CN116120888B - A low-temperature hardening-resistant silicone optical bonding adhesive and its preparation and application - Google Patents
A low-temperature hardening-resistant silicone optical bonding adhesive and its preparation and application Download PDFInfo
- Publication number
- CN116120888B CN116120888B CN202310085924.5A CN202310085924A CN116120888B CN 116120888 B CN116120888 B CN 116120888B CN 202310085924 A CN202310085924 A CN 202310085924A CN 116120888 B CN116120888 B CN 116120888B
- Authority
- CN
- China
- Prior art keywords
- substance
- bonding adhesive
- low
- optical bonding
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明涉及一种耐低温硬化的有机硅光学贴合胶及其制备和应用，属于粘结剂领域。本发明提供一种耐低温硬化的有机硅光学贴合胶，所述光学贴合胶包括下述配比的原料：乙烯基硅油+物质B的总质量100重量份，增粘树脂5～40重量份，具有硅氢官能团的线性聚硅氧烷1～20重量份，催化活性物质占M的0.1～50ppm，阻聚剂占M的0.001～1％；乙烯基硅油+物质B+增粘树脂+具有硅氢官能团的线性聚硅氧烷的总质量记为M；所述物质B的结构式为式I所示。本发明所得有机硅光学贴合胶在‑60℃～‑50℃的条件下低温冷冻，不结晶硬化，且透明度高，雾度低，黄变指数低。
The present invention relates to a low-temperature hardening-resistant silicone optical bonding adhesive and its preparation and application, belonging to the field of adhesives. The present invention provides a low-temperature hardening-resistant silicone optical bonding adhesive, the optical bonding adhesive comprises the following raw materials: 100 parts by weight of the total mass of vinyl silicone oil + substance B, 5 to 40 parts by weight of tackifying resin, 1 to 20 parts by weight of linear polysiloxane with silane functional groups, 0.1 to 50 ppm of catalytically active substances in M, and 0.001 to 1% of polymerization inhibitor in M; the total mass of vinyl silicone oil + substance B + tackifying resin + linear polysiloxane with silane functional groups is recorded as M; the structural formula of the substance B is shown in Formula I. The silicone optical bonding adhesive obtained by the present invention is low-temperature frozen under the conditions of -60°C to -50°C, does not crystallize and harden, and has high transparency, low haze, and low yellowing index.
Description
Technical Field
The invention relates to low-temperature-hardening-resistant organic silicon optical laminating adhesive, and preparation and application thereof, and belongs to the field of adhesives.
Background
The current commercialized liquid optical transparent adhesive of organic silicon mainly uses a hydrosilylation system, and the curing type of the adhesive comprises light/heat dual curing and heat curing.
With the development of 3C display and vehicle-mounted display in recent years, the organic silicon optical adhesive has the advantages of yellowing resistance, high touch sensitivity, high and low temperature resistance and the like compared with the traditional acrylic optical adhesive, and is widely applied to the application fields of vehicle-mounted and large-size commercial display screens and the like.
The traditional organic silicon optical laminating adhesive has a general molecular main chain with a polydimethylsiloxane structure, has a double-helix structure, has a regular molecular chain, and generally has a hardening phenomenon at-40 ℃ when frozen at low temperature. Dynamic mechanical analysis is used to find (DYNAMIC MECHANICAL ANALYSIS, DMA) that the silicon has obvious modulus transition near-40 ℃ and second obvious modulus transition behavior at-120 ℃, and analysis shows that the silicon has obvious modulus transition near-40 ℃ to be the crystallization behavior of polydimethylsiloxane molecules, and the second modulus transition behavior at-120 ℃ is the glass transition of the organosilicon.
When the screen is used in extremely cold areas below-40 ℃, the phenomenon of crystallization and hardening of glue can occur, so that the excessive internal stress on the surface of the screen can be caused, the display effect and the touch sensitivity are affected, and therefore, the improvement of the crystallinity of the traditional organic silicon optical laminating adhesive is particularly important.
Disclosure of Invention
Aiming at the defect that the existing organic silicon optical adhesive has obvious low-temperature crystallization hardening phenomenon at about minus 40 ℃, the invention partially damages the molecular regularity of the cured organic silicon optical adhesive by modifying the molecular structure, improves the low-temperature crystallization performance, is frozen at low temperature of minus 60 ℃ to minus 50 ℃, does not crystallize and harden, has high transparency, low haze and low yellowing index, and provides the optical adhesive touch screen with excellent comprehensive performance, which can be used in extremely cold environment conditions of minus 60 ℃ to minus 50 ℃.
The technical scheme of the invention is as follows:
The first technical problem to be solved by the invention is to provide the low-temperature-hardening-resistant organic silicon optical laminating adhesive, which comprises the following raw materials in proportion:
Wherein the catalytic active substance is a substance which plays a catalytic role in the catalyst (substance E), and the total mass of vinyl silicone oil, substance B, tackifying resin and linear polysiloxane with a silicon-hydrogen functional group is recorded as M;
The structural formula of the substance B is shown in the formula I:
Wherein R 1 is an alkyl group, an aryl group or an aralkyl group having 2 to 20 carbon atoms other than methyl, or a functional group containing an oxygen heteroatom, and 150.ltoreq.y+z.ltoreq. 2000,0.03.ltoreq.z/(y+z.ltoreq.0.2. Preferably, the method comprises the steps of, 200 is less than or equal to (y+z) and more than or equal to 1000.
Further, R 1 is an alkyl group having 3 to 12 carbon atoms, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, a methacryloxypropyl group, a 3- (2, 3-glycidoxypropyl) propyl group, a 2- (3, 4-epoxycyclohexane) ethyl group or the like, and is preferably a hexyl group, an octyl group or a phenyl group.
Further, the mass ratio of the vinyl silicone oil to the substance B is 10-90:90-10, preferably 30-80:70-20, and more preferably 50-80:50-20.
Preferably, the addition amount of the tackifying resin is 10 to 20 parts by weight.
Preferably, the catalytic active substance accounts for 1-10 ppm of M.
Preferably, the polymerization inhibitor accounts for 0.01-0.2% of M.
Further, the substance B is prepared by mixing a monomer containing dimethyl disulfide functionality with a monomer containing R 1 and a monomer containing dimethyl disulfide functionality in a ratio such that 0.03.ltoreq.z/(y+z). Ltoreq.0.2 in formula I, co-hydrolyzing under acidic or alkaline conditions, adding 1, 3-divinyl-1, 3-tetramethyldisiloxane and a catalytic substance, and performing equilibrium condensation reaction to obtain the substance B, wherein the ratio of the monomer containing dimethyl disulfide functionality to the monomer containing R 1 and methyl disulfide functionality is such that 0.03.ltoreq.z/(y+z). Ltoreq.0.2 in formula I. The crystallization temperature of the organic silicon optical bonding adhesive is reduced by utilizing the substance B for the first time.
In the preparation method of the substance B, the monomer containing the dimethyldiolyzing functionality is selected from dimethyldimethoxy silane, dimethyldiethoxy silane and the like.
In the preparation method of the substance B, the monomer containing R 1 and the di-hydrolysis functionality of methyl is selected from methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, methyl hexyl dimethoxy silane, methyl hexyl diethoxy silane, methyl octyl dimethoxy silane, methyl octyl diethoxy silane and the like.
Further, in the preparation method of the substance B, the catalytic substance is selected from one of tetramethyl ammonium hydroxide or silicon alkoxide thereof, potassium hydroxide, lithium hydroxide or tetrabutyl phosphonium hydroxide.
Further, the linear polysiloxanes with a hydrosilylation functionality (substance D-i.e. terminal and/or pendant hydrogen containing silicone oils) have the structural formula II and/or III:
In the formula II, o is more than or equal to 10 and less than or equal to 45, and in the formula III, p+q is more than or equal to 20 and less than or equal to 80,0.2, and q/(p+q) is more than or equal to 0.6.
Further, the linear polysiloxane (substance D) with the silicon hydride functional group is a mixture of substances shown in a formula II and a formula III, wherein the mass ratio of the substances shown in the formula II to the substances shown in the formula III in the mixture is 5-95:95-5, preferably 70-90:30-10.
Further, in the linear polysiloxane having a silicon hydride functional group, the molar ratio of the silicon hydride functional group (Si-H) in the formula II and the formula III to the vinyl silicone oil and the terminal vinyl functional group (Si-Vi) of the substance B is 0.5 to 0.9.
Further, the structure of the vinyl silicone oil is shown as a formula IV:
In the formula IV, vi represents vinyl, m is an integer of 150-2000, n is an integer of 0-30, and (m+n) satisfies the requirement of 300-200000 mPa.s for the viscosity of the vinyl polysiloxane at room temperature of 25 ℃, when n=0, the vinyl polysiloxane represented by (I) is a terminal vinyl polysiloxane, and when n is an integer of >0, the vinyl polysiloxane represented by (I) is a terminal vinyl polysiloxane.
Further, the tackifying resin (substance C) is an MQ resin with a structure (R 2 3SiO0.5)a(SiO2)d, wherein R 2 is C 1～C10 -containing alkyl (such as methyl, ethyl, propyl) or benzene ring-containing aryl, etc., preferably R 2 is all methyl, i.e. the tackifying resin is methyl MQ resin.
Further, the catalyst (substance E) is a metal compound or complex having hydrosilylation catalytic activity.
Preferably, the catalyst is selected from the group consisting of metal complexes of platinum, palladium, rhodium, and the like, preferably platinum.
More preferably, the catalyst is selected from chloroplatinic acid, complexes of chloroplatinic acid and isopropanol, complexes of chloroplatinic acid and divinyl tetramethyl disiloxane or complexes of chloroplatinic acid and 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane, preferably complexes of chloroplatinic acid and divinyl tetramethyl disiloxane, namely Karstedt's catalyst, compounds containing Pt and having conjugated olefin structures, such as trimethyl (methylcyclopentadienyl) platinum (IV) and bis (acetylacetonato) platinum (II), and the like, preferably Karstedt's catalyst having thermal catalytic activity.
Further, the polymerization inhibitor (substance F) is at least one of 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane and the like, preferably 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane.
The second technical problem to be solved by the invention is to provide a preparation method of the low-temperature-hardening-resistant organosilicon optical laminating adhesive, wherein the preparation method comprises the step of uniformly blending the raw materials to prepare the organosilicon optical laminating adhesive.
Further, the preparation method of the low-temperature-hardening-resistant organic silicon optical laminating adhesive comprises the following steps:
The method comprises the steps of preparing the double-component low-temperature-resistant optical cement:
the preparation method comprises the steps of (1) pre-dispersing and mixing vinyl silicone oil (substance A), substance B and tackifying resin (substance C) uniformly to prepare a basic sizing material, taking a part of the basic sizing material, stirring and mixing the catalyst (substance E) and the polymerization inhibitor (substance F) uniformly to prepare a first component, stirring and mixing the rest of the basic sizing material and linear polysiloxane (substance D) with a silicon hydride functional group uniformly to prepare a second component, mixing the first component uniformly when in use, removing bubbles, and blending the basic sizing material in the first component and the basic sizing material in the second component according to any proportion;
the second method comprises the steps of preparing single-component low-temperature-resistant optical cement:
The preparation method comprises the steps of pre-dispersing vinyl silicone oil, a substance B and tackifying resin, adding a catalyst and a polymerization inhibitor, stirring and mixing uniformly, adding linear polysiloxane with a silicon-hydrogen functional group, stirring and mixing uniformly, and finally filtering and packaging to obtain the organosilicon optical laminating adhesive.
Further, in the first or second method, the pre-dispersing or stirring means stirring for 10 to 30 minutes at a stirring speed of 30 to 35 Hz.
In the first method, the mixing ratio of the component A and the component B can be adjusted according to the reaction molar ratio of Si-H to Si-Vi, preferably 1:1 to 4:1, and more preferably 1:1.
In the first method, the components A and B are uniformly mixed when in use, and the mixture can be used after bubbles are removed.
The third technical problem to be solved by the invention is to indicate that the low-temperature-hardening-resistant organic silicon optical laminating adhesive is used in display screens, touch screens and other optical devices.
The invention has the beneficial effects that:
The invention provides a low-temperature-hardening-resistant organic silicon optical laminating adhesive, and preparation and application thereof, which can be used for laminating an organic silicon optical adhesive of a touch screen, and compared with the traditional organic silicon optical adhesive, a cured product of the organic silicon optical laminating adhesive has lower crystallization temperature, is frozen at low temperature of minus 60 ℃ to minus 50 ℃, cannot be hardened by crystallization, has high transparency, low haze and low yellowing index, and can be used for laminating the touch screen under extremely cold environment conditions of minus 60 ℃ to minus 50 ℃. The low-temperature-hardening-resistant organic silicon optical laminating adhesive provided by the invention can be cured by light activation or heating, is mainly used for laminating substrates and cover plates of display screens, touch screens, other optical devices and the like, can meet the requirements of processes such as adhesive scraping, adhesive dispensing, adhesive scraping, slit coating and the like, and can be applied under extremely cold environmental conditions ranging from minus 60 ℃ to minus 50 ℃.
Drawings
Fig. 1 is a graph of DMA modulus for example 3, example 7, and comparative example 3.
Detailed Description
The invention provides low-temperature-hardening-resistant organic silicon optical laminating adhesive, which mainly comprises the following components:
vinyl silicone oils (e.g., polydimethyl siloxane with terminal vinyl groups);
Substance B, vinyl-terminated polysiloxane substituted with other functional groups compared with partial methyl;
a substance C, tackifying resin;
Substance D, linear polysiloxane with hydrosilyl functional group;
a substance E, a catalyst;
substance F, polymerization inhibitor.
The preparation of the substance A is well known to the person skilled in the art, and is generally obtained by ring-opening polymerization of a dimethylsiloxane ring mixture (DMC) and 1, 3-divinyl-1, 3-tetramethyldisiloxane under the catalysis of tetramethylammonium hydroxide silicon alkoxide, heating to break enzyme, and decomposing a catalyst to remove low molecules. Can also be obtained through commercial channels, such as RH-Vi series vinyl silicone oil of Ningbo Hirudo materials science and technology Co., ltd., jiangsu Koch, new materials Co., ltdV-series vinyl silicone oils.
Substance B is a vinyl-terminated polysiloxane with partial methyl groups replaced by other functional groups, and the structure is shown as follows:
Wherein R 1 is other functional groups of the substituted methyl, R 1 can be other alkyl groups except the methyl, such as alkyl groups with 2-20 carbon atoms, preferably alkyl groups with 3-12 carbon atoms, preferably hexyl, octyl and the like, R 1 can also be aryl or aralkyl groups, such as phenyl, naphthyl, benzyl, phenethyl and the like, preferably phenyl. R 1 can also be an oxygen heteroatom containing functional group such as methacryloxypropyl, 3- (2, 3-glycidoxypropyl), 2- (3, 4-epoxycyclohexane) ethyl, and the like.
The values of y and z in the substance B are 150-2000 (y+z), preferably 200-1000,0.03 (y+z) z/(y+z) 0.2, so that the viscosity of the substance B is 300-35000 mPa.s at 25 ℃, and the refractive index of the substance B at 25 ℃ is 1.41-1.44. If z/(y+z) <0.03, (B) cannot effectively destroy the regularity of the molecular chain segments of the cured product, the cured product is frozen at a low temperature of-60 ℃ to-50 ℃, and the product is easy to crystallize, if z/(y+z) >0.2, the refractive index of (B) may be greater than 1.44, and the phenomenon of fogging of the cured product due to the refractive index and polarity difference after mixing of the substances A and B may occur, thereby affecting the transparency and haze of the cured product.
Substance C is a tackifying resin, and its structure is an MQ resin as shown below:
(R2 3SiO0.5)a(SiO2)d
Wherein a is more than or equal to 30 and less than or equal to 45,15 and d is more than or equal to 50, a:d=0.6-0.9:1, R 2 is C 1～C10 -containing alkyl such as methyl, ethyl, propyl or benzene ring-containing aryl, and the like, and R 2 is preferably methyl, namely the substance C is methyl MQ resin.
The preparation of substance C is well known to the practitioners in the industry, as prepared by the sodium silicate method according to patent US 2676182 or synthetically according to patent US 4774310 or patent CN 102775612A, using the orthosilicate method. Can also be obtained from commercial brands, such as XJY-8205 of Jiangxi Xinjia New Material Co., ltd, DY-MQ102N of Shandong Dayi chemical Co., ltd.
The content of the substance C is 5 to 40 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the composition of the substance A and the substance B. The addition of substance C can improve the adhesion of the cured product to a substrate such as glass, PC, etc., and improve adhesion.
Substance D is a linear polysiloxane with a hydrosilylation functional group, and the structure of the substance D comprises the following two structures (D-1) and/or (D-2);
in (D-1), o satisfies the condition that o is more than or equal to 10 and less than or equal to 45, and (D-1) is commonly called hydrogen-containing silicone oil in the organosilicon industry, and mainly plays a role in improving toughness and elongation of a cured product, if o is less than 10, although (D-1) can be toughened in a reaction, the o is easy to volatilize when heated, the reliability of a display screen is not good, and if o is more than 45, the reactive functional groups are too few and the activity is low, and the (D-1) cannot play a role in toughening well.
In (D-2), p and q satisfy 20.ltoreq.p+q.ltoreq. 80,0.2.ltoreq.q/(p+q). Ltoreq.0.6, (D-2) are commonly called side hydrogen silicone oil in the organosilicon industry, if p+q <20, (D-2) is heated and volatilized easily, the reliability of a display screen is not favored, p+q >80 is avoided, the viscosity of (D-2) is overlarge, the reaction activity is slow, the curing speed is slower, q/(p+q) <0.2 is low in content of silicon hydrogen functional groups and not easy to cure and crosslink, if q/(p+q) >0.8 is high in content of silicon hydrogen functional groups, bubbles are easy to appear in a glue layer after high-temperature reliability aging, and visual effect is affected.
Preferably, the substance D consists of (D-1) and (D-2), and the total amount of (D-1) and (D-2) is 1 to 20 parts by weight, compared with 100 parts by weight of the composition of the substance A and the substance B, and the molar ratio of the silicon-hydrogen functional group (Si-H) in (D-1) and (D-2) to the terminal vinyl functional group (Si-Vi) of the substance A and the substance B is 0.5 to 0.9. 100 parts of a mixture (D) comprising (D-1) and (D-2) mixed together, wherein the ratio of (D-1) to (D-2) is 5-95:95-5, preferably 70-90:30-10.
The preparation processes of (D-1) and (D-2) are also well known to the industry practitioners and can be achieved by the relevant equilibrium ring-opening reactions. And also commercially available, such as the RH-H series silicone oils available from Ningbo Hirudo materials technologies Inc., the D series and SH series available from Jiangsu Koch materials Inc.
The catalyst E is a metal compound or complex having hydrosilylation catalytic activity, such as a metal complex of platinum, palladium, rhodium, or the like, preferably a metal complex of platinum. The catalyst has heat-sensitive and photosensitive activities, and can rapidly catalyze hydrosilylation after heating or photo-activation. Among them, the catalyst having the thermosensitive catalytic activity is chloroplatinic acid, a complex of chloroplatinic acid and isopropyl alcohol, a complex of chloroplatinic acid and divinyl tetramethyl disiloxane or a complex of chloroplatinic acid and 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane, preferably a complex of chloroplatinic acid and divinyl tetramethyl disiloxane, namely Karstedt catalyst. The catalyst having photosensitivity is a compound containing Pt and having a conjugated olefin structure, such as trimethyl (methylcyclopentadienyl) platinum (IV) and bis (acetylacetonato) platinum (II), etc. The above catalyst is preferably a Karstedt catalyst having a thermosensitive catalytic activity.
The polymerization inhibitor F is one or more of 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane and the like, preferably 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane.
The invention provides a low-temperature-hardening-resistant organosilicon optical laminating adhesive, which is packaged in a form of single component or double components, preferably double components. When the double-component adhesive is used for packaging, substances A, B and C can be premixed uniformly to prepare basic sizing materials, a part of the basic sizing materials are mixed with substances E and F to prepare a first component, the rest of the basic sizing materials are mixed with substances D to prepare a second component, and the first component and the second component are mixed uniformly when in use, and the adhesive can be used after removing bubbles. The mixing ratio of the component A and the component B can be adjusted according to the reaction molar ratio of Si-H and Si-Vi, and is preferably 1:1-4:1, and more preferably 1:1.
The following describes the invention in further detail with reference to examples, which are not intended to limit the invention thereto.
Example 1 preparation of phenyl-substituted terminal vinyl-containing polysiloxane B1:
Adding 3600g deionized water and 12.5g potassium hydroxide into a 10L four-neck flask with a stirring, condensing and refluxing water diversion device, setting the reaction temperature to 80 ℃, adding 273g methyl phenyl dimethoxy silane, 2832g dimethyl dimethoxy silane for refluxing reaction for 2 hours under the condition of 70-80 ℃, adding 2000g toluene for extraction, heating to the reflux temperature, gradually separating alcohol generated by the reaction, finally cooling, standing and layering to obtain supernatant of an upper hydrolysate, and washing toluene liquid for 2-3 times to neutrality.
Heating the hydrolysate, setting the oil temperature to 120 ℃ and distilling under reduced pressure to remove toluene, adding 18.6g of 1, 3-divinyl-1, 3-tetramethyl disiloxane and 1g of tetramethyl ammonium hydroxide into the hydrolysate, carrying out equilibrium condensation reaction for 4 hours at 100-110 ℃, then heating to 160 ℃ to decompose tetramethyl sodium hydroxide by using a breaking enzyme, and removing low molecules under reduced pressure to obtain the vinyl polysiloxane at the end B of the invention, wherein z=15, y=236, z/(y+z) =0.06, the viscosity is 1380mpa.s, the refractive index at 25 ℃ is 1.4180, and the vinyl content is 0.27wt%.
Comparative example 1 preparation of phenyl-substituted terminal vinyl-containing polysiloxane B2:
Adding 3600g of deionized water and 12.5g of potassium hydroxide into a 10L four-neck flask with a stirring, condensing and refluxing water diversion device, setting the reaction temperature to 80 ℃, adding 1005g of methyl phenyl dimethoxy silane when the material temperature reaches 45 ℃, refluxing and reacting for 2 hours under the condition of 70-80 ℃, adding 2000g of toluene for extraction, heating to the reflux temperature, gradually separating alcohol generated by the reaction, finally cooling, standing and layering to obtain supernatant of an upper hydrolysate, and washing the toluene liquid for 2-3 times to be neutral.
Heating the hydrolysate, setting the oil temperature to 120 ℃ and distilling under reduced pressure to remove toluene, adding 18.6g of 1, 3-divinyl-1, 3-tetramethyl disiloxane and 1g of tetramethyl ammonium hydroxide into the hydrolysate, carrying out equilibrium condensation reaction for 4 hours under the condition of 100-110 ℃, then heating to 160 ℃ to decompose tetramethyl sodium hydroxide by using a breaking enzyme, decompressing to remove low molecules, and obtaining a substance B, namely vinyl polysiloxane, wherein z=55.22, y=195.78, z/(y+z) =0.22, the viscosity is 2000mPa.s, the 25 ℃ refractive index is 1.4510, and the vinyl content is 0.24%.
Comparative example 2 preparation of phenyl-substituted terminal vinyl-containing polysiloxane B3:
adding 3600g deionized water and 12.5g potassium hydroxide into a 10L four-neck flask with a stirring, condensing and refluxing water diversion device, setting the reaction temperature to 80 ℃, adding 46g methyl phenyl dimethoxy silane when the material temperature reaches 45 ℃, then carrying out reflux reaction for 2 hours under the condition of 70-80 ℃, adding 2000g dimethyl dimethoxy silane, extracting, heating to reflux temperature, gradually separating alcohol generated by the reaction, finally cooling, standing and layering to obtain supernatant of an upper hydrolysate, and washing toluene liquid for 2-3 times to neutrality.
Heating the hydrolysate, setting the oil temperature to 120 ℃ and distilling under reduced pressure to remove toluene, adding 18.6g of 1, 3-divinyl-1, 3-tetramethyl disiloxane and 1g of tetramethyl ammonium hydroxide into the hydrolysate, carrying out equilibrium condensation reaction for 4 hours at 100-110 ℃, then heating to 160 ℃ to decompose tetramethyl sodium hydroxide by using a breaking enzyme, and removing low molecules under reduced pressure to obtain a substance B, namely vinyl polysiloxane, wherein z=2.56, y=250, z/(y+z) =0.01 in the molecule B, the viscosity is 1410mPa.s, the refractive index at 25 ℃ is 1.4092, and the vinyl content is 0.22wt%.
Example 2 preparation of alkyl-substituted vinyl-terminated polysiloxane B4:
Adding 3600g deionized water and 12.5g potassium hydroxide into a 10L four-neck flask with a stirring, condensing and refluxing water diversion device, setting the reaction temperature to 80 ℃, adding 557g octyl methyl dimethoxy silane when the material temperature reaches 45 ℃, refluxing 2760g dimethyl dimethoxy silane for 2 hours under the condition of 70-80 ℃, adding 2000g toluene for extraction, heating to the reflux temperature, gradually separating alcohol generated by the reaction, finally cooling, standing and layering to obtain supernatant of an upper hydrolysate, and washing toluene liquid for 2-3 times to neutrality.
Heating the hydrolysate, setting the oil temperature to 120 ℃ and distilling under reduced pressure to remove toluene, adding 18.6g of 1, 3-divinyl-1, 3-tetramethyl disiloxane and 1g of tetramethyl ammonium hydroxide into the hydrolysate, carrying out equilibrium condensation reaction for 4 hours at 100-110 ℃, then heating to 160 ℃ to decompose tetramethyl sodium hydroxide by using a breaking enzyme, decompressing and removing low molecules to obtain a substance B, namely vinyl polysiloxane with a molecular weight of B, wherein z=2.56, y=230, z/(y+z) =0.1, the viscosity is 1220mpa.s, the refractive index at 25 ℃ is 1.4172, and the vinyl content is 0.21wt%.
Examples 3 to 7 preparation of low temperature resistant optical cement:
1) The raw materials used are:
substance a-polydimethylsiloxane with terminal vinyl groups (vinyl silicone oil):
A1-RH-Vi 301, ningbo Ruohao Hirudo New Material technologies Co., ltd., viscosity 100000mPa.s, vinyl content 0.06wt.%;
A2-RH-Vi 1320, ningbo Ruo Hirudo New Material technologies Co., ltd., viscosity 2000mPa.s, vinyl content 0.23wt.%;
A3-RH-Vi 311, ningbo Ruohao Hirudo New Material technologies Co., ltd., viscosity 500mPa.s, vinyl content 0.43wt.%;
substance B-phenyl-or alkyl-substituted terminal vinyl polysiloxane:
b1-the product of example 1 of the present invention;
b2-the preparation of comparative example 1 according to the invention;
b3-the preparation of comparative example 2 according to the invention;
B4-obtained by the preparation of inventive example 2.
Substance C-tackifying resin C-Jiangxi Xinjia exemplary New Material Co., ltd. Methyl MQ resin brand XJY-8205.
Substance D-linear polysiloxane with a hydrosilylation function (terminal hydrogen containing silicone oil):
(D-1) -terminal hydrogen silicone oil, D-15, jiangsu family unfortunately New materials Co., ltd, viscosity 15mPa.s, hydrogen content of 0.12%, and (D-2) -side hydrogen silicone oil, SH-50, jiangsu family unfortunately New materials Co., ltd, viscosity 50mPa.s, hydrogen content of 0.5%;
Substance E-catalyst-Karstedt catalyst (Pt-5000) with a Pt content of 5000ppm, manufactured by Shanghai He Lishi Industrial technology materials Co., ltd.
Substance F-polymerization inhibitor-1, 3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane (ViD 4) with purity more than or equal to 95% prepared by Zhejiang qu orange organic silicon limited company.
2) The preparation method comprises the following steps:
The raw materials are uniformly mixed according to the proportion of the table 1 to prepare the photo-curing organic silicon LOCA, the preparation process is that a planetary stirring kettle is used, firstly, substances A, B and C are put into the planetary stirring kettle and are stirred at high speed (the stirring speed is 30-35 Hz) for 10min to be pre-dispersed, then substances E and F are added and are stirred at high speed (the stirring speed is 30-35 Hz) for 20min, then substances D are added and are stirred at high speed (the stirring speed is 30-35 Hz) for 30min, the single-component low-temperature-resistant optical cement is obtained through filtration and packaging, and performance test is carried out after curing, and the raw material proportions of the examples are shown in the table 1.
3) Performance test:
The test method is that the viscosity is that tested at 25 ℃ using a Brookfield dvs+viscometer, the light transmittance and haze test is that using a pick chemistry 4775 projection haze meter, the yellowing index test is that using an shimadzu instrument UV2600I ultraviolet visible spectrophotometer, and the crystallization temperature is that tested using a TA DMA850 dynamic analyzer, the performance of each example and comparative example is shown in table 2.
Comparative examples 3-5 preparation of silicone optical bonding adhesive:
The preparation method is the same as that of examples 3-7, the raw material ratios are shown in Table 1, and the performance results are shown in Table 2.
Table 1 raw materials (parts by weight) in examples 3 to 7 and comparative examples 3 to 5
In the table, pt-5000 means that the content of Pt is 5000ppm.
Table 2 results of the properties of the optical gums obtained in examples 3 to 7 and comparative examples 3 to 5
As can be seen from the data in Table 2, the organosilicon optical bonding adhesive prepared according to the invention has lower crystallization temperature than the conventional polydimethylsiloxane series optical bonding adhesive with a full methyl structure, does not harden after being frozen at-55 ℃ for 96 hours, and has excellent low temperature resistance. Meanwhile, after other functional groups substituted for methyl are introduced, the polymer has better compatibility with the traditional polydimethylsiloxane polymer, high transparency, low haze and yellowing resistance, and can be applied to an optical laminating touch screen used in a low-temperature environment. Example 3, example 7 and comparative example 3 have DMA modulus curves as shown in fig. 1, with the crystallization temperature being reduced from-44.94 ℃ to-57.26 ℃ after the introduction of the phenyl-containing substituted vinyl-terminated polysiloxane, and from-44.94 ℃ to-55.41 ℃ after the introduction of the octyl-containing substituted vinyl-terminated polysiloxane.
The description of the present invention is to be construed as illustrative and not restrictive, and it is intended that all such modifications and variations in the techniques of the present invention be included within the scope of the invention.
Claims (18)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310085924.5A CN116120888B (en) | 2023-01-18 | 2023-01-18 | A low-temperature hardening-resistant silicone optical bonding adhesive and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310085924.5A CN116120888B (en) | 2023-01-18 | 2023-01-18 | A low-temperature hardening-resistant silicone optical bonding adhesive and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116120888A CN116120888A (en) | 2023-05-16 |
| CN116120888B true CN116120888B (en) | 2025-05-02 |
Family
ID=86295260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310085924.5A Active CN116120888B (en) | 2023-01-18 | 2023-01-18 | A low-temperature hardening-resistant silicone optical bonding adhesive and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116120888B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964327A (en) * | 2019-12-16 | 2020-04-07 | 杭州之江新材料有限公司 | High-refractive-index transparent silica gel and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101259887B1 (en) * | 2009-08-04 | 2013-05-02 | 한국과학기술원 | Transparent siloxane resin composition for optics |
-
2023
- 2023-01-18 CN CN202310085924.5A patent/CN116120888B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964327A (en) * | 2019-12-16 | 2020-04-07 | 杭州之江新材料有限公司 | High-refractive-index transparent silica gel and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 加成型甲基苯基乙烯基硅橡胶的合成及低温性能研究;段理垒;李军明;;有机硅材料;20170420(S1);37-41 * |
| 徐晓秋.透明、高折射率加成型硅橡胶的制备及改性MQ树脂的补强研究.中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑.2012,(02),B016-189. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116120888A (en) | 2023-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5704168B2 (en) | Novel organosilicon compound, thermosetting resin composition containing the organosilicon compound, cured resin, and sealing material for optical semiconductor | |
| CN106317894B (en) | Silicon composition, reflecting coating and preparation method thereof and the photovoltaic module including it | |
| TWI679244B (en) | Addition-curable silicone resin composition, method for producing the same, and optical semiconductor device | |
| KR101437664B1 (en) | Silicon-containing compound, curable composition and cured product | |
| CN103201317B (en) | Thermally stable compositions containing resin-linear organosiloxane block copolymers | |
| JP5793824B2 (en) | Organosilicon compound, thermosetting composition containing the organosilicon compound, and sealing material for optical semiconductor | |
| CN110291156B (en) | Curable silicone composition, cured product thereof, and optical display | |
| TWI816893B (en) | Ultraviolet curable polysiloxane adhesive composition and method for manufacturing laminate | |
| JP6243567B1 (en) | Curable polyorganosiloxane composition and use thereof | |
| CN108463508B (en) | Condensation-reactive polysiloxane composition and cured product | |
| JPWO2009044763A1 (en) | Sealant for display element | |
| TW201307440A (en) | Organopolysiloxane and method for producing the same | |
| WO2020140856A1 (en) | High refractive index silica gel for full lamination of liquid crystal display screen | |
| TW202012543A (en) | Silicone composition | |
| CN109661435A (en) | Hardening resin composition, its solidfied material and semiconductor device | |
| JP7530708B2 (en) | Curable organosilicon resin composition | |
| CN103571209A (en) | Addition-curable silicone composition and semiconductor device | |
| JP2011042760A (en) | Composition for thermosetting silicone resin | |
| WO2015136820A1 (en) | Curable resin composition | |
| WO2017096945A1 (en) | Organic silicon compound containing boron, sealant for solar cell assembly and solar cell assembly | |
| CN116120888B (en) | A low-temperature hardening-resistant silicone optical bonding adhesive and its preparation and application | |
| JP2018002969A (en) | Curable organosilicon resin composition | |
| CN109476920A (en) | Curable resin composition, cured product thereof, and semiconductor device | |
| CN109266010B (en) | Low-temperature-resistant transparent silicone gel composition for filling liquid crystal touch screen | |
| TWI898121B (en) | Organic polysiloxane composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |