceptible to electrode corrosion etc..On the other hand, inorganic oxide height reflected
In the case of microgranule is scattered in the method for organic resin, these inorganic oxide particles, first make in suitable organic solvent
Manufacture particle dispersion liquid with substantial amounts of dispersion stabilizer, after being added to resin, organic solvent is distilled off and manufactures.
, the long-term storing stability of microgranule dispersion resin etc. has problems, and in order to improve the dispersion stabilization with resin, must
Substantial amounts of dispersion stabilizer must be mixed, there is the problem being difficult to obtain the balance etc. of refractive index and dispersion stabilization.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 05-164901
Patent documentation 2: Japanese Patent Laid-Open 2005-350531
Patent documentation 3: Japanese Patent Laid-Open 2007-270099
Patent documentation 4: Japanese Patent Laid-Open 2007-308631
Summary of the invention
Invent technical problem to be solved
It is an object of the invention to following resin supply to optical material and the field of electronic material, i.e. this resin is not
Use the inorganic oxide particle using the dispersion stabilizer as foreign body, and be entirely free of the change being susceptible to resin self
The heavy atoms such as the bromine of the problems such as the electrode corrosion of normal complexion circuit and sulfur, by basic 4 kinds of units of the organic resin of carbon, hydrogen, nitrogen and oxygen
Element is constituted, transparent and have the high refraction of refractive index more than 1.60, and the xanthochromia of film is few.
Particularly provide a kind of by operation before the sealing of light emitting diode being coated on photosemiconductor it is thus possible to
Improve transparency height, high index of refraction and resin-coated dose of high-light-fastness of light extraction efficiency.
Solve the technical scheme that technical problem is used
The present inventor has carried out conscientiously studying, found that have 1,3,5-triazines by use in order to achieve the above object
Ring and can solve the problem that directly in conjunction with the new compound (hereinafter also referred to specific compound) having aromatic ring on triazine ring
State technical problem, thus complete the present invention.
That is, the present invention has techniques below content.
(1) a kind of compound represented with following formula [1],
[changing 1]
In formula, R1And R2Being separately hydrogen atom or methyl, n is the integer of 2～10.
(2) compound as described in above-mentioned (1), wherein, with the R in the compound that above-mentioned formula [1] represents1For methyl, R2For
Hydrogen atom, n is 2～4.
(3) a kind of polymer, its by the homopolymerization of the compound described in above-mentioned (1) or (2) or with other monomer copolymerizations and
Obtain.
(4) polymer as described in above-mentioned (3), wherein, other monomers above-mentioned are selected from vinyl monomer, acrylic compounds list
More than one of body, methacrylic monomer, allylic monomers and Malaysia acrylic monomer.
(5) polymer as described in above-mentioned (3) or (4), wherein, other monomers above-mentioned are selected from vinyl acetate, benzene second
Alkene, tertiary ethylene carbonate (Japanese: バ サ チ ッ Network acid PVC ニ Le), acrylic acid, acrylic amide, there is the ring of carbon number 1～18
The acrylate of the alkyl of shape, straight-chain or branching type, methacrylic acid, Methacrylamide, there is the ring of carbon number 1～18
The methacrylate of the alkyl of shape, straight-chain or branching type, aromatic series allyl ester, the allyl compound containing heterocycle, Malaysia
Acid, maleic anhydride, maleimide and there is ring-type, the straight-chain of carbon number 1～18 or the maleic acid list of the alkyl of branching type
More than one of ester and maleic acid diester.
(6) polymer as according to any one of above-mentioned (3)～(5), wherein, relative to the compound of above-mentioned formula [1]
90～100 weight %, as other monomers above-mentioned selected from vinyl monomer, acrylic monomer, methacrylic monomer,
The total amount of more than one monomer of allylic monomers and Malaysia acrylic monomer is 0～10 weight %.
(7) polymer as according to any one of above-mentioned (3)～(6), wherein, above-mentioned homopolymerization or the copolymerization with other monomers
It is the radical polymerization using radical polymerization initiator.
(8) polymer as described in above-mentioned (7), wherein, above-mentioned radical polymerization is the use of the solution of organic solvent and gathers
Close.
(9) a kind of resin solution, it contains the polymer according to any one of above-mentioned (3)～(8).
(10) a kind of resin-coated dose, it is characterised in that by relative to the resin described in above-mentioned (9) of 100 weight portions
Resin solid content in solution, blend 0.1～10 weight portions selected from epoxy resin and the cross-linking agent of amino resin
Obtain.
(11) resin-coated dose as described in above-mentioned (10), wherein, above-mentioned amino resin is to have 2 in intramolecular
The melmac of above alkoxy methyl.
(12) a kind of epithelium, it is characterised in that by using resin-coated dose described in above-mentioned (10) or (11) to obtain,
And its refractive index at wavelength 633nm is more than 1.60.
The effect of invention
The compound of the present invention is the new compound that document is unknown, containing use this compound be polymerized obtained by poly-
Resin-coated dose of compound can form the resin involucra of the performance balance excellence of the transparency, high index of refraction, yellowing resistance etc., and
Show the thermostability of excellence.
The light of the light-emitting component of resin-coated dose such as light emitting diode etc. of the present invention takes out smears, CCD and CMOS passes
The photo detector of sensor, photoelectrical coupler etc., the smears of light harvesting smears, optical material and waveguide etc. of solaode
Like that, can be used on the industrial circle of the electronic material etc. simultaneously requiring high transparent, high index of refraction, high-light-fastness.
Detailed description of the invention
<specific compound>
The compound of the present invention represents with following formula [1].
[changing 2]
In formula, R1And R2Being separately hydrogen atom or methyl, n is the integer of 2～10.
R in formula1, from the viewpoint of polymerisation reactivity, preferably methyl.
R in formula2, from the viewpoint of dissolubility, preferably hydrogen atom.
In formula, n is the integer of 2～10, but from the viewpoint of polymerisation reactivity, dissolubility etc., preferably 2～6, more preferably
It is 2～4.
With in the compound that formula (1) represents, R1、R2With the preferred compositions of n it is: R1For methyl, R2For hydrogen or methyl, n is 2
～6.
Preferred combination is: R1For methyl, R2For hydrogen, n is 2～4.
For why being obtained in that the former of the effect of the present invention according to resin-coated dose of compound using the present invention
Very clear and definite because being not already, but it is considered owing to passing through on triazine skeleton directly in conjunction with phenyl, it is possible to improve the heat-resisting of compound
Property.
<synthetic method of specific compound>
The synthetic method of specific compound can synthesize by combining the technology in Synthetic Organic Chemistry, limits the most especially
Fixed.Such as can synthesize with following methods.
Specific compound can make compound (i) and methacrylic acid 2-hydroxyl by shown in synthetic schemes described as follows (A)
Arrcostab or the reaction of acrylic acid 2-hydroxyalkyl acrylate synthesize.
[changing 3]
The compound represented by formula (i) in synthetic schemes (A), can be such by synthetic schemes described as follows (B), makes three
Grignard reagent reaction represented by polychlorostyrene cyanogen and formula (ii) synthesizes.
[changing 4]
Additionally, can be by, shown in synthetic schemes described as follows (C), making 2-hydroxyethyl methacrylate or acrylic acid 2-hydroxyl
After base ethyl ester and Cyanuric Chloride are synthesized compound (iii), then it is made to react with the compound represented by compound (iv)
Synthesis.
[changing 5]
The raw material used in above-mentioned synthetic schemes (A)～(C), can use commercially available compound as required, it is also possible to
Additionally synthesize use.
<polymer and resin solution>
The polymer of the present invention can be the homopolymer of specific compound, it is also possible to be to make specific compound and can carry out altogether
Poly-selected from vinyl monomer, acrylic monomer, methacrylic monomer, allylic monomers and Malaysia acrylic monomer
Polymer obtained by more than one copolymerization.But, in the case of being somebody's turn to do, in order to keep high index of refraction, it is generally desirable to relative to 90～100
The specific compound of weight %, can with its copolymerization selected from vinyl monomer, acrylic monomer, methacrylic monomer and
More than one total amount of Malaysia acrylic monomer is 0～10 weight %, preferably 0～5 weight %.
As can be with the vinyl monomer of specific compound copolymerization, acrylic monomer, methacrylic monomer, allyl
Base class monomer and Malaysia acrylic monomer, as long as can the monomer of copolymerization can be then any monomer, as concrete example, can enumerate
Following monomer.
As vinyl monomer, the fragrance same clans such as styrene, divinylbenzene, vinyl naphthalene, divinyl naphthalene can be enumerated
Vinyl compound；The vinyl esters such as vinyl acetate, tertiary ethylene carbonate, hexanedioic acid vinyl ester；Methyl vinyl ketone, ethyl
The vinyl ketones such as vinyl ketone；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether；End has the poly-of vinyl
Dimethyl siloxane, end have the polydiphenylsiloxane of vinyl, end has the polydimethylsiloxane of vinyl-and poly-
Diphenylsiloxane copolymer, side chain have the polydimethylsiloxane of vinyl, side chain has the poly-diphenyl silicon of vinyl
Oxygen alkane, side chain have the silicone containing vinyl such as polydimethylsiloxane-polydiphenylsiloxane copolymer of vinyl
Deng.Wherein, preferably vinyl acetate, styrene, tertiary ethylene carbonate.
As the concrete example of acrylic monomer, acrylic acid, acrylic acid methyl ester., 1-Octyl acrylate, acrylic acid ten can be enumerated
The acrylicacidandesters classes such as octaester；There is ring-type, the straight-chain of carbon number 1～18 or the esters of acrylic acid of the alkyl of branching type；Double
Phenols epoxy resin be combined with acrylic acid obtained by bisphenol epoxy acrylate, novolac epoxy resin be combined with acrylic acid and
Novolak epoxyacrylate, cresol novolac epoxy resin and acrylic acid react obtained by cresol novolac ring
The Epoxy Acrylates such as oxypropylene acid esters；The polyester of polyethylene glycol phthalate, poly-phthalic acid butanediol ester etc.
Polyester acrylic esters obtained by being combined with acrylic acid；Isophorone diisocyanate class polyurethane, hexa-methylene two Carbimide.
Esters polyurethane etc. be combined with acrylic acid obtained by urethane acrylate class etc..Wherein, preferably acrylic acid, acrylamide
Class, there is ring-type, the straight-chain of carbon number 1～18 or the acrylate of the alkyl of branching type.
As the concrete example of methacrylic monomer, methacrylic acid, methyl methacrylate, metering system can be enumerated
Methacrylic acid and the esters thereof such as misery ester, octadecyl methacrylate；There is ring-type, straight-chain or the branch of carbon number 1～18
The methacrylate of the alkyl of type；Bisphenol-type epoxy resin be combined with methacrylic acid obtained by bisphenol epoxies methacrylic acid
Ester, novolac epoxy resin be combined with methacrylic acid obtained by novolak type epoxy methacrylate, cresol phenol
The epoxy methacrylic acids such as cresol novolac epoxy methacrylate obtained by formaldehyde epoxy resin and metering system acid reaction
Esters；Obtained by the polyester of polyethylene glycol phthalate, poly-phthalic acid butanediol ester etc. is combined with methacrylic acid
Polyester methacrylate class；Isophorone diisocyanate class polyurethane, hexamethylene diisocyanate class polyurethane etc. with
Urethane methacrylate class etc. obtained by methacrylic acid combination.Wherein, preferably methacrylic acid, Methacrylamide
Class, there is ring-type, the straight-chain of carbon number 1～18 or the methacrylate etc. of the alkyl of branching type.
As the concrete example of allylic monomers, the aromatic series allyl esters such as diallyl phthalate can be enumerated；Cyanogen
The allyl compound etc. containing heterocycle such as urea acid triallyl, triallyl isocyanurate.
As the concrete example of Malaysia acrylic monomer, maleic acid, maleic anhydride, monomethyl maleate, maleic acid two can be enumerated
The maleic acids such as methyl ester and esters thereof；Have ring-type, the straight-chain of carbon number 1～18 or the maleic mono-ester of the alkyl of branching type and
Maleic acid diester；Maleic anhydride and the polyalcohols such as ethylene glycol or neopentyl glycol react obtained by unsaturated polyester esters；Maleic acid
Acid anhydride and monoamine react obtained by single maleimide such as phenyl maleimide, N-cyclohexylmaleimide；Maleic anhydride
With diamine react obtained by the bismaleimide amine etc. such as diphenyl ether BMI.Wherein, preferably maleic acid, horse
Come anhydride, maleimide, there is ring-type, the straight-chain of carbon number 1～18 or the maleic mono-ester of the alkyl of branching type and horse
Carry out acid diesters etc..
As polyreaction, it is desirable to the polymerization initiator as spike employs free-radical polymerised polymerization
The radical polymerization of initiator.As the initiator of this radical polymerization, as long as the organic peroxies such as benzoyl peroxide
The redox type initiators etc. such as the azo type polymerization initiator such as compound, azodiisobutyronitrile, cumene hydroperoxide/cobalt naphthenate
Commonly used polymerization initiator, then can be any initiator.It is preferably the azo type polymerization such as azodiisobutyronitrile to cause
Agent.
As the method for polymerization, any one method in polymerisation in solution, polymerisation in bulk, suspension polymerisation etc. can be used.Body
In polymerization, suspension polymerisation etc., prepared resin is dissolved in suitable solvent and makes resin solution.In the present invention, use has
The solution polymerization process of machine solvent is suitable, for the kind of organic solvent, as long as the polymerization of specific compound can be manufactured
Thing or the solvent of copolymer, be not particularly limited.
In the case of this solution polymerization process, the resin solution after polymerization can use as the resin solution of the present invention, but also
Can in order to remove the purpose of the residual monomer etc. of trace, will polymerization after resin solution in the poor solvent of alcohol or hydrocarbon etc. again
Precipitation, manufactures resin solution by resinous principle filtration, dried being again dissolved in organic solvent.
The resin solution of the present invention is provided that a kind of resin-coated dose, this resin-coated dose by the coating on base material and
It is dried, the refractive index at mensuration wavelength 633nm can be formed and be more than 1.60, be preferably the transparent resin film of more than 1.61.In tree
In the stage of lipoprotein solution, resin molding is the film formed by thermoplastic resin, by blending cross-linking agent in resin solution, and can be further
Improve physical property.
<resin-coated dose>
Resin-coated dose of the present invention can be become by the resin solid of the resin solution relative to the 100 weight portion present invention
Point, blend 0.1～10 weight portions, preferably 1～5 the obtaining selected from epoxy resin and the cross-linking agent of amino resin of weight portion
Arrive.
Resin-coated dose of the present invention can give the performance as the resin by the resin solution gained of the present invention, and also
The performance of solvent resistance, thermostability, mechanical properties etc. can be given.
In this cross-linking agent, as epoxy resin, liquid bisphenol A type epoxy resin, solid-state bisphenol A-type asphalt mixtures modified by epoxy resin can be enumerated
Fat, liquid bisphenol F type epoxy resin, solid-state bisphenol f type epoxy resin, novolac type epoxy resin, cresol novolac type
Epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, triglycidyl isocyanurate, methyl-prop
Olefin(e) acid ethylene oxidic ester polymer, glycidyl methacrylate copolymer, epoxidised soybean oil etc..Wherein, preferably hydrogen
Change bisphenol A type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin etc..
As amino resin, it is generally desirable to intramolecular has the Lauxite of the alkoxy methyl of more than 2, trimerization
Melamine resin or benzoguanamine resin, it is therefore especially desired to intramolecular has the tripolycyanamide tree of the alkoxy methyl of more than 2
Fat.
Embodiment
The present invention will be described in more detail for embodiment shown below, but the present invention is not construed as being limited by this.
The assay method and the analytical equipment that use in embodiment are as described below.
<mensuration of NMR>
By the compound dissolution of gained in deuterochloroform, add tetramethylsilane (TMS) 0.05 weight % as internal standard,
Use 400MHz's1H NMR (Varian Co., Ltd. (バ リ ア Application society) system) is measured.
<xanthochromia degree and the mensuration of light transmission>
The spectrophotometer UV-3100PC using Shimadzu Corporation (Jin Zuosuo society) to make measures xanthochromia degree
With the light transmittance at wavelength 400nm.
<mensuration of refractive index>
Use the automatic elliptical polarization instrument instrument DVA-that Co., Ltd. of ditch buttocks optics industry institute (buttocks optics Gong Suo society) makes
FLVW determines the refractive index measured at wavelength 633nm.
<sunproof evaluation>
On the quartz base plate being formed with epithelium, use the Ci4000 that Aunar Lai Si Co., Ltd. (ア ト ラ ス society) makes,
Radiant intensity at 300～400nm is 60W/m2Under conditions of irradiate 72 hours, have rated the change of the xanthochromia degree after pre-irradiation
Amount.
(embodiment 1)
The synthesis of specific compound [M1]
Adding 38.5g Cyanuric Chloride and 385g oxolane in 1L (liter) four-hole boiling flask, ice bath cools down.Temperature 0 DEG C
Under, the tetrahydrofuran solution of the phenyl-magnesium-chloride of 2 mol/L of dropping 240ml, then, it is stirred at room temperature 15 hours.To reaction
Liquid adds 1 equivalent (Japanese: the fixed) hydrochloric acid of 300mL, extracts by ethyl acetate.After separating organic layer, to organic layer
Middle interpolation saturated sodium bicarbonate aqueous solution, separates the organic layer of ethyl acetate.In organic layer, add anhydrous magnesium sulfate, filter
Rear use rotary evaporator is distilled off solvent.By residue with silica gel column chromatography (effluent use hexane/ethyl acetate=3/1)
It is purified, obtains the midbody compound that 42.8g represents with (L1).
[changing 6]
10.0g midbody compound (L1) is joined in 300mL four-hole boiling flask, then adds 100g oxolane and carry out molten
Solve.Solution is cooled to temperature 0 DEG C, adds 1.8g sodium hydride, dropping 5.3g 2-hydroxyethyl methacrylate and 80g tetrahydrochysene furan
The solution muttered, stirs 30 minutes.In reactant liquor, add 15 weight % aqueous ammonium chloride solutions, extract by ethyl acetate.To
Organic layer after separation adds anhydrous magnesium sulfate, after filtration, uses rotary evaporator that solvent is distilled off.By residue silica gel
Column chromatography (effluent uses hexane/ethyl acetate=3/1) is purified, and obtains 9.7g white solid.
This white solid1The measurement result of H NMR is as follows.According to this result, confirm that the white solid of gained is
The compound represented with following formula (M1).
1H-NMR(400MHz,CDCl3):δ8.66-8.61(m,4H),7.64-7.50(m,6H),6.15-6.12(m,1H),
5.57-5.53(m,1H),4.94-4.89(m,2H),4.66-4.61(m,2H),1.94-1.90(m,3H)
[changing 7]
(comparing synthesis example 1)
The synthesis of compound [M2]
15.0g Cyanuric Chloride, 12.7g 2-hydroxyethyl methacrylate and 150g tetra-is added in 500mL four-hole boiling flask
Hydrogen furan, is cooled with an ice bath.At temperature 0 DEG C, add 3.9g sodium hydride, be then stirred at room temperature 3 hours.Add further
The 4-phenol of 12.5g, 2.9g sodium hydroxide, 23g oxolane and the aqueous solution of 30g water.Then 15 weight % ammonium chloride are added
Aqueous solution, extracts by ethyl acetate.Organic layer after separating adds anhydrous magnesium sulfate, after filtration, uses rotary evaporation
Device is distilled off solvent.Residue is purified by recrystallization, obtains the intermediate that 21.7g represents with (L2).
[changing 8]
In 500mL four-hole boiling flask, add 21.4g midbody compound (L2) and 170g acetone, drip 9.3g under reflux
4-phenol, 2.2g sodium hydroxide, 43g acetone and the aqueous solution of 43g water.Then 15 weight % aqueous ammonium chloride solutions, mistake are added
The crystallization that filter generates.Crystallization is purified by recrystallization, obtains 25.2g white solid (yield 89%).
This white solid1The measurement result of H NMR is as follows.According to this result, confirm that the white solid of gained is
The polymerizable monomer represented with following formula (M2).
1H NMR(400MHz,CDCl3):δ7.62-7.52(m,8H),7.46-7.39(m,4H),7.39―7.33(m,
2H),7.26-7.21(m,4H),6.13-6.10(m,1H),5.62-5.56(m,1H),4.65-4.58(m,2H),4.48-4.42
(m,2H),1.95-1.92(m,3H)
[changing 9]
(comparing synthesis example 2)
The synthesis of compound [M3]
15.0g Cyanuric Chloride, 12.7g 2-hydroxyethyl methacrylate and 150g tetra-is added in 500mL four-hole boiling flask
Hydrogen furan, is cooled with an ice bath.At temperature 0 DEG C, add 3.9g sodium hydride, be stirred at room temperature 3 hours.Add 14.9g further
Phenol, 6.3g sodium hydroxide and the aqueous solution of 60g water, be heated to temperature 50 C, stirs 2 hours.It is then cooled to room temperature, adds
15 weight % aqueous ammonium chloride solutions, extract by ethyl acetate.Organic layer after separating adds anhydrous magnesium sulfate, filters
Rear use rotary evaporator is distilled off solvent.By residue with silica gel column chromatography (effluent use hexane/ethyl acetate=3/1)
It is purified, obtains 20.5g white solid.
This white solid1The measurement result of H NMR is as follows.According to this result, confirm that the white solid of gained is
The polymerizable monomer represented with following formula (M3).
1H NMR(400MHz,CDCl3):δ7.43-7.34(m,4H),7.28-7.22(m,2H),7.19―7.12(m,
4H),6.14-6.08(m,1H),5.60-5.55(m,1H),4.58-4.52(m,2H),4.42-4.37(m,2H),1.94-1.90
(m,3H)
[changing 10]
[the manufacture example of resin solution]
(embodiment 2)
In the there-necked flask with nitrogen ingress pipe put into 8.6g polymerizable monomer (M1), 0.5g methacrylic acid and
21g as the Ketohexamethylene of solvent, stir make 1L nitrogen by capillary tube bubbling (Bubbling).Then, take out
Capillary tube, the gas phase being passed through in flask by the nitrogen of trace is to completely cut off air.Then, flask is heated, reach in interior temperature
The moment of 85 DEG C, 0.3g is as the 1 of polymerization initiator, 1-bis-(tertiary hexyl peroxy)-3,3,5-hexamethylene in interpolation, starts to gather
Close.After 85 DEG C of reactions 3 hours, it is warming up to 115 DEG C and makes its ripening 2 hours.It is then cooled to room temperature, obtain high refraction resin
Solution P1.
(comparing manufacture example 1)
In the there-necked flask with nitrogen ingress pipe put into 8.6g polymerizable monomer (M2), 0.5g methacrylic acid and
21g as the Ketohexamethylene of solvent, stir make 1L nitrogen by capillary tube bubbling.Then, capillary tube is taken out, by micro-
The gas phase that the nitrogen of amount is passed through in flask is to completely cut off air.Then, flask is heated, when interior temperature reaches 85 DEG C,
0.3g is as the 1 of polymerization initiator, 1-bis-(tertiary hexyl peroxy)-3,3,5-hexamethylene in interpolation, starts polymerization.In 85 DEG C of reactions
After 3 hours, it is warming up to 115 DEG C and makes its ripening 2 hours.It is then cooled to room temperature, obtain high refraction resin solution Q1.
(comparing manufacture example 3)
In the there-necked flask with nitrogen ingress pipe put into 8.6g polymerizable monomer (M3), 0.5g methacrylic acid and
21g as the Ketohexamethylene of solvent, stir make 1L nitrogen by capillary tube bubbling.Then, capillary tube is taken out, by micro-
The gas phase that the nitrogen of amount is passed through in flask is to completely cut off air.Then, flask is heated, when interior temperature reaches 85 DEG C,
0.3g is as the 1 of polymerization initiator, 1-bis-(tertiary hexyl peroxy)-3,3,5-hexamethylene in interpolation, starts polymerization.In 85 DEG C of reactions
After 3 hours, it is warming up to 115 DEG C and makes its ripening 2 hours.It is then cooled to room temperature, obtain high refraction resin solution Q2.
[manufacture of high refraction resin smears]
(embodiment 3)
Epoxy resin Co., Ltd. of Japan (ジ ャ パ Application エ Port is dissolved in the high refractive index resins solution P1 of embodiment 2
キ シ レ ジ Application society) hydrogenated bisphenol A epoxy resin (YX-8000) made, with epoxy resin relative to the high refraction of 100 weight portions
The weight rate of rate resin is that the condition of 5 weight portions blends, and obtains high index of refraction smears C1.
(comparative example 1)
The hydrogenation dissolving epoxy resin Co., Ltd. of Japan in comparing the high refractive index resins solution Q1 manufacturing example 1 is double
Phenol A epoxy resin (YX-8000), is 5 weight with epoxy resin relative to the weight rate of the high refractive index resins of 100 weight portions
The condition of part blends, and obtains high index of refraction smears D1.
(comparative example 2)
The hydrogenation dissolving epoxy resin Co., Ltd. of Japan in comparing the high refractive index resins solution Q2 manufacturing example 2 is double
Phenol A epoxy resin (YX-8000), is 5 weight with epoxy resin relative to the weight rate of the high refractive index resins of 100 weight portions
The condition of part blends, and obtains high index of refraction smears D2.
[evaluation of high refraction resin smears]
(embodiment 4)
Spin coater is used to be coated on the quartz plate of 4cm × 4cm by the high refraction resin smears C1 of embodiment 3,
After being dried 1 hour in 100 DEG C so that it is solidify 1 hour in 150 DEG C, obtain the transparent high refraction resin coating that thickness is 5 microns
The epithelium of agent C1.Appearance transparent, does not find coloring.
Additionally, relative to the high refraction resin smears C1 of 100 weight portions, blend 500 weight portion Ketohexamethylene, preparation dilution
Solution.Use prepared dilute solution, and use spin coater to be coated with on silicon, after being dried 1 hour in 100 DEG C, make
It solidifies 1 hour in 150 DEG C, makes the epithelium of the high refraction resin smears C1 of thickness 100 nanometer, for detecting refractive index.
Determine the light transmission of the epithelium of the high refraction resin smears C1 that thickness is 5 microns.Saturating at wavelength 400nm
The rate of penetrating is 96.8%, and xanthochromia degree is 0.65.
Additionally, determine the refractive index of the epithelium of the high refraction resin smears C1 that thickness is 100 nanometers.Measure wavelength
Refractive index at 633nm is 1.617.
Additionally, carried out light fastness test, find that the variable quantity of xanthochromia degree is 1.23.
(comparative example 3)
Spin coater is used to be coated on the quartz plate of 4cm × 4cm by the high refraction resin smears D1 of comparative example 1,
After being dried 1 hour in 100 DEG C so that it is solidify 1 hour in 150 DEG C, obtain the transparent high refraction resin coating that thickness is 5 microns
The epithelium of agent D1.Appearance transparent, does not find coloring.
Additionally, relative to the high refraction resin smears D1 of 100 weight portions, blend 500 weight portion Ketohexamethylene, preparation dilution
Solution.Use prepared dilute solution, and use spin coater to be coated with on silicon, after being dried 1 hour in 100 DEG C, make
It solidifies 1 hour in 150 DEG C, makes the epithelium of the high refraction resin smears D1 of thickness 100 nanometer, for detecting refractive index.
Determine the light transmission of the epithelium of the high refraction resin smears D1 that thickness is 5 microns.Saturating at wavelength 400nm
The rate of penetrating is 96.9%, and xanthochromia degree is 0.58.
Additionally, determine the refractive index of the epithelium of the high refraction resin smears D1 that thickness is 100 nanometers.Measure wavelength
Refractive index at 633nm is 1.619.
Additionally, carried out light fastness test, find that the variable quantity of xanthochromia degree is 2.00.
(comparative example 4)
Spin coater is used to be coated on the quartz plate of 4cm × 4cm by the high refraction resin smears D2 of comparative example 2,
After being dried 1 hour in 100 DEG C so that it is solidify 1 hour in 150 DEG C, obtain the transparent high refraction resin coating that thickness is 5 microns
The epithelium of agent D2.Appearance transparent, does not find coloring.
Additionally, relative to the high refraction resin smears D2 of 100 weight portions, blend 500 parts by weight of cyclohexane, preparation dilution
Solution.Use prepared dilute solution, and use spin coater to be coated with on silicon, after being dried 1 hour in 100 DEG C, make
It solidifies 1 hour in 150 DEG C, makes the epithelium of the high refraction resin smears D2 of thickness 100 nanometer, for detecting refractive index.
Determine the light transmission of the epithelium of the high refraction resin smears D2 that thickness is 5 microns.Saturating at wavelength 400nm
The rate of penetrating is 97.7%.
Additionally, determine the refractive index of the epithelium of the high refraction resin smears D2 that thickness is 100 nanometers.Measure wavelength
Refractive index at 633nm is 1.578.
[table 1]
According to the result of table 1, use the transparency of epithelium obtained by the transparent high refraction smears of embodiment 4 high, and
Even if as the constitution element of organic resin, being entirely free of the element beyond 4 kinds of elements of de-carbon, hydrogen, oxygen and nitrogen, refractive index exists
Measure at wavelength 633nm also above 1.60, also demonstrate high-light-fastness.
On the other hand, although the epithelium obtained by comparative example 3 demonstrates and the epithelium same degree obtained by embodiment 4
Refractive index, but light resistance is problematic, comparative example 4 and the refractive index of the epithelium obtained is problematic.
The probability utilized in industry
Resin-coated dose of the present invention demonstrates the characteristic of high transparent, high index of refraction, and excellent in light-resistance, so at light
Learn in field of electronic materials the light of the light-emitting component as light emitting diode etc. take out smears, CCD and cmos sensor or
The photo detector of photoelectrical coupler etc., the light harvesting smears of solaode, lens pillar (Japanese: レ Application チ キ ュ ラ レ
Application ズ) etc. the smears of optical material, waveguide etc. etc. extremely useful.Additionally, also be used as the industry such as glass and plastic lens
The smears of material.
Here quote the description of Japanese patent application 2012-052024, power that on March 8th, 2012 files an application
The full content of profit claim and specification digest is as the announcement of description of the invention.
Claims (12)
1. the compound represented with following formula [1],
[changing 1]
In formula, R1And R2Being separately hydrogen atom or methyl, n is the integer of 2～10.
2. compound as claimed in claim 1, it is characterised in that with the R in the compound that described formula [1] represents1For methyl,
R2For hydrogen atom, n is 2～4.
3. a polymer, it is characterised in that by the homopolymerization of the compound described in claim 1 or 2 or be total to other monomers
Gather and obtain.
4. polymer as claimed in claim 3, it is characterised in that other monomers described are selected from vinyl monomer, acrylic acid
More than one of class monomer, methacrylic monomer, allylic monomers and Malaysia acrylic monomer.
5. the polymer as described in claim 3 or 4, it is characterised in that other monomers described are selected from vinyl acetate, benzene second
Alkene, tertiary ethylene carbonate, acrylic acid, acrylic amide, there is ring-type, the straight-chain of carbon number 1～18 or the alkyl of branching type
Acrylate, methacrylic acid, Methacrylamide, there is ring-type, the straight-chain of carbon number 1～18 or the first of the alkyl of branching type
Base acrylate, aromatic series allyl ester, allyl compound containing heterocycle, maleic acid, maleic anhydride, maleimide and
There are more than one of ring-type, the straight-chain of carbon number 1～18 or the maleic mono-ester of the alkyl of branching type and maleic acid diester.
6. polymer as claimed in claim 3, it is characterised in that be 100 weight % with the weight that copolymer is all, described formula
The amount of compound [1] is 90～100 weight %, as other monomers described selected from vinyl monomer, acrylic monomer,
The total amount of more than one monomer of methacrylic monomer, allylic monomers and Malaysia acrylic monomer is 0～10 weights
Amount %.
7. polymer as claimed in claim 3, it is characterised in that described homopolymerization or the copolymerization with other monomers are to use freely
The radical polymerization of base polymerization initiator.
8. polymer as claimed in claim 7, it is characterised in that described radical polymerization is the use of the solution of organic solvent
Polymerization.
9. a resin solution, it is characterised in that containing the polymer according to any one of claim 3～8.
10. one kind resin-coated dose, it is characterised in that by the resin solution described in the claim 9 relative to 100 weight portions
In resin solid content, blend the obtaining selected from epoxy resin and the cross-linking agent of amino resin of 0.1～10 weight portions.
11. the most resin-coated doses, it is characterised in that described amino resin is to have in intramolecular
The melmac of the alkoxy methyl of more than 2.
12. 1 kinds of epitheliums, it is characterised in that by using resin-coated dose described in claim 10 or 11 to obtain, and its
Refractive index at wavelength 633nm is more than 1.60.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012052024 | 2012-03-08 | ||
| JP2012-052024 | 2012-03-08 | ||
| PCT/JP2013/056192 WO2013133345A1 (en) | 2012-03-08 | 2013-03-06 | Resin coating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104284913A CN104284913A (en) | 2015-01-14 |
| CN104284913B true CN104284913B (en) | 2016-12-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380023942.5A Active CN104284913B (en) | 2012-03-08 | 2013-03-06 | Resin-coated dose |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6194881B2 (en) |
| KR (1) | KR102038722B1 (en) |
| CN (1) | CN104284913B (en) |
| TW (1) | TWI586656B (en) |
| WO (1) | WO2013133345A1 (en) |
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| KR20220157380A (en) * | 2020-04-03 | 2022-11-29 | 닛뽕소다 가부시키가이샤 | Two-component adhesive composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05164901A (en) | 1991-12-18 | 1993-06-29 | Kureha Chem Ind Co Ltd | High-refractive index synthetic resin lens |
| JP4041615B2 (en) * | 1999-03-26 | 2008-01-30 | 富士フイルム株式会社 | Polymer ultraviolet absorber and organic material, photographic element and silver halide photographic photosensitive material containing the polymer ultraviolet absorber |
| JP4363553B2 (en) * | 1999-05-14 | 2009-11-11 | 富士フイルム株式会社 | Electrolyte composition, photoelectric conversion element and photoelectrochemical cell |
| ATE284910T1 (en) * | 2000-01-05 | 2005-01-15 | Cambridge Display Tech Ltd | POLYMERS, THEIR PRODUCTION AND USE |
| JP2005097377A (en) * | 2003-09-24 | 2005-04-14 | Fuji Photo Film Co Ltd | Alignment layer, polymer, retardation plate using it, its preparing method and liquid crystal display device |
| JP4309807B2 (en) | 2004-06-09 | 2009-08-05 | 三井化学株式会社 | Method for producing plastic lens comprising episulfide sulfur atom-containing resin |
| JP5453707B2 (en) | 2006-05-19 | 2014-03-26 | 住友大阪セメント株式会社 | Zirconia-containing epoxy resin composition, transparent composite containing the same, light-emitting element, and optical semiconductor device |
| JP4749201B2 (en) | 2006-03-31 | 2011-08-17 | 三井化学株式会社 | Composition for sealing a semiconductor light emitting device |
| TW200806763A (en) * | 2006-07-21 | 2008-02-01 | Aica Kogyo Co Ltd | Coating agent for antireflection film and antireflection film |
| US20100090588A1 (en) * | 2006-08-21 | 2010-04-15 | Hodogaya Chemical Co., Ltd. | Compound having triazine ring structure substituted with pyridyl group and organic electroluminescent device |
| JP5229879B2 (en) * | 2007-06-08 | 2013-07-03 | 日本化薬株式会社 | (Meth) acrylate compound, resin composition containing the same, and cured product thereof |
| KR101617655B1 (en) * | 2009-08-13 | 2016-05-03 | 닛산 가가쿠 고교 가부시키 가이샤 | Transparent high-refractive-index resin composition |
| JP6146576B2 (en) * | 2011-12-21 | 2017-06-14 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using the same |
-
2013
- 2013-03-06 KR KR1020147027860A patent/KR102038722B1/en active IP Right Grant
- 2013-03-06 CN CN201380023942.5A patent/CN104284913B/en active Active
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| TW201350470A (en) | 2013-12-16 |
| WO2013133345A1 (en) | 2013-09-12 |
| KR20140130746A (en) | 2014-11-11 |
| JP6194881B2 (en) | 2017-09-13 |
| TWI586656B (en) | 2017-06-11 |
| JPWO2013133345A1 (en) | 2015-07-30 |
| KR102038722B1 (en) | 2019-10-30 |
| CN104284913A (en) | 2015-01-14 |
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