CN115960294A - Acrylic resin for thiourea prepolymer modified optical film and preparation method thereof - Google Patents
Acrylic resin for thiourea prepolymer modified optical film and preparation method thereof Download PDFInfo
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- CN115960294A CN115960294A CN202310040206.6A CN202310040206A CN115960294A CN 115960294 A CN115960294 A CN 115960294A CN 202310040206 A CN202310040206 A CN 202310040206A CN 115960294 A CN115960294 A CN 115960294A
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 136
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 46
- 239000012788 optical film Substances 0.000 title claims abstract description 33
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000005276 aerator Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 14
- 125000003700 epoxy group Chemical group 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- IBPADELTPKRSCQ-UHFFFAOYSA-N 9h-fluoren-1-yl prop-2-enoate Chemical compound C1C2=CC=CC=C2C2=C1C(OC(=O)C=C)=CC=C2 IBPADELTPKRSCQ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- NDRHXLIHKZPWNE-UHFFFAOYSA-N SC1=CC=C(C=C1)C1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound SC1=CC=C(C=C1)C1=CC=CC=2C3=CC=CC=C3CC12 NDRHXLIHKZPWNE-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an acrylate resin for a thiourea prepolymer modified optical film and a preparation method thereof, wherein the resin comprises the following components: 100 parts of acrylate monomer, 10-30 parts of thiourea prepolymer, 1-5 parts of acid monomer, 1-5 parts of catalyst and 100-140 parts of solvent. Because the amino reaction activity of the thiourea is low, the thiourea prepolymer is synthesized from thiourea and a heterocyclic compound with polyfunctional epoxy, and a part of epoxy groups are reserved to react with carboxyl in acrylic resin, so that the thiourea prepolymer is easily connected to a main resin structure. The hydroxyl obtained by ring opening of the epoxy group can increase the adhesive force of the resin to the film, and the introduction of the polyfunctionality can improve the crosslinking degree of the resin so as to improve the scratch resistance of the surface coating of the film.
Description
Technical Field
The invention relates to the technical field of coating resin synthesis, in particular to acrylic resin for a thiourea prepolymer modified optical film and a preparation method thereof.
Background
The liquid crystal display optical film is an optical film formed by the principle of multiple refraction and focusing of light generated by a microstructure, and comprises a brightness enhancement film, a diffusion film, a reflection film and the like. The brightness enhancement film and the diffusion film are both required to be formed on the surface of a PET film with very good transparency by precisely forming a layer of optical film combined by a prism structure with uniform dispersion and a back light diffusion layer by using acrylate resin. When the light-equalizing structure is applied to a liquid crystal display, light is refracted and diffracted for multiple times through the diffusion layer, so that the light-equalizing function is achieved, and light display is more uniform and softer. Because the PET film is generally obtained by a biaxial stretching method, the thickness tolerance of the PET film hardly meets the requirement of an optical film, and a layer of acrylate resin coating is usually coated on the surface of the PET film to adjust the thickness to be uniform and reduce the refractive index, so that the uniform diffusion of a light source is realized, the transparency is improved, the haze is reduced, and the service performance of the optical film is improved. At present, the acrylate resin has the defects of poor adhesion, easy brittle fracture at low temperature, easy stickiness at high temperature, low refractive index and the like, which limits the application of the acrylate resin to a certain extent, so that the acrylate resin is very necessary to be modified.
The refractive index and dispersion of the resin used for optical films are key performance indexes, and in order to improve the refractive index of the optical resin, the introduction of sulfur element is one of the most common and effective methods. The TANGNIUM uses 4, 4-dihydroxy diphenyl sulfide, 4-dihydroxy diphenyl sulfone and acryloyl chloride to carry out nucleophilic substitution reaction, so as to synthesize the acrylate monomers M-1 and M-2 containing phenyl sulfide and phenyl sulfone group, and because the acrylate monomers are rich in benzene ring and sulfur element, the refractive index of the homopolymerized high-light-transmittance optical film can reach about 1.60, and is greatly improved compared with PMMA (1.49). You et al synthesized sulfur-containing acrylate monomers with higher sulfur content and 4,4' -BADS and 2,7-BAST through multi-step reaction, and then produced two optical films 3SMEA and APMEA with high refractive index, low birefringence and good light transmittance respectively through photopolymerization, and the refractive indexes thereof are 1.6544 and 1.6669 respectively. Chu et al use 9,9' -bis (4-mercaptophenyl) fluorene as a basic raw material to replace bisphenol fluorene and introduce two sulfur atoms to synthesize a high-refractive-index resin monomer, wherein the refractive index of the resin monomer is increased from 1.617 to about l.640 of diether fluorene acrylate. Usually, high-refractive-index groups such as benzene rings are introduced while sulfur is introduced, but the yellowing and high dispersion of the optical resin are inevitably caused by the high benzene ring content in the polymer. Matsuda et al synthesized several sulfur-containing acrylate monomers and homopolymers thereof, wherein the resins containing a benzene ring structure had a high refractive index, but had an Abbe number of only 27.8 and a high degree of dispersion, which decreased the clarity of the material.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide an acrylate resin for a thiourea prepolymer modified optical film and a preparation method thereof, wherein thiourea and a heterocyclic compound with epoxy with multiple functionality are synthesized to obtain the acrylate resin, a part of reserved epoxy groups can react with carboxyl in the acrylate resin, so that the epoxy groups can be easily grafted to a main resin structure, the adhesion of the resin to the film can be increased by hydroxyl obtained by ring opening of the epoxy groups, and the introduction of the multiple functionality can improve the crosslinking degree of the resin, so that the scratch resistance of a film surface coating is improved.
In order to solve the technical problems, the invention provides the following technical scheme:
an acrylate resin for a thiourea prepolymer modified optical film, the resin consisting of: 100 parts by weight of acrylate monomer, 10-30 parts by weight of thiourea prepolymer, 1-5 parts by weight of acid monomer, 1-5 parts by weight of catalyst and 100-140 parts by weight of solvent; the thiourea prepolymer is prepared from 100 parts by weight of thiourea, 50-150 parts by weight of polyfunctional epoxy heterocyclic compound and 1-3 parts by weight of tetrabutylammonium bromide through the following steps:
1) Dividing the polyfunctional heterocyclic epoxy compound into two parts, adding the first part of polyfunctional epoxy heterocyclic compound, thiourea and tetrabutylammonium bromide into a reaction kettle, stirring and heating to 120 ℃, keeping the temperature for 30min, introducing air with the temperature not lower than 115 ℃ and not higher than 125 ℃ into the reaction kettle through an aerator during the heat preservation, wherein the aperture of an aeration hole on the aerator is 0.1-0.15mm, and the aeration quantity is 0.6-1.0m 3 /h；
2) Adding a second part of polyfunctional epoxy heterocyclic compound into the reaction kettle, stirring and heating to 140 ℃ for reaction for 2 hours, and obtaining thiourea prepolymer after the reaction is finished; wherein before the second part of the polyfunctional epoxy heterocyclic compound is added into the reaction kettle, the aerator stops introducing air into the reaction kettle, the temperature is raised to 140 ℃, the reaction kettle is kept at the temperature for 30min, air with the temperature not lower than 135 ℃ and not higher than 145 ℃ is introduced into the reaction kettle through the aerator during the heat preservation, and the air flow is 0.8-1.2m 3 /h。
The weight ratio of the first part of the polyfunctional epoxy heterocyclic compound to the second part of the polyfunctional epoxy heterocyclic compound is 1-1.
The thiourea prepolymer modified acrylate resin for the optical film is characterized in that the acrylate monomer is one or a combination of methyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
The acrylic resin for the thiourea prepolymer modified optical film is characterized in that the acid monomer is one of acrylic acid and methacrylic acid.
The thiourea prepolymer is used for modifying the acrylate resin for the optical film, and the catalyst is one of benzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
The thiourea prepolymer modified acrylate resin for the optical film is prepared by mixing a solvent and a solvent, wherein the solvent is one or a combination of more of toluene, xylene, n-butyl acetate and sec-butyl acetate.
The thiourea prepolymer modified acrylate resin for the optical film is characterized in that the multifunctional epoxy heterocyclic compound is one or a combination of two of 1,3, 5-triglycidyl-S-triazine trione, 1, 3-diepoxyethylene- [1,3] diazepidine-2, 4-diketone and 1,3,5, 7-tetracyclooxymethyl- [1,3,5,7] tetraaza-2, 4,6, 8-tetraketone.
The preparation method of the acrylic resin for the thiourea prepolymer modified optical film comprises the following steps:
1) Adding a solvent into the reaction kettle, introducing nitrogen, starting stirring, and heating to 100 ℃;
2) Dropwise adding a mixed solution of an acrylate monomer, an acid monomer and 80% of a catalyst for 2 hours, and reacting for 2 hours under heat preservation;
3) Adding the thiourea prepolymer, heating to 120 ℃, adding 20% of catalyst, and reacting for 10 hours;
4) Adding a small amount of polymerization inhibitor, cooling and discharging.
The technical scheme of the invention achieves the following beneficial technical effects:
1. the thiourea prepolymer adopted by the invention is synthesized from thiourea and a heterocyclic compound with multiple functionality epoxy, a part of reserved epoxy groups can react with carboxyl in acrylate resin, so that the epoxy groups can be easily connected to a main resin structure, the hydroxyl groups obtained by ring opening of the epoxy groups can increase the adhesive force of the resin to a film, and the introduction of the multiple functionality can improve the crosslinking degree of the resin, so that the scratch resistance of a film surface coating is improved.
2. Meanwhile, the introduction of the nitrogen-containing heterocyclic ring can improve the refractive index of the polymer, improve the temperature resistance and ultraviolet aging resistance of the resin and avoid the defects of yellowing and increased dispersion of the optical resin caused by the introduction of the aromatic ring.
3. The resin is coated on the surface of the optical film, so that the light transmittance of the film can be improved, and the haze can be reduced.
Detailed Description
Example 1
In this example, 50 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 15 parts by weight of n-butyl methacrylate, 5 parts by weight of hydroxyethyl acrylate, 20 parts by weight of a thiourea prepolymer, 3 parts by weight of an acrylic monomer, 2 parts by weight of a catalyst, 70 parts by weight of xylene, and 55 parts by weight of n-butyl acetate. The synthesis method comprises the following steps:
1) Adding a solvent into the reaction kettle, introducing nitrogen, starting stirring, and heating to 100 ℃;
2) Dropwise adding a mixed solution of an acrylate monomer, an acid monomer and 80% of a catalyst for 2 hours, and reacting for 2 hours under heat preservation;
3) Adding thiourea prepolymer, heating to 120 ℃, adding 20% of catalyst, and reacting for 10 hours;
4) Adding a small amount of polymerization inhibitor, cooling and discharging.
The thiourea prepolymer is prepared from 100 parts by weight of thiourea, 100 parts by weight of 1,3, 5-triglycidyl-S-triazine trione and 1 part by weight of tetrabutylammonium bromide through the following steps:
1) Dividing the polyfunctional heterocyclic epoxy compound into two parts, adding the first part of the polyfunctional heterocyclic epoxy compound, thiourea and tetrabutylammonium bromide into a reaction kettle, stirring and heating to 120 ℃, preserving heat by 30min, introducing air with the temperature of 123 ℃ into the reaction kettle through an aerator during the heat preservation period, wherein the aperture of an aeration hole on the aerator is 0.15mm, and the ventilation volume is 1.0m 3 /h；
2) Adding a second part of polyfunctional epoxy heterocyclic compound into the reaction kettle, stirring and heating to 140 ℃ for reaction for 2 hours, and obtaining a thiourea prepolymer after the reaction is finished; wherein before the second part of the polyfunctional epoxy heterocyclic compound is added into the reaction kettle, the aerator stops introducing air into the reaction kettle, the temperature is raised to 140 ℃, the reaction kettle is kept at the temperature for 30min, air with the temperature of 143 ℃ is introduced into the reaction kettle through the aerator during the heat preservation, and the air flow is 1.2m 3 H is used as the reference value. The weight ratio of the first part of the multifunctional epoxy heterocyclic compound to the second part of the multifunctional epoxy heterocyclic compound is 1.
Example 2
The thiourea prepolymer modified acrylate resin in this example differs from example 1 in that: in this example n-butyl methacrylate was replaced by sec-butyl methacrylate.
Example 3
The difference between the thiourea prepolymer modified acrylate resin in this example and that in example 1 is: in this example, 3 parts of acrylic monomer was replaced with 1 part of acrylic monomer.
Example 4
The thiourea prepolymer modified acrylate resin in this example is different from that in example 1 in that: in this example, 3 parts of acrylic monomer was replaced with 5 parts of acrylic monomer. .
Example 5
The difference between the thiourea prepolymer modified acrylate resin in this example and that in example 1 is: in this example 55 parts by weight of n-butyl acetate were replaced by 55 parts by weight of xylene.
Example 6
The difference between the thiourea prepolymer modified acrylate resin in this example and that in example 1 is: in this example 100 parts by weight of 1,3, 5-triglycidyl-S-triazinetrione are replaced by 100 parts by weight of 1, 3-bisethoxyethylmethyl- [1,3] diazepinyl-2, 4-dione.
Example 7
The thiourea prepolymer modified acrylate resin in this example is different from that in example 1 in that: in this example, 100 parts by weight of 1,3, 5-triglycidyl-S-triazinetrione are replaced by 100 parts by weight of 1,3,5, 7-tetracyclooxymethyl- [1,3,5,7] tetraaza-2, 4,6, 8-tetraone.
Example 8
The thiourea prepolymer modified acrylate resin in this example is different from that in example 1 in that: in this example, 100 parts by weight of 1,3, 5-triglycidyl-S-triazinetrione were replaced by 50 parts by weight of 1,3, 5-triglycidyl-S-triazinetrione.
Example 9
The difference between the thiourea prepolymer modified acrylate resin in this example and that in example 1 is: in this example, 100 parts by weight of 1,3, 5-triglycidyl-S-triazinetrione were replaced by 150 parts by weight of 1,3, 5-triglycidyl-S-triazinetrione.
Example 10
The thiourea prepolymer modified acrylate resin in this example is different from that in example 1 in that: in this example 20 parts by weight of thiourea prepolymer was replaced by 10 parts by weight of thiourea prepolymer.
Example 11
The difference between the thiourea prepolymer modified acrylate resin in this example and that in example 1 is: in this example 20 parts by weight of thiourea prepolymer was replaced by 30 parts by weight of thiourea prepolymer.
Comparative example 1
Comparative example 1 is different from example 1 in that 20 parts by weight of thiourea prepolymer was replaced with methyl methacrylate.
Comparative example 2
Comparative example 2 is different from example 1 in that no aerator was used during the synthesis process of the thiourea prepolymer.
Samples were prepared using the acrylic resin for thiourea prepolymer-modified optical films prepared in examples 1 to 11 and the modified acrylic resins prepared in comparative example 1 and comparative example 2, and viscosity, refractive index, abbe number, light transmittance and haze were measured, and the results are shown in table 1.
TABLE 1 results of acrylic resin Performance test in examples 1 to 11 and comparative example 1 and comparative example 2
| Sample name | Viscosity/cp | Refractive index | Abbe number | Transmittance/% | Haze/% |
| Example 1 | 2650 | 1.69 | 44 | 91.1 | 1.5 |
| Example 2 | 2600 | 1.67 | 45 | 90.7 | 1.6 |
| Example 3 | 2400 | 1.67 | 45 | 90.7 | 1.6 |
| Example 4 | 2750 | 1.7 | 44 | 91.3 | 1.5 |
| Example 5 | 2500 | 1.67 | 45 | 90.6 | 1.7 |
| Example 6 | 2700 | 1.7 | 43 | 91.2 | 1.4 |
| Example 7 | 2800 | 1.72 | 40 | 91.4 | 1.8 |
| Example 8 | 2500 | 1.7 | 40 | 91.2 | 1.8 |
| Example 9 | 2800 | 1.66 | 45 | 90.5 | 1.5 |
| Example 10 | 2500 | 1.65 | 47 | 90.4 | 1.4 |
| Example 11 | 2750 | 1.7 | 41 | 91.5 | 1.7 |
| Comparative example 1 | 2600 | 1.5 | 36 | 89.7 | 2.7 |
| Comparative example 2 | 2700 | 1.6 | 40 | 90 | 2.2 |
Remarking:
(1) The viscosity was measured at room temperature with a rotational viscometer while controlling the solid content of the resin at 50%;
(2) The refractive index and Abbe number are measured by casting the acrylate resin into sample strips with the same thickness in a silica gel mold;
(3) The transmittance and haze were measured by coating an acrylate resin having a thickness of 2 μm on a 125 μm PET optical film, and drying the film (the original film of PET had a transmittance of 89.5% and a haze of 3.2%).
From the results shown in table 1, it is understood that the refractive index, abbe number, and light transmittance of the acrylic resin for a thiourea prepolymer-modified optical film obtained by modification with a thiourea prepolymer are improved to a high degree, and the haze is significantly reduced. The acrylic resin for the thiourea prepolymer modified optical film obtained by modifying the thiourea prepolymer prepared by introducing high-temperature gas into the reaction liquid by using the aerator in the thiourea prepolymer synthesis process has better refractive index, abbe number and light transmittance and lower haze.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.
Claims (8)
1. An acrylate resin for a thiourea prepolymer modified optical film, characterized in that the resin is composed of the following components: 100 parts by weight of acrylate monomer, 10-30 parts by weight of thiourea prepolymer, 1-5 parts by weight of acid monomer, 1-5 parts by weight of catalyst and 100-140 parts by weight of solvent; the thiourea prepolymer is prepared from 100 parts by weight of thiourea, 50-150 parts by weight of polyfunctional epoxy heterocyclic compound and 1-3 parts by weight of tetrabutylammonium bromide through the following steps:
1) Dividing the polyfunctional heterocyclic epoxy compound into two parts, adding the first part of polyfunctional epoxy heterocyclic compound, thiourea and tetrabutylammonium bromide into a reaction kettle, stirring and heating to 120 ℃, keeping the temperature for 30min, introducing air with the temperature not lower than 115 ℃ and not higher than 125 ℃ into the reaction kettle through an aerator during the heat preservation, wherein the aperture of an aeration hole on the aerator is 0.1-0.15mm, and the air throughput is 0.6-1.0m 3 /h；
2) Adding a second part of polyfunctional epoxy heterocyclic compound into the reaction kettle, stirring and heating to 140 ℃ for reaction for 2 hours, and obtaining a thiourea prepolymer after the reaction is finished; wherein before the second part of the polyfunctional epoxy heterocyclic compound is added into the reaction kettle, the aerator stops introducing air into the reaction kettle, the temperature is raised to 140 ℃, the reaction kettle is kept for 30min, air with the temperature not lower than 135 ℃ and not higher than 145 ℃ is introduced into the reaction kettle through the aerator during the heat preservation period, and the air flow is 0.8-1.2m 3 /h。
2. The acrylic resin for a thiourea prepolymer modified optical film according to claim 1, wherein the weight ratio of the first part of the polyfunctional epoxy heterocyclic compound to the second part of the polyfunctional epoxy heterocyclic compound is 1.
3. The acrylate resin for the thiourea prepolymer modified optical film according to claim 1, wherein the acrylate monomer is one or more of methyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
4. The acrylic resin for a thiourea prepolymer modified optical film of claim 1, wherein the acid monomer is one of acrylic acid and methacrylic acid.
5. The acrylate resin for the thiourea prepolymer modified optical film according to claim 1, wherein the catalyst is one of benzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
6. The acrylic resin for the thiourea prepolymer modified optical film of claim 1, wherein the solvent is one or a combination of more of toluene, xylene, n-butyl acetate and sec-butyl acetate.
7. The acrylate resin for thiourea prepolymer modified optical film according to claim 1, wherein the polyfunctional epoxy heterocyclic compound is one or a combination of two of 1,3, 5-triglycidyl-S-triazinetrione, 1, 3-diepoxyethylmethyl- [1,3] diazepinyl-2, 4-dione, 1,3,5, 7-tetracycloxymethyl- [1,3,5,7] tetraaza-2, 4,6, 8-tetraone.
8. The method of preparing the acrylate resin for the thiourea prepolymer modified optical film according to any one of claims 1 to 7, comprising the steps of:
1) Adding a solvent into the reaction kettle, introducing nitrogen, starting stirring, and heating to 100 ℃;
2) Dropwise adding a mixed solution of an acrylate monomer, an acid monomer and 80% of a catalyst for 2 hours, and reacting for 2 hours under heat preservation;
3) Adding the thiourea prepolymer, heating to 120 ℃, adding 20% of catalyst, and reacting for 10 hours;
4) Adding a small amount of polymerization inhibitor, cooling and discharging.
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| CN1723418A (en) * | 2002-10-09 | 2006-01-18 | 日产化学工业株式会社 | Composition for forming antireflection film for lithography |
| CN104844784A (en) * | 2015-04-13 | 2015-08-19 | 长江大学 | Epoxy resin flexible curing agent and synthetic method thereof |
| CN104961857A (en) * | 2015-06-30 | 2015-10-07 | 中国乐凯集团有限公司 | Modified (methyl) acrylate resin and preparation method |
| CN109054607A (en) * | 2018-06-15 | 2018-12-21 | 苏州益可泰电子材料有限公司 | Heat-barrier material and preparation method thereof |
| WO2021193635A1 (en) * | 2020-03-27 | 2021-09-30 | 関西ペイント株式会社 | Epoxy resin and electrodeposition coating |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1723418A (en) * | 2002-10-09 | 2006-01-18 | 日产化学工业株式会社 | Composition for forming antireflection film for lithography |
| CN104844784A (en) * | 2015-04-13 | 2015-08-19 | 长江大学 | Epoxy resin flexible curing agent and synthetic method thereof |
| CN104961857A (en) * | 2015-06-30 | 2015-10-07 | 中国乐凯集团有限公司 | Modified (methyl) acrylate resin and preparation method |
| CN109054607A (en) * | 2018-06-15 | 2018-12-21 | 苏州益可泰电子材料有限公司 | Heat-barrier material and preparation method thereof |
| WO2021193635A1 (en) * | 2020-03-27 | 2021-09-30 | 関西ペイント株式会社 | Epoxy resin and electrodeposition coating |
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