CN110938401B - Special adhesive for bulletproof material - Google Patents
Special adhesive for bulletproof material Download PDFInfo
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- CN110938401B CN110938401B CN201911297801.8A CN201911297801A CN110938401B CN 110938401 B CN110938401 B CN 110938401B CN 201911297801 A CN201911297801 A CN 201911297801A CN 110938401 B CN110938401 B CN 110938401B
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- monomer
- epoxy
- modified
- special adhesive
- bulletproof material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
Abstract
The invention relates to the technical field of sulfur-containing compounds, and particularly relates to a special adhesive for a bulletproof material. The adhesive is prepared by modifying a mercapto monomer and epoxy resin, quickly pre-polymerizing at a reaction temperature by heating under a vacuum condition, then quickly cooling, and quenching the pre-polymerization reaction to obtain a prepolymer; the modified mercapto monomer has better rigidity and a three-dimensional network structure, and is beneficial to increasing the toughness of the adhesive. Experimental results show that the special adhesive for the bulletproof material, which is prepared by the preparation method, has the advantages of high product light transmittance, high curing speed, high bonding strength, strong impact deformation resistance and very good application prospect.
Description
Technical Field
The invention relates to the technical field of sulfur-containing compounds, and particularly relates to a special adhesive for a bulletproof material.
Background
The bulletproof glass has the light and image transmission performance of the glass, and also has the protection capability on bullet shooting, can be used as military defense, guard glass of bank counters, jewelry, gold and silver ornaments and other valuable article display cabinets and other specific working and living places, and is formed by scientifically combining a plurality of pieces of transparent glass with different thicknesses and different physical properties, a plurality of pieces of PVB/PU films and an impact-resistant organic transparent plate. Since the glass and the PVB/PU film are bonded very firmly and almost integrally, and the PVB film and the impact-resistant organic transparent plate have good toughness due to the high hardness of the glass, the impact energy of the glass and the PVB/PU film is weakened to a low degree or even zero after the glass is contacted by bullets, so that the glass cannot penetrate.
Bullet-proof glass generally has the following three-layer structure:
a bearing layer: the layer is first subjected to impact and breaks, generally glass with large thickness and high strength is adopted, and the bullet can be damaged or the shape of the bullet can be changed, so that the bullet loses the capability of continuing advancing.
Transition layer: generally, organic gluing materials are adopted, so that the bullet has strong bonding force and good light resistance, can absorb part of impact energy, and changes the advancing direction of the bullet. A layer of very firm and transparent organic gluing material is sandwiched in the laminated glass, so that the bullet shooting can be effectively prevented, and the bullet shooting protective glass also has the performances of surge impact resistance, explosion resistance, shock resistance, no crack after impact and the like.
A safety protection layer: the layer is made of high-strength glass or high-strength transparent organic materials, has good elasticity and toughness, can absorb most of impact energy, and ensures that bullets cannot penetrate through the layer.
Chenyuhong in the research on the formation and application of transparent polyurethane film mentioned the manufacture, casting and performance test of transparent Polyurethane (PUR) film, and described that the PUR film has better optical performance and bulletproof effect in the manufacture of high-performance laminated transparent material. In the field of adhesives for bulletproof purposes, foreign research starts earlier, and foreign transparent adhesives for bulletproof purposes have the characteristics of small density, strong adhesion, high light transmittance and the like, but in the practical application process, as the monomer components of the adhesives contain groups easy to yellow, the bulletproof appliances are caused to have a yellow phenomenon after being used for a period of time, the light transmittance is influenced, and the observation of external conditions in the using process is not facilitated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the special adhesive for the bulletproof material, which selects the group with the light yellowing resistance and the toughness skeleton as the modified main body, contains sulfydryl and is modified and enhanced, has high light transmittance, high curing speed, high bonding strength and strong impact deformation resistance, overcomes the defect that the transparent bulletproof adhesive is easy to yellow, and has very good application prospect.
The invention provides a special adhesive for a bulletproof material, and a preparation method of the special adhesive comprises the following steps:
under the drying condition, adding a modified mercapto monomer and epoxy resin into a reactor, heating to the reaction temperature under the vacuum condition to perform rapid prepolymerization, then rapidly cooling, and quenching the prepolymerization reaction to obtain a prepolymer. The reaction equation is as follows:
the purpose of rapid quenching is to control the degree of prepolymerization, and without rapid quenching, the molecular weight increases and the liquid becomes too viscous.
Preferably, the epoxy resin is a predominantly aliphatic epoxy resin, including 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate or bis (2, 3-epoxycyclopentyl) ether or 2, 3-epoxycyclopentylcyclopentyl ether or vinylcyclohexene diepoxide or diisoprenyl diepoxide or 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ', 4 ' -epoxy-6 ' -methylcyclohexylmethyl ester or 3, 4-epoxycyclohexylcarboxylic acid-3 ', 4 ' -epoxycyclohexylmethyl ester or bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate (formula VII) or dicyclopentadiene diepoxide (formula VIII) or any combination thereof.
Preferably, the prepolymerization temperature is controlled to be 60-180 ℃, and the prepolymerization time is controlled to be 10-60 min.
Preferably, the molar ratio of the modified mercapto monomer to the epoxy resin is (0.5-10): 1.
preferably, the heating rate is controlled to be 1-10 ℃/5min, the rapid cooling rate is controlled to be 1-5 ℃/min, and the temperature is rapidly reduced to be below 45 ℃.
In the above reaction process, the modified mercapto monomer is synthesized by reacting thiol with isocyanate, and the reaction formula is as follows:
the specific process is as follows:
adding mercaptan and isocyanate into a reactor, then adding an organic amine promoter (catalyst), preserving heat, stirring for reaction, cooling to room temperature after the reaction is finished to obtain a crude product, then washing with water, and refining to remove water to obtain a modified mercapto monomer; wherein, the thiol end groups are all sulfydryl, and the rigid skeleton end groups of the isocyanate are all isocyanate groups.
After the reaction, water washing is required in order to remove the residual catalyst. Through modification, the monomer has better rigidity and a three-dimensional network structure, and is beneficial to increasing the toughness of the adhesive.
Preferably, the thiol is selected from 1, 4-benzenedithiol (formula i) or 2, 5-di-linear alkylmercapto-1, 4-dithiane (formula ii) or branched polyalkyl thiols thereof (formula iii) or 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane or 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane or 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane or any combination thereof.
Preferably, the isocyanate is non-yellowing isocyanate, and is particularly preferably selected from one or more of methylene type, aliphatic type and alicyclic type, and the three groups in the non-yellowing type determine that yellowing is not easy to occur in illumination.
More preferably, the isocyanate is selected from XDI, TMXDI, HDI, TMHDI, HTDI, or one or more selected from cyclohexane-1, 4-diisocyanate (formula IV), norbornane diethyl isocyanate (formula V), and 4, 4-diisocyanate dicyclohexylpropane (formula VI).
Preferably, the molar ratio of the mercaptan to the isocyanate in the reactor is (0.2-5): 1.
preferably, the organic amine accelerator can be aliphatic amine or alcohol amine compounds or aromatic amines;
more preferred organic amine accelerators are selected from the group consisting of N, N-dimethylcyclohexylamine or bis (2-dimethylaminoethyl) ether or N, N ' -tetramethylalkylenediamine or triethylamine, N-dimethylbenzylamine or N-ethylmorpholine or N-methylmorpholine or N, N ' -diethylpiperazine or triethanolamine or DMEA or N, N ' -dimethylpyridine or dibutyltin dilaurate or any combination thereof in an amount of 0.3 to 10% by weight of the reactants.
Preferably, the reaction temperature is 50-160 ℃, the stirring speed is 100-;
preferably, the amount of water used for washing is 0.5-2 times of the mass of the crude modified mercapto monomer, the washing time is 30-60min, the water removal temperature is 80-95 ℃, and the water removal is carried out for 1-4h under vacuum conditions.
Preferably, the synthesis of the modified sulfhydryl monomer is carried out in a nitrogen protection atmosphere, so as to prevent the chromaticity of the product from being influenced.
The inventor further discloses a method for processing a film sample by using the adhesive special for the transparent bulletproof material, which comprises the following steps: and (3) injecting the prepolymer into a mold by using a pouring device, carrying out photocuring by adopting ultraviolet irradiation of a certain wave band, and opening the mold after a certain time to obtain a film sample.
Preferably, the wavelength of the ultraviolet ray is controlled to be 350-420 nm, and the exposure time is 5-100S.
Preferably, 0.3 to 10 wt% of a mold release agent is added.
The invention mainly develops research aiming at the transition layer of the organic bonding material of the bulletproof glass, adopts thiol monomers different from the prior art, screens a series of isocyanate monomers with rigid and tough structures, changes the types of atoms or atomic groups on a large molecular chain by a block and graft method, and improves the bonding strength and the impact deformation resistance of the adhesive on the whole. Due to the introduction of sulfydryl, rigidity and toughness groups, the light transmittance of the transparent adhesive is improved to over 90 percent, the transparent adhesive has the advantage of rapid curing at a lower temperature after being initiated by ultraviolet rays, the defects of low curing speed, high energy consumption, long production period and poor performance of the adhesive in the existing wet preparation process of the bulletproof glass are overcome, the production period of the safety glass is shortened, the process is simpler, and the transparent adhesive is more suitable for batch production.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention, and the following embodiments are all completed by adopting the conventional prior art except for the specific description.
Example 1
(1) Under the protection of nitrogen, 284 g of 1, 4-benzenedithiol and 188 g of XDI are firstly added into a flask, then 5 g of promoter dibutyltin dilaurate is added, the temperature is 80 ℃, the stirring speed is 200 r/min, the reaction is kept for 50min, and the temperature is cooled to the room temperature.
(2) Adding 400 g of ultrapure water, stirring and washing for 40min, standing for layering, then cutting into water, and refining and dewatering at 85 ℃ under a vacuum condition to obtain 460 g of modified sulfhydryl monomer. Through modification, the monomer has a better three-dimensional network structure, and is beneficial to increasing the toughness of the adhesive.
(3) And (3) under the condition that the humidity is less than 10 percent, 160 g of dicyclopentadiene diepoxide and 230 g of the modified sulfydryl monomer obtained in the step (2) are added into a reactor, the temperature is increased to 60 ℃ at the temperature-increasing rate of 2 ℃/min under the vacuum condition, the reaction temperature is quickly prepolymerized for 15min, and then the temperature is quickly reduced to 35 ℃ at the temperature-reducing rate of 5 ℃/min.
And (3) detecting the performance:
taking 100g of a sample, adding 2 g of a release agent, uniformly stirring, injecting the prepolymer into a dumbbell-shaped film sample preparation mold in a laboratory by using a pouring device, carrying out photocuring by adopting 370-420nm ultraviolet irradiation, and opening the mold after 60S time to obtain a film sample 1 with the thickness of 2mm, wherein the structure is as follows:
example 2
(1) In the nitrogen protection atmosphere, 284 g of 1, 4-benzenedithiol and 260 g of cyclohexane-1, 4-diisocyanate are firstly added into a flask, 5 g of accelerating agent dibutyltin dilaurate is then added, the reaction is kept for 45min under the conditions that the temperature is 70 ℃ and the stirring speed is 200 r/min, and the reaction is cooled to the room temperature.
(2) Adding 500 g of ultrapure water, stirring and washing for 40min, standing for layering, then cutting into water, and refining and dewatering at 90 ℃ under a vacuum condition to obtain 530 g of modified sulfhydryl monomer. Through modification, the monomer has a better three-dimensional network structure, and is beneficial to increasing the toughness of the adhesive.
(3) And (3) under the condition that the humidity is less than 10 percent, 160 g of dicyclopentadiene diepoxide and 260 g of the modified sulfydryl monomer obtained in the step (2) are added into a reactor, the temperature is increased to 65 ℃ at the temperature-increasing rate of 3 ℃/min under the vacuum condition, the reaction temperature is quickly prepolymerized for 10min, and then the temperature is quickly reduced to 45 ℃ at the temperature-reducing rate of 7 ℃/min.
And (3) detecting the performance:
and (3) taking 100g of a sample, adding 2.5 g of a release agent, uniformly stirring, injecting the prepolymer into a dumbbell-shaped film sample preparation mold in a laboratory by using a pouring device, carrying out photocuring by adopting 370-420nm ultraviolet irradiation, and opening the mold after 70S time to obtain a film sample 2 with the thickness of 2 mm.
Example 3
(1) Under the protection of nitrogen, 189 g of 2, 5-dimethylene mercapto-1, 4-dithiane and 215 g of TMXDI are firstly added into a flask, then 5 g of promoter dibutyltin dilaurate is added, the reaction is kept for 55min under the conditions that the temperature is 80 ℃ and the stirring speed is 200 r/min, and the reaction is cooled to the room temperature.
(2) Adding 350 g of ultrapure water, stirring and washing for 40min, standing for layering, then cutting into water, and refining and dewatering at 75 ℃ under a vacuum condition to obtain 380 g of modified sulfhydryl monomer. Through modification, the monomer has a better three-dimensional network structure, and is beneficial to increasing the toughness of the adhesive.
(3) Under the condition that the humidity is less than 10 percent, 200 g of adipic acid di (3, 4-epoxy-6-methyl cyclohexyl methyl ester) and 190 g of the modified sulfydryl monomer in the step (2) are added into a reactor, the temperature is increased to 60 ℃ under the temperature increase rate of 2 ℃/min under the vacuum condition, the rapid prepolymerization is carried out for 20min, and then the temperature is rapidly reduced to 40 ℃ at the temperature reduction rate of 5 ℃/min.
And (3) detecting the performance:
and (3) adding 2 g of release agent into 100g of sample, uniformly stirring, injecting the prepolymer into a dumbbell-shaped film sample preparation mold in a laboratory by using a pouring device, carrying out photocuring by adopting 370-420nm ultraviolet irradiation, and opening the mold after 80S to obtain a film sample 3 with the thickness of 2 mm.
The samples of the examples were tested for their performance, with the following parameters:
therefore, the special adhesive for the bulletproof material provided by the invention has excellent performance, the light transmittance of the adhesive is improved to more than 90%, the adhesive has the advantage of rapid curing at a lower temperature after being initiated by ultraviolet rays, the defects of low curing speed, high energy consumption, long production period and poor adhesive performance in the existing wet preparation process of bulletproof glass are overcome, the production period of safety glass is shortened, and the process is simpler.
Claims (6)
1. The special adhesive for the bulletproof material is characterized by comprising the following steps:
under the drying condition, adding a modified mercapto monomer and epoxy resin into a reactor, under the vacuum condition, heating to the reaction temperature for fast prepolymerization, then quickly cooling, and quenching the prepolymerization reaction to obtain a prepolymer;
the modified mercapto monomer is synthesized by reacting mercaptan and isocyanate, the end group of the modified mercapto monomer is mercapto, and the molar ratio of the mercaptan to the isocyanate is (0.2-5): 1;
the thiol is selected from 1, 4-benzenedithiol or 2, 5-di-linear alkyl mercapto-1, 4-dithiane; the isocyanate is selected from one or more of XDI, TMXDI and cyclohexane-1, 4-diisocyanate;
the epoxy resin is aliphatic epoxy resin and comprises bis (2, 3-epoxy cyclopentyl) ether, 2, 3-epoxy cyclopentyl ether, vinylcyclohexene diepoxide, diisopropadiene diepoxide, 3, 4-epoxy-6-methyl cyclohexyl methyl formate-3 ', 4 ' -epoxy-6 ' -methyl cyclohexyl methyl ester, 3, 4-epoxy cyclohexyl methyl formate-3 ', 4 ' -epoxy cyclohexyl methyl ester, adipic acid bis (3, 4-epoxy-6-methyl cyclohexyl methyl ester) or dicyclopentadiene diepoxide or any combination thereof;
the mol ratio of the modified sulfhydryl monomer to the epoxy resin is (0.5-10): 1.
2. the special adhesive for the bulletproof material as claimed in claim 1, wherein the prepolymerization temperature is controlled to be 60-180 ℃, and the prepolymerization time is controlled to be 10-60 min.
3. The special adhesive for the bulletproof material of claim 1, wherein the heating rate is controlled to be 1-10 ℃/5min, the rapid cooling rate is controlled to be 1-5 ℃/min, and the temperature is rapidly reduced to be below 45 ℃.
4. The special adhesive for the bulletproof material of claim 1, wherein the modified mercapto monomer is synthesized by the following specific processes: adding mercaptan and isocyanate into a reactor, then adding an organic amine promoter, preserving heat, stirring for reaction, cooling to room temperature after the reaction is finished to obtain a crude product, then washing with water, and refining to remove water to obtain the modified mercapto monomer.
5. The special adhesive for the bulletproof material as defined in claim 4, wherein the organic amine accelerator is aliphatic amine or alcohol amine compound or aromatic amine, and the addition amount is 0.3-10 wt% of the reactants; the synthesis of the modified sulfhydryl monomer is carried out under the protection of nitrogen.
6. The special adhesive for the bulletproof material as defined in claim 4, wherein the reaction temperature is 50-160 ℃, the stirring speed is 100-; the water consumption of the water washing is 0.5-2 times of the mass of the crude product of the modified sulfhydryl monomer, the water washing time is 30-60min, the water removal temperature is 80-95 ℃, and the water removal is carried out for 1-4h under the vacuum condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911297801.8A CN110938401B (en) | 2019-12-13 | 2019-12-13 | Special adhesive for bulletproof material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911297801.8A CN110938401B (en) | 2019-12-13 | 2019-12-13 | Special adhesive for bulletproof material |
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| Publication Number | Publication Date |
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| CN110938401A CN110938401A (en) | 2020-03-31 |
| CN110938401B true CN110938401B (en) | 2020-09-25 |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821166A (en) * | 1970-09-01 | 1974-06-28 | Phillips Petroleum Co | Polymercaptan epoxy resin hardener |
| US3742006A (en) * | 1970-09-01 | 1973-06-26 | Phillips Petroleum Co | A polymercaptan composition |
| US6913798B2 (en) * | 2000-06-21 | 2005-07-05 | Mitsui Chemicals, Inc. | Sealing material for plastic liquid crystal display cells including two-component epoxy resin composition |
| CN102086363A (en) * | 2010-12-16 | 2011-06-08 | 厦门大学 | Epoxy resin adhesive using modified multielement sulfur alcohol as solidifying agent and preparation method thereof |
| DE102014202609B4 (en) * | 2014-02-13 | 2020-06-04 | tooz technologies GmbH | Amine-catalyzed thiol curing of epoxy resins |
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Address after: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee after: Yifeng New Material Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee before: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. |