WO2015143591A1 - 一种透明有机硅凝胶粘接剂 - Google Patents

一种透明有机硅凝胶粘接剂 Download PDF

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WO2015143591A1
WO2015143591A1 PCT/CN2014/001069 CN2014001069W WO2015143591A1 WO 2015143591 A1 WO2015143591 A1 WO 2015143591A1 CN 2014001069 W CN2014001069 W CN 2014001069W WO 2015143591 A1 WO2015143591 A1 WO 2015143591A1
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formula
group
compound
resin
equal
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PCT/CN2014/001069
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French (fr)
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石东
姬金宏
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苏州桐力光电技术服务有限公司
石东
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Priority to US15/129,374 priority Critical patent/US9994745B2/en
Publication of WO2015143591A1 publication Critical patent/WO2015143591A1/zh

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the invention relates to a transparent silicone gel adhesive, in particular to an optical grade transparent silicone gel gel adhesive, which can be used for bonding glass, PC board, PMMA, etc., and is suitable for processing touch screens and liquid crystal display panels.
  • Optical components, etc. belong to the field of new silicone electronic packaging protective materials.
  • adhesives which can be applied to transparent optical elements include epoxy resin adhesives, rubber type adhesives, modified acrylic resin adhesives, and polyurethane adhesives.
  • the disadvantage of epoxy resin is that the yellowing resistance is relatively poor, and at the same time, its resistance to cracking and impact is also lacking.
  • a disadvantage of the rubber type adhesive is poor storage stability.
  • the disadvantage of polyurethane binders is that the temperature resistance is relatively poor and it is easy to hydrolyze at high temperatures. OCA water gel for touch screens, which are currently widely used, has relatively large limitations due to the high cost and price, and the cumbersome process.
  • the technical solution adopted by the present invention is: a transparent silicone gel adhesive which is mixed by the A component and the B component in a mass ratio of 1:1.
  • the A component consists of the material of the blank:
  • Base material 60 to 95 parts by weight
  • the catalyst is a platinum group metal catalyst
  • the B component consists of a blank by weight of material:
  • the binder is at least one of a compound conforming to the formula (1), a compound conforming to the formula (2), a compound conforming to the formula (3), and a compound conforming to the formula (4);
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • c is greater than or equal to 20
  • d is greater than or equal to 30, and e is greater than or equal to 10;
  • f is greater than or equal to 30
  • g is greater than or equal to 10
  • h is greater than or equal to 10
  • i is greater than or equal to 10
  • branched silicone oil is thinned with increasing viscosity. This shear thinning effect is beneficial to the dispersion of other components in the silicone gel, and its use and adhesion are both Higher than ordinary linear silicone oil, branched silicone oil can improve its flexibility and surface adhesion.
  • the crosslinking agent is at least one of the compounds conforming to the general formula (5);
  • the excipient comprises a mixture of an MQ resin conforming to the general formula (6) or an MQ resin conforming to the general formula (6) and a terminal vinyl silicone oil; wherein the mass ratio between the MQ resin and the terminal vinyl silicone oil is 0.3 to 0.4: 0.6 to 0.7;
  • the auxiliary material further comprises a mixture of MT resin or MT resin and terminal vinyl silicone oil; the mass ratio between the MT resin and the terminal vinyl silicone oil is 0.3-0.4:0.6-0.7;
  • Me represents a methyl group
  • the excipient further comprises an adhesion promoter prepared by mixing the C component and the D component, and the mass ratio between the C component and the D component is 10 to 90:10.
  • the C component is at least one of a compound conforming to the formula (7), a compound conforming to the formula (8), a compound conforming to the formula (9), and a compound conforming to the formula (10);
  • the B component is at least one of the compounds conforming to the general formula (11);
  • the inhibitor is at least one of an alkynol compound and an olefin-containing cyclic siloxane oligomer.
  • the platinum group metal catalyst is chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum-vinylsiloxane complex, chloroplatinic acid and olefin complex, and platinum-olefin complex. At least one of them.
  • the amount of catalyst added is only sufficient to be effective as a hydrosilylation reaction catalyst, and the amount can be varied depending on the desired curing rate. If the amount is too large, the reaction becomes uneconomical.
  • platinum group metal catalyst needs to have good storage stability, and has good compatibility with colloid and suitable catalytic activity. Its content ranges from 0.0005 to 0.6%, depending on the content of platinum.
  • a suitable catalyst can adjust the addition reaction of silicon hydride, and preparing a colloid of different curing conditions according to requirements, and appropriately increasing the amount of the platinum catalyst can also make the colloid have a certain flame retardant property.
  • the platinum group metal catalyst is a platinum-vinylsiloxane complex.
  • the inhibitor is selected from the group consisting of 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1- Hexyn-3-ol, 1-hexynyl-1-cyclohexanol, 3-phenyl-1-butyn-3-ol, 2-methyl-3-butyn-2-ol and tetramethyltetra Vinylcyclotetrasiloxane, pyridine, unsaturated amide.
  • inhibitor can adjust the vulcanization rate, meet the suitable working time and storage life, and ensure the storage stability requirement of the silicone gel;
  • the molar ratio of the inhibitor alkynol/platinum group metal catalyst is preferably 40, too high will make the colloid The surface is not flat, too low, the curing speed is too fast, resulting in reduced working time and is not economical.
  • the olefin group in the compound of the formula (1) is a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group or a heptenyl group.
  • R 1 and R 2 in the compound of the formula (1) represent a methyl group
  • R 3 and R 4 represent a vinyl group
  • the vinyl content is 0.005 to 0.5% by weight
  • the compound of the formula (1) has a viscosity of 300 to 30,000 cps
  • the advantage of the technical scheme is that the linear vinyl silicone oil is used as a matrix material to adjust the viscosity of the product, the double bonds are concentrated at both ends, and the molecular chain is Long-chain alkanes have no substituents on the side chain, and the internal frictional resistance generated by the molecules during the movement of the segments is small, reducing internal friction.
  • R 1 represents a methyl group
  • R 2 , R 3 and R 4 represent a vinyl group
  • the vinyl content is 0.01 to 10%
  • the viscosity of the compound is 50 to 10000 centipoise
  • the advantage of adopting the technical scheme is that the vinyl group of the side group can increase more crosslinking points and improve the mechanical properties such as the glass strength of the final colloid;
  • R 1 , R 2 and R 3 represent a methyl group
  • R 4 represents a vinyl group
  • the vinyl content is 0.001 to 0.5%
  • the viscosity of the compound is from 500 to 10,000 cps.
  • the advantage of adopting this technical solution is that the colloid needs to adjust the viscosity of the colloid through a plasticizer, and the polydimethylsiloxane having no reactive group will permeate under long-term conditions, which seriously affects the colloid on the optical device.
  • the performance of the linear silicone oil with a single-ended reactive group can not only adjust the final viscosity of the product, but also react as a reactive group, without causing oil leakage in the final product.
  • R 5 and R 8 in the compound of the formula (5) represent a methyl group
  • R 6 and R 7 represent a hydrogen group
  • the hydrogen-containing compound of the formula (5) The amount is 0.005 to 1%
  • the viscosity of the compound according to the general formula (5) is 5 to 200 centipoise
  • the advantage of adopting the technical scheme is that the linear hydrogen-containing silicone oil can be used as a crosslinking agent or as a crosslinking agent.
  • a chain extender in which a Me 3 SiO 0.5 link encapsulated polymethylhydrogensiloxane can be used as an anti-yellowing agent.
  • the active hydrogen-terminated organohydrogenpolysiloxane has higher activity, and the strength and toughness of the silicone gel can be improved by adjusting the amount of addition thereof, so that the product has good mechanical properties.
  • R 6 , R 7 and R 8 represent a methyl group
  • R 5 represents a hydrogen group
  • the compound of the formula (5) has a hydrogen content of 0.005 - 2%
  • the compound of the formula (5) has a viscosity of 10 to 100 centipoise
  • the advantage of adopting the technical scheme is that the hydrogen group of the side group can increase more crosslinking points, and the crosslinking density is high, and the crosslinking is high.
  • the mechanical properties of the final strength and toughness of the colloid are examples of the mechanical properties of the final strength and toughness of the colloid.
  • R 8 represents a methyl group
  • R 5 , R 6 and R 7 represent a hydrogen group
  • the compound of the formula (5) has a hydrogen content of 0.001 ⁇ 10%
  • the compound of the formula (5) has a viscosity of 10 to 300 cps.
  • the surface of the cross-linked material has a certain self-adhesiveness to be attached to the surface of the device.
  • the ratio of the silicon hydrogen to the vinyl is usually adjusted to 0.5 to 1.0.
  • a preferred technical solution is that, in the MQ resin, R 9 represents a methyl group, and the M/Q ratio of the MQ resin is 0.6 to 1.2; the advantage of adopting the technical solution is that the methyl MQ resin has a certain heat resistance. Sexual and low temperature resistance, with certain flexibility, hard but not brittle, resistant to aging, UV, water, and because it has no reactive groups, it can reduce the linear shrinkage of the final product, making it better in optical devices. Used on.
  • R 9 represents a vinyl group, and the content of the vinyl group is less than or equal to 10 w%.
  • vinyl MQ resin has good compatibility and dispersibility, and the siloxane link has a reinforcing effect, which can react with the crosslinking agent to produce a strong chemical bond. Improve mechanical properties. It also acts as a tackifier.
  • the addition of MQ resin can introduce organic chain links to enhance the viscosity, without affecting the viscosity of the system, affecting the light transmittance, and not changing the embrittlement of the base rubber.
  • the temperature is such that it maintains good low-temperature adhesion, and does not lose adhesion even after reaching the glass transition temperature, and its good compatibility and light transmittance satisfy the use on the optical device.
  • the crosslink density By adjusting the crosslink density, the mechanical properties and flame retardancy of the silicone gel are improved; the film has good high and low temperature resistance, and the inherent bond strength and flexibility of the colloid are maintained.
  • the ratio of M/Q of the MQ resin is 0.8.
  • the smaller M/Q ratio makes the production difficult and easy to gel.
  • the larger M/Q ratio is the liquid MQ resin, the molecular weight is lower, the cohesive energy between the molecules is decreased, and the mechanical properties cannot be improved.
  • the silicone gel has a non-crosslinking functional group adhesion from the surface, a product of the MQ resin type tackifying component, or a side chain length and a terminal end of the non-crosslinking functional group by adjusting the addition amount of the non-reactive adhesive component.
  • the type of the functional group or the like shows adhesion.
  • the MQ resin is a solid white powder, it needs to be mixed with the terminal vinyl silicone oil and mixed to form a liquid blend.
  • the mixing ratio is resin: the silicone oil is between 0.3:0.7, and the ratio is 0.4. Between: 0.6.
  • the present invention has the following advantages and effects compared with the prior art:
  • the invention is a two-component addition transparent AB silicone gel adhesive (hereinafter referred to as silicon gel), which has good adhesion to glass, PC board and PMMA, and these materials are commonly used for touch screen cover. material.
  • Silicone gels are characterized by low cost and simple process operation. Its refractive index is between 1.40 and 1.43. It is a colorless transparent gel with a light transmittance of over 92%. It has certain elasticity and recovery, can resist external impact, and can maintain long-lasting adhesion. It can be fully cured at room temperature or when heated, with good economy and reliability.
  • the adhesion promoter of the present invention is an excellent interface reinforcing agent which can improve the bonding ability between the silicone gel and the surface to be pasted.
  • Figure 1 is an infrared spectrum of an MT silicone resin.
  • Figure 2 is a nuclear magnetic hydrogen spectrum of MT silicone resin.
  • Figure 3 is a nuclear magnetic silicon spectrum of an MT silicone resin.
  • Example 1 A transparent silicone gel adhesive
  • a transparent silicone gel adhesive prepared by mixing A component and B component in a mass ratio of 1:1; the A component is weighted by a blank Material composition:
  • the catalyst is chloroplatinic acid.
  • the B component consists of a blank by weight of material:
  • binder is a compound conforming to the formula (1).
  • R 1 and R 2 in the compound of the formula (1) represent a methyl group
  • R 3 and R 4 represent a vinyl group
  • the vinyl content is 0.05% by weight
  • the crosslinking agent conforms to the compound of the formula (5).
  • R 5 and R 8 in the compound of the formula (5) represent a methyl group
  • R 6 and R 7 represent a hydrogen group
  • the compound having the formula (5) has a hydrogen content of 0.05. %
  • the compound of the formula (5) has a viscosity of 90 cps
  • the excipient contains an MQ resin conforming to the general formula (6).
  • the excipient also contains an MT resin.
  • Me represents a methyl group
  • R 9 represents a methyl group
  • the M/Q ratio of the MQ resin is 0.8.
  • the excipient further comprises an adhesion promoter prepared by mixing the C component and the D component, and the mass ratio between the C component and the D component is 30:70;
  • the component C is a mixture of a compound of the formula (7), a compound of the formula (8), a compound of the formula (9) and a compound of the formula (10); A compound conforming to the formula (11).
  • the mass ratio between the compound of the formula (7), the compound of the formula (8), the compound of the formula (9) and the compound of the formula (10) is 1:1:1:1. .
  • the preparation method of the adhesion promoter the components C and D are weighed according to the components and then uniformly mixed.
  • the preparation method of the MT resin includes the following steps:
  • the first step adding anhydrous toluene, absolute ethanol and methyltrimethoxysilane to the reaction vessel, and then under the condition of 50-70 ° C under nitrogen protection, specifically, the reaction vessel is placed under a nitrogen atmosphere.
  • the temperature conditions and the nitrogen protection conditions are indispensable, and then trifluoromethanesulfonic acid is first added as a catalyst to the reaction vessel, and then acetic acid is added dropwise to the reaction vessel to react the methyltrimethoxysilane with the acetic acid.
  • An intermediate product is obtained; wherein the molar ratio between the methyltrimethoxysilane and the acetic acid is 1:1.
  • the second step removing the solvent in the reaction vessel; the method for removing the solvent is specifically heating and evaporation.
  • the third step adding 80-100 ° C to the reaction vessel, adding tetramethyldihydrodisiloxane, and then adding acetic acid, acetic acid and the first step to the reaction vessel Intermediate product reacts to form silanol, silanol
  • the MT resin is obtained by blocking with tetramethyldihydrodisiloxane; after cooling, washing with water, distillation, a pure MT silicone resin is obtained.
  • the molar ratio between the tetramethyldihydrodisiloxane and methyltrimethoxysilane is 1:0.5; the molar ratio between the acetic acid and methyltrimethoxysilane It is 1:1.
  • the simplified planar structure of the obtained MT resin is as follows, and a portion which is not shown is a repeating silicon oxide structural unit.
  • a simplified perspective view of the prepared MT resin is as follows:
  • 2965cm -1 absorption peak is CH
  • 1268cm -1 is the Si-CH 3 absorption peaks
  • 1018cm -1 is the absorption peak of Si-O-Si.
  • the mass ratio between the MQ resin conforming to the general formula (6), the MT resin, and the adhesion promoter was 1:1:0.3.
  • the transparent silicone gel adhesive is prepared by weighing each raw material in the above weight range, adding it to a mixer, evacuating to a vacuum of -0.1 to -0.05 MPa, and using a dispersing mixer of 50 to 500 rpm. After stirring for 0.5 to 3 hours, the mixture was uniformly stirred, and respectively filled and sealed to obtain the AB component silicone gel.
  • the obtained transparent silicone gel adhesive for optical use is colorless and transparent in appearance, and has a light transmittance of 97% (measured by an ultraviolet spectrophotometer) in the range of 400-700 nm.
  • the basic color parameter L is 90.2, a is -2.01, and b is 0.62.
  • the change is small and not yellow.
  • Mechanical properties tensile strength 0.3MPa; good adhesion strength, 180° peel strength for glass is 0.4KN/m, lap shear strength reaches 1.0MPa, flame retardant performance is good, reaching UL94-V0.
  • the refractive index is 1.42.
  • Embodiments 2-8 A transparent silicone gel adhesive
  • a transparent silicone gel adhesive is composed of A component and B component according to 1 A mass ratio of 1 is mixed and prepared.
  • Binder catalyst Excipient Embodiment 2 85 parts by weight 0.2 parts by weight 25 parts by weight Embodiment 3 95 parts by weight 0.3 parts by weight 15 parts by weight Embodiment 4 90 parts by weight 0.5 parts by weight 20 parts by weight Embodiment 5 67 parts by weight 0.1 parts by weight 5 parts by weight Embodiment 6 85 parts by weight 0.15 parts by weight 30 parts by weight
  • Binder Crosslinker Inhibitor Excipient Embodiment 2 65 parts by weight 7 parts by weight 0.1 parts by weight 2 parts by weight Embodiment 3 85 parts by weight 13 parts by weight 0.2 parts by weight 5 parts by weight Embodiment 4 70 parts by weight 9 parts by weight 0.1 parts by weight 10 parts by weight Embodiment 5 69 parts by weight 5 parts by weight 0.25 parts by weight 8 parts by weight Embodiment 6 90 parts by weight 18 parts by weight 0.5 parts by weight 15 parts by weight
  • Example 2 A compound conforming to the formula (1) and a compound according to the formula (2) were mixed in a mass ratio of 1:1.
  • R 1 represents a methyl group
  • R 2 , R 3 , R 4 represent a vinyl group
  • the viscosity of the compound according to the formula (1) is 7000 cps
  • a is equal to 20 and b is equal to 30.
  • Example 3 A compound conforming to the formula (3), in the formula (3), c is equal to 20, d is equal to 30, and e is equal to 10.
  • Example 4 A compound conforming to the formula (2) and a compound according to the formula (4) were mixed in a mass ratio of 1:1.5.
  • a is equal to 20 and b is equal to 35.
  • f is equal to 30, g is equal to 10, h is equal to 10, and i is equal to 10.
  • Example 5 a compound according to formula (1), a compound according to formula (2), a compound according to formula (3) and a compound according to formula (4) in a mass ratio of 1:0.5:1.5:1 a mixture of components.
  • R 1 , R 2 and R 3 represent a methyl group
  • R 4 represents a vinyl group
  • the vinyl content is 0.05%
  • the viscosity of the compound according to the formula (1) is 6500 cps.
  • a is equal to 25 and b is equal to 30.
  • c is equal to 22
  • d is equal to 30, and e is equal to 15.
  • f is equal to 30, g is equal to 15, h is equal to 10, and i is equal to 20.
  • Example 6 A mixture of a compound of the formula (2), a compound of the formula (3) and a compound of the formula (4) in a mass ratio of 0.8:0.5:1.
  • a is equal to 25 and b is equal to 30.
  • c is equal to 22
  • d is equal to 30, and e is equal to 15.
  • f is equal to 30, g is equal to 15, h is equal to 10, and i is equal to 20.
  • Example 2 Alcohol-modified chloroplatinic acid.
  • Example 3 Platinum-vinylsiloxane complex.
  • Example 5 A mixture of an alcohol-modified chloroplatinic acid and a platinum-vinylsiloxane complex in a mass ratio of 1:1.
  • Example 2 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 1:1:1.
  • R 9 represents a vinyl group, and the content of the vinyl group is 4 w%.
  • the M/Q ratio is 0.8.
  • Preparation method of MT resin First step: adding anhydrous toluene, absolute ethanol and dimethyldiethoxysilane to the reaction vessel, and then under the condition of 50-70 ° C under nitrogen protection, specifically refers to The reaction vessel was placed under a nitrogen atmosphere, and the temperature conditions and nitrogen protection conditions were indispensable.
  • the second step removing the solvent in the reaction vessel; the method for removing the solvent is specifically heating and evaporation.
  • the third step adding 80-100 ° C to the reaction vessel, adding tetramethyldihydrodisiloxane, and then adding acetic acid, acetic acid and the first step to the reaction vessel
  • the intermediate product reacts to form a silyl group, and the silyl group is blocked with tetramethyldihydrodisiloxane to prepare an MT resin.
  • acetic anhydride such as tetramethyldihydrodisiloxane is added to absorb the water formed in the third step. After cooling, washing with water and distillation, a pure MT silicone resin is obtained.
  • the molar ratio between the tetramethyldihydrodisiloxane and dimethyldiethoxysilane is 1:0.52; the acetic acid and dimethyldiethoxysilane are both The molar ratio between the two was 1:1.05.
  • Example 3 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 1:0.5:1.
  • R 9 represents an ethyl group.
  • the M/Q ratio is 0.7.
  • the preparation method of the MT resin is the same as that of the first embodiment.
  • Example 4 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 0.5:1:1.
  • R 9 represents a cyclopentyl group.
  • a 0.3
  • b 1.
  • the M/Q ratio is 0.9.
  • Method for preparing MT resin First step: adding a mixture of anhydrous toluene, absolute ethanol, n-propyltrimethoxysilane and methyltripropoxysilane, n-propyltrimethoxysilane and a to the reaction vessel The mass ratio between the two groups of bispropoxysilane was 1:1.
  • the reaction vessel is placed under a nitrogen atmosphere, the temperature conditions and the nitrogen protection conditions are indispensable, and then trifluoromethanesulfonate is first added to the reaction vessel as a a catalyst, followed by dropwise adding acetic acid to the reaction vessel to react a mixture of n-propyltrimethoxysilane and methyltripropoxysilane with the acetic acid to obtain an intermediate product; wherein the n-propyl group
  • the molar ratio between the mixture of trimethoxysilane and methyltripropoxysilane and acetic acid was 1:1.1.
  • the second step removing the solvent in the reaction vessel; the method for removing the solvent is specifically heating and evaporation.
  • the third step adding 80-100 ° C to the reaction vessel, adding tetramethyldihydrodisiloxane, and then adding acetic acid, acetic acid and the first step to the reaction vessel
  • the intermediate product reacts to form a silyl group, and the silyl group is blocked with tetramethyldihydrodisiloxane to prepare an MT resin.
  • acetic anhydride such as tetramethyldihydrodisiloxane is added to absorb the water formed in the third step. After cooling, washing with water and distillation, a pure MT silicone resin is obtained.
  • the molar ratio between the tetramethyldihydrodisiloxane and a mixture of n-propyltrimethoxysilane and methyltripropoxysilane is 1:0.5; the acetic acid and n-propyl
  • the molar ratio between the mixture of the trimethoxysilane and the methyltripropoxysilane is 1:1.
  • Example 5 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 0.5:0.8:1.
  • R 9 represents a propenyl group.
  • a 0.2
  • b 1.1.
  • the M/Q ratio is 1.2.
  • Preparation method of MT resin First step: adding anhydrous toluene, absolute ethanol and trimethylethoxysilane to the reaction vessel, and then under the condition of 50-70 ° C under nitrogen protection, specifically refers to the reaction The vessel was placed under a nitrogen atmosphere, and the temperature conditions and nitrogen protection conditions were indispensable.
  • trifluoromethanesulfonate and copper triflate were added as catalysts (ruthenium triflate and trifluoromethyl) to the reaction vessel.
  • ruthenium triflate and trifluoromethyl were added as catalysts (ruthenium triflate and trifluoromethyl) to the reaction vessel.
  • a mass ratio between the copper sulfonate is 1:1
  • acetic acid is added dropwise to the reaction vessel to react the trimethylethoxysilane with the acetic acid to obtain an intermediate product;
  • the molar ratio between trimethylethoxysilane and acetic acid is 1:1.1.
  • the second step removing the solvent in the reaction vessel; the method for removing the solvent is specifically heating and evaporation.
  • the third step adding 80-100 ° C to the reaction vessel, adding tetramethyldihydrodisiloxane, and then adding acetic acid, acetic acid and the first step to the reaction vessel
  • the intermediate product reacts to form a silyl group, and the silyl group is blocked with tetramethyldihydrodisiloxane to prepare an MT resin.
  • acetic anhydride such as tetramethyldihydrodisiloxane is added to absorb the water formed in the third step. After cooling, washing with water and distillation, a pure MT silicone resin is obtained.
  • the molar ratio between the tetramethyldihydrodisiloxane and the trimethylethoxysilane is 1:0.55; between the acetic acid and the trimethylethoxysilane The molar ratio is 1:1.
  • Example 6 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 0.7:0.8:1.
  • the M/Q ratio is 0.9.
  • the MT resin is produced by the prior art, and is specifically disclosed in the Chinese Patent Publication No. CN102875810A, published on January 16, 2013, entitled "Phenyl-containing MT-type resin and its preparation method".
  • adhesion promoters in the excipients used in the components A of Examples 2 to 6 are as follows:
  • Example 2 The mass ratio between the C component and the D component is 90:10.
  • Example 3 The mass ratio between the C component and the D component was 40:60.
  • the mass ratio between the compound of the formula (2), the compound of the formula (3), and the compound of the formula (4) is 1:2:1.
  • Example 4 The mass ratio between the C component and the D component was 50:50.
  • the mass ratio between the compound of the formula (2) and the compound of the formula (4) is 1:2.
  • Example 5 The mass ratio between the C component and the D component was 45:55. The mass ratio between the compound of the formula (1) and the compound of the formula (3) is 1:1.
  • Example 6 The mass ratio between the C component and the D component was 20:80. The mass ratio between the compound of the formula (1) and the compound of the formula (2) conforming to the formula (4) is 1:1:1.
  • Example 2 A compound conforming to the formula (1) and a compound according to the formula (2) were mixed in a mass ratio of 1:1.
  • R 1 represents a methyl group
  • R 2 , R 3 , R 4 represent a vinyl group
  • the viscosity of the compound according to the formula (1) is 7000 cps
  • a is equal to 20 and b is equal to 30.
  • Example 3 A compound conforming to the formula (2) and a compound according to the formula (4) were mixed in a mass ratio of 1:1.5.
  • a is equal to 20 and b is equal to 35.
  • f is equal to 30, g is equal to 10, h is equal to 10, and i is equal to 10.
  • Embodiment 4 A compound conforming to the formula (3), in the formula (3), c is equal to 20, d is equal to 30, and e is equal to 10.
  • Example 5 a compound according to formula (1), a compound according to formula (2), a compound according to formula (3) and a compound according to formula (4) in a mass ratio of 1:0.5:1.5:1 a mixture of components.
  • R 1 , R 2 and R 3 represent a methyl group
  • R 4 represents a vinyl group
  • the vinyl content is 0.05%
  • the viscosity of the compound according to the formula (1) is 6500 cps.
  • a is equal to 25 and b is equal to 30.
  • c is equal to 22
  • d is equal to 30, and e is equal to 15.
  • f is equal to 30, g is equal to 15, h is equal to 10, and i is equal to 20.
  • Example 6 A mixture of a compound of the formula (2), a compound of the formula (3) and a compound of the formula (4) in a mass ratio of 0.8:0.5:1.
  • a is equal to 25 and b is equal to 30.
  • c is equal to 22
  • d is equal to 30, and e is equal to 15.
  • f is equal to 30, g is equal to 15, h is equal to 10, and i is equal to 20.
  • the compound of the formula (5) has a viscosity of 100 cps.
  • the compound of the formula (5) has a viscosity of 80 cps;
  • Embodiment 5 The same as the fourth embodiment.
  • Embodiment 6 The same as the third embodiment.
  • Example 2 Tetramethyltetravinylcyclotetrasiloxane.
  • Example 5 A mixture of 3-methyl-1-butyn-3-ol and 2-methyl-3-butyn-2-ol in a mass ratio of 1:1.
  • Example 2 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 1:1:1.
  • R 9 represents a vinyl group, and the content of the vinyl group is 4 w%.
  • the M/Q ratio is 0.8.
  • Preparation method of MT resin First step: adding anhydrous toluene, absolute ethanol and dimethyldiethoxysilane to the reaction vessel, and then under the condition of 50-70 ° C under nitrogen protection, specifically refers to The reaction vessel was placed under a nitrogen atmosphere, and the temperature conditions and nitrogen protection conditions were indispensable.
  • the second step removing the solvent in the reaction vessel; the method for removing the solvent is specifically heating and evaporation.
  • the third step adding 80-100 ° C to the reaction vessel, adding tetramethyldihydrodisiloxane, and then adding acetic acid, acetic acid and the first step to the reaction vessel
  • the intermediate product reacts to form a silyl group, and the silyl group is blocked with tetramethyldihydrodisiloxane to prepare an MT resin.
  • acetic anhydride such as tetramethyldihydrodisiloxane is added to absorb the water formed in the third step. After cooling, washing with water and distillation, a pure MT silicone resin is obtained.
  • the molar ratio between the tetramethyldihydrodisiloxane and dimethyldiethoxysilane is 1:0.52; the acetic acid and dimethyldiethoxysilane are both The molar ratio between the two was 1:1.05.
  • Example 3 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 0.7:0.8:1.
  • the M/Q ratio is 0.9.
  • the MT resin is produced by the prior art, and is specifically disclosed in the Chinese Patent Publication No. CN102875810A, published on January 16, 2013, entitled "Phenyl-containing MT-type resin and its preparation method".
  • Example 4 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 0.5:1:1.
  • R 9 represents a cyclopentyl group.
  • a 0.3
  • b 1.
  • the M/Q ratio is 0.9.
  • Method for preparing MT resin First step: adding a mixture of anhydrous toluene, absolute ethanol, n-propyltrimethoxysilane and methyltripropoxysilane, n-propyltrimethoxysilane and a to the reaction vessel The mass ratio between the two groups of bispropoxysilane was 1:1.
  • the reaction vessel is placed under a nitrogen atmosphere, the temperature conditions and the nitrogen protection conditions are indispensable, and then trifluoromethanesulfonate is first added to the reaction vessel as a a catalyst, followed by dropwise adding acetic acid to the reaction vessel to react a mixture of n-propyltrimethoxysilane and methyltripropoxysilane with the acetic acid to obtain an intermediate product; wherein the n-propyl group
  • the molar ratio between the mixture of trimethoxysilane and methyltripropoxysilane and acetic acid was 1:1.1.
  • the second step removing the solvent in the reaction vessel; the method for removing the solvent is specifically heating and evaporation.
  • the third step adding 80-100 ° C to the reaction vessel, adding tetramethyldihydrodisiloxane, and then adding acetic acid, acetic acid and the first step to the reaction vessel
  • the intermediate product reacts to form a silyl group, and the silyl group is blocked with tetramethyldihydrodisiloxane to prepare an MT resin.
  • acetic anhydride such as tetramethyldihydrodisiloxane is added to absorb the water formed in the third step. After cooling, washing with water and distillation, a pure MT silicone resin is obtained.
  • the molar ratio between the tetramethyldihydrodisiloxane and a mixture of n-propyltrimethoxysilane and methyltripropoxysilane is 1:0.5; the acetic acid and n-propyl
  • the molar ratio between the mixture of the trimethoxysilane and the methyltripropoxysilane is 1:1.
  • Example 5 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 0.5:0.8:1.
  • R 9 represents a propenyl group.
  • a 0.2
  • b 1.1.
  • the M/Q ratio is 1.2.
  • Preparation method of MT resin First step: adding anhydrous toluene, absolute ethanol and trimethylethoxysilane to the reaction vessel, and then under the condition of 50-70 ° C under nitrogen protection, specifically refers to the reaction The vessel was placed under a nitrogen atmosphere, and the temperature conditions and nitrogen protection conditions were indispensable.
  • trifluoromethanesulfonate and copper triflate were added as catalysts (ruthenium triflate and trifluoromethyl) to the reaction vessel.
  • ruthenium triflate and trifluoromethyl were added as catalysts (ruthenium triflate and trifluoromethyl) to the reaction vessel.
  • a mass ratio between the copper sulfonate is 1:1
  • acetic acid is added dropwise to the reaction vessel to react the trimethylethoxysilane with the acetic acid to obtain an intermediate product;
  • the molar ratio between trimethylethoxysilane and acetic acid is 1:1.1.
  • the second step removing the solvent in the reaction vessel; the method for removing the solvent is specifically heating and evaporation.
  • the third step adding 80-100 ° C to the reaction vessel, adding tetramethyldihydrodisiloxane, and then adding acetic acid, acetic acid and the first step to the reaction vessel Intermediate product reacts to form silanol, silanol
  • the MT resin was prepared by blocking with tetramethyldihydrodisiloxane.
  • acetic anhydride such as tetramethyldihydrodisiloxane is added to absorb the water formed in the third step. After cooling, washing with water and distillation, a pure MT silicone resin is obtained.
  • the molar ratio between the tetramethyldihydrodisiloxane and the trimethylethoxysilane is 1:0.55; between the acetic acid and the trimethylethoxysilane The molar ratio is 1:1.
  • Example 6 The mass ratio between the MQ resin, the MT resin and the adhesion promoter conforming to the general formula (6) was 1:0.5:1.
  • R 9 represents an ethyl group.
  • the M/Q ratio is 0.7.
  • the preparation method of the MT resin is the same as that of the first embodiment.
  • adhesion promoters in the excipients used in the components B of Examples 2 to 6 are as follows:
  • Example 2 The mass ratio between the C component and the D component is 90:10.
  • Example 3 The mass ratio between the C component and the D component was 40:60.
  • the mass ratio between the compound of the formula (2), the compound of the formula (3), and the compound of the formula (4) is 1:2:1.
  • Example 4 The mass ratio between the C component and the D component was 50:50.
  • the mass ratio between the compound of the formula (2) and the compound of the formula (4) is 1:2.
  • Example 5 The mass ratio between the C component and the D component was 45:55. The mass ratio between the compound of the formula (1) and the compound of the formula (3) is 1:1.
  • Example 6 The mass ratio between the C component and the D component was 20:80. The mass ratio between the compound of the formula (1) and the compound of the formula (2) conforming to the formula (4) is 1:1:1.
  • the preparation method of the transparent silicone gel adhesive of Examples 2 to 6 is the same as that of the first embodiment.
  • the properties of the optical transparent silicone gel adhesive prepared in Example 2 were as follows: the appearance was colorless and transparent, and the light transmittance was 98% (measured by an ultraviolet spectrophotometer) in the range of 400-700 nm.
  • the basic color parameter L is 90.2, a is -2.01, and b is 0.62.
  • the change is small and not yellow.
  • Mechanical properties tensile strength 0.25MPa; good adhesion strength, 180° peel strength for glass is 0.4KN/m, lap shear strength reaches 1.0MPa, flame retardant performance is good, reaching UL94-V0.
  • the refractive index is 1.43.
  • the properties of the optical transparent silicone gel adhesive prepared in Example 3 the appearance is colorless and transparent, at 400-700 nm Within the range, the light transmittance is 95% (measured by an ultraviolet spectrophotometer).
  • the basic color parameter L is 90.2, a is -2.01, and b is 0.62.
  • the change is small and not yellow.
  • Mechanical properties tensile strength 0.20MPa; good adhesion strength, 180° peel strength for glass is 0.4KN/m, lap shear strength reaches 1.0MPa, flame retardant performance is good, reaching UL94-V0.
  • the refractive index is 1.40.
  • the properties of the optical transparent silicone gel adhesive prepared in Example 4 were colorless and transparent, and the light transmittance was 96.5% (measured by an ultraviolet spectrophotometer) in the range of 400-700 nm.
  • the basic color parameter L is 90.2, a is -2.01, and b is 0.62.
  • the change is small and not yellow.
  • Mechanical properties tensile strength 0.28MPa; good adhesion strength, 180° peel strength for glass is 0.4KN/m, lap shear strength reaches 1.0MPa, flame retardant performance is good, reaching UL94-V0.
  • the refractive index is 1.42.
  • the properties of the optical transparent silicone gel adhesive prepared in Example 5 were as follows: the appearance was colorless and transparent, and the light transmittance was 95% (measured by an ultraviolet spectrophotometer) in the range of 400-700 nm.
  • the basic color parameter L is 90.2, a is -2.01, and b is 0.62.
  • the change is small and not yellow.
  • Mechanical properties tensile strength 0.25MPa; good adhesion strength, 180° peel strength for glass is 0.41KN/m, lap shear strength reaches 1.0MPa, flame retardant performance is good, reaching UL94-V0.
  • the refractive index is 1.40.
  • the properties of the transparent transparent silicone gel adhesive prepared in Example 6 were as follows: the appearance was colorless and transparent, and the light transmittance was 97% (measured by an ultraviolet spectrophotometer) in the range of 400-700 nm.
  • the basic color parameter L is 90.2, a is -2.01, and b is 0.62.
  • the change is small and not yellow.
  • Mechanical properties tensile strength 0.25MPa; good adhesion strength, 180° peel strength for glass is 0.4KN/m, lap shear strength reaches 1.0MPa, flame retardant performance is good, reaching UL94-V0.
  • the refractive index is 1.43.

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Abstract

一种透明有机硅凝胶粘接剂，所述透明有机硅凝胶粘接剂由A组分和B组分按照1∶1的质量比例混合后制得；所述A组分由下料60～95重量份的基料，0.1～0.5重量份的催化剂和5～40重量份的辅料组成，所述B组分由60～95重量份的基料、5～20重量份的交联剂、0.1～0.5重量份的抑制剂和1～20重量份的辅料组成。本发明为双组份加成型透明AB硅凝胶粘接剂，对玻璃、PC板、PMMA有很好的粘接性。本发明的折射率介于1.40～1.43，为无色透明凝胶体、光透过率在92％以上，具有一定的弹性和回复性，可以抵抗外部冲击，并且可以保持持久的粘合性。在室温或加温时，可完全固化，具有很好的经济性和可靠性。

Description

一种透明有机硅凝胶粘接剂 技术领域
本发明涉及一种透明有机硅凝胶粘接剂，特别涉及一种光学级透明有机硅凝凝胶粘接剂，可用于粘接玻璃、PC板、PMMA等，适用于加工触摸屏和液晶显示板等光学元件，属于新型的有机硅酮电子封装防护材料技术领域。
背景技术
在工业界中，可适用于透明光学元件上的粘接剂有环氧树脂粘结剂、橡胶型粘结剂、改性丙烯酸树脂粘结剂、聚氨酯粘结剂等材料。
环氧树脂的缺点在于耐黄变性能比较差，同时，其抗开裂和冲击的性能也有欠缺。橡胶型粘结剂的缺点是储存稳定性差。聚氨酯粘结剂缺点是耐温性比较差，高温下易水解。目前被广泛使用的触摸屏用OCA水胶由于成本和售价太高，而且工艺繁琐，有比较大的局限性。
发明内容
本发明目的是提供一种透明有机硅凝胶粘接剂。
为达到上述目的，本发明采用的技术方案是：一种透明有机硅凝胶粘接剂，所述透明有机硅凝胶粘接剂由A组分和B组分按照1∶1的质量比例混合后制得；所述A组分由下料重量份的材料组成：
基料    60～95重量份；
催化剂  0.1～0.5重量份；
辅料    5～40重量份；
所述催化剂为铂族金属催化剂；
所述B组分由下料重量份的材料组成：
Figure PCTCN2014001069-appb-000001
其中，所述基料为符合通式(1)的化合物、符合通式(2)的化合物、符合通式(3)的化合物和符合通式(4)的化合物中的至少一种；
Figure PCTCN2014001069-appb-000002
式中，R1代表碳原子数为1～6的烷基；R2、R3、R4各自独立地代表碳原子数为1～6的烷基或者碳原子数为2～8的烯烃基；x＝5～40，y＝1～30；
Figure PCTCN2014001069-appb-000003
式中，a大于或等于20，b大于或等于30；
Figure PCTCN2014001069-appb-000004
式中，c大于或等于20，d大于或等于30，e大于或等于10；
Figure PCTCN2014001069-appb-000005
式中，f大于或等于30，g大于或等于10，h大于或等于10，i大于或等于10；
采用支链型硅油的优点是：支链型的硅油随粘度的增大而变稀，这种剪切变稀效应有利于硅凝胶中其它成分的分散，它的使用感和粘接性均高于普通的线性硅油，带支链的硅油可以提高其柔韧性和表面粘合性能。
所述交联剂为符合通式(5)的化合物中的至少一种；
Figure PCTCN2014001069-appb-000006
式中，R8代表碳原子数为1～6的烷基；R5、R6、R7各自独立地代表碳原子数为1～6的烷基或者氢基，且R5、R6和R7中的至少一个为氢基；j＝10～30，k＝1～10；
所述辅料包含符合通式(6)的MQ树脂或者符合通式(6)的MQ树脂与端乙烯基硅油的混合物；其中，所述MQ树脂与端乙烯基硅油两者之间的质量比例为0.3～0.4∶0.6～0.7；
所述辅料还包含MT树脂或者MT树脂与端乙烯基硅油的混合物；所述MT树脂与端乙烯基硅油两者之间的质量比例为0.3～0.4∶0.6～0.7；
(Me3SiO0.5)l(R9Me2SiO0.5)m(SiO2)    (6)；
式中，Me代表甲基；R9代表碳原子数为1～6的烷基、环丙基、环丁基、环戊基、环己基或者碳原子数为2～7的烯烃基；l＝0～1.5，m＝0～1.5，且l+m＝1.3～1.8；
所述辅料还包含粘结促进剂，该粘结促进剂由C组分和D组分混合后制得，所述C组分和D组分两者之间的质量比例为10～90∶10～90；所述C组分为符合通式(7)的化合物、符合通式(8)的化合物、符合通式(9)的化合物和符合通式(10)的化合物中的至少一种；所述B组分为符合通式(11)的化合物中的至少一种；
Figure PCTCN2014001069-appb-000008
式中，q＝3～6、r＝2～6、s＝6～12、t＝2～6、u＝3～6、v＝6～12、w＝1～12。
所述抑制剂为炔醇类化合物和含烯烃基环状硅氧烷低聚物中的至少一种。
优选的技术方案为：所述铂族金属催化剂是氯铂酸、醇改性的氯铂酸、铂-乙烯基硅氧烷配合物、氯铂酸与烯烃络合物和铂-烯烃配合物中的至少一种。催化剂的加入量仅仅需要足以有效的作为氢化硅烷化反应催化剂即可，该量可以根据所需的固化速率来改变。若该量过大，该反应就会变得不经济。
铂族金属催化剂作为一种加成型的催化剂，需要做到良好的保存稳定性，并且和胶体具有较好的相容性以及适宜的催化活性。它的含量范围为0.0005-0.6％之间，具体由铂的含量来定。
采用上述进一步方案的有益效果是：选择适宜的催化剂可以调节硅氢的加成反应，按照要求做出不同固化条件的胶体，适当提高铂金催化剂的量还可以使胶体具有一定的阻燃性能。
优选的技术方案为：所述铂族金属催化剂为铂-乙烯基硅氧烷配合物。
优选的技术方案为：所述抑制剂选自3-甲基-1-丁炔-3-醇，3-甲基-1-戊炔-3-醇，3，5-二甲基-1-己炔-3-醇，1-己炔基-1-环己醇，3-苯基-1-丁炔-3-醇，2-甲基-3-丁炔-2-醇和四甲基四乙烯基环四硅氧烷、吡啶、不饱和酰胺。添加抑制剂可以调节硫化速度，满足适宜的工作时间和储存寿命，保证了硅凝胶的贮存稳定性要求；抑制剂炔醇/铂族金属催化剂的摩尔比最佳为40，太高会使胶体表面不平整，太低则固化速度过快，造成工作时间减少，而且也不经济。
优选的技术方案为：所述符合通式(1)的化合物中的烯烃基为乙烯基、烯丙基、丁烯基、戊烯基、己烯基或庚烯基。
优选的技术方案为：所述符合通式(1)的化合物中的R1和R2代表甲基，R3和R4代表乙烯基，且乙烯基含量为0.005～0.5wt％；所述符合通式(1)的化合物的粘度为300～30000厘泊；采用该技术方案的优点是：线性的乙烯基硅油作为基体原料，可以调节产品的黏度，双键集中在两端，分子主链为长链的烷烃，侧链上没有取代基，分子在做链段的运动时产生的内摩擦阻力较小，减少内耗。
或者，所述符合通式(1)的化合物中的R1代表甲基，R2、R3和R4代表乙烯基，且乙烯基含量为0.01～10％；所述符合通式(1)的化合物的粘度为50～10000厘泊；采用 该技术方案的优点是：侧基的乙烯基可以增加更多的交联点，提高最终胶体的玻璃强度等力学性能；
或者，所述符合通式(1)的化合物中的R1、R2和R3代表甲基，R4代表乙烯基，且乙烯基含量为0.001～0.5％；所述符合通式(1)的化合物的粘度为500～10000厘泊。采用该技术方案的优点是：胶体需要通过增塑剂来调整胶体的黏度，采用没有反应活性基团的聚二甲基硅氧烷会在长期的条件下渗油，严重影响胶体在光学器件上的性能，而具有单端有反应活性基团的线性硅油不但可以调整产品最终的粘度度，而且可以作为反应基团体反应上去，不会造成最终产品渗油。
优选的技术方案为：所述符合通式(5)的化合物中的R5和R8代表甲基，R6和R7代表氢基，且所述符合通式(5)的化合物的含氢量为0.005～1％；所述符合通式(5)的化合物的粘度为5～200厘泊；采用该技术方案的优点是：线性的含氢基硅油既可以作为交联剂，又可作为一种扩链剂，其中的Me3SiO0.5链接封装的聚甲基氢硅氧烷可以作为一种抗黄剂。活性氢封端的有机氢聚硅氧烷具有更高的活性，通过调节它的加入量可以提高硅凝胶的强度和韧性，使产品具有很好的机械性能。
或者，所述符合通式(5)的化合物中的R6、R7和R8代表甲基，R5代表氢基，且所述符合通式(5)的化合物的含氢量为0.005～2％；所述符合通式(5)的化合物的粘度为10～100厘泊；采用该技术方案的优点是：侧基的氢基可以增加更多的交联点，交联密度高，提高最终胶体的强度韧性等力学性能。
或者，所述符合通式(5)的化合物中的R8代表甲基，R5、R6和R7代表氢基，且所述符合通式(5)的化合物的含氢量为0.001～10％；所述符合通式(5)的化合物的粘度为10～300厘泊。采用该技术方案的优点是：该含氢硅油可以提供可以控制的活性氢的质量分数，活性氢的质量分数越高，体系中可以参加交联反应的活性点就越多，反应活性就越大，交联密度就越高。通过调节交联成分的种类和用量，使交联物表面具有一定自粘性，使其贴附在器件表面。采用上述基料，调节硅氢和乙烯基比例通常为0.5～1.0。
优选的技术方案为：所述MQ树脂中，R9代表甲基，所述MQ树脂的M/Q的比值为0.6～1.2；采用该技术方案的优点是：甲基MQ树脂具有一定的耐热性和耐低温性，具有一定的柔韧性，硬但是不脆，耐老化，耐紫外，耐水，由于其没有活性基团，它可以降低最终产品的线收缩率，使其更好的在光学器件上使用。
或者，所述MQ树脂中，R9代表乙烯基，且乙烯基的含量小于或等于10w％。采用该技术方案的优点是：作为补强剂，乙烯基MQ树脂具有很好的相容性和分散性，硅氧烷链接具有补强效果，可以与交联剂发生反应，产生牢固的化学结合，提高力学性能。它还作为一种增粘剂，MQ树脂的加入，可以引进有机链节，起到增粘的作用，而且不会 影响体系的粘度，不会影响透光率，不会改变基胶的脆化温度，使其保持良好的低温粘附性，即使达到玻璃化温度也不会失去粘附性，它较好的相容性和透光率满足了在光学器件上的使用。通过调节交联密度，提高硅凝胶的机械性能以及阻燃性能；使其具有较好的耐高低温性，保持胶体固有的粘结强度和柔韧性。
优选的技术方案为：所述MQ树脂的M/Q的比值为0.8。较小的M/Q比值造成制作困难，容易凝胶，较大的M/Q比值即为液体MQ树脂，分子量偏低，分子之间的内聚能下降，不能较好的改善力学性能。
硅凝胶具有来自表面的非交联官能团的粘合性，加入MQ树脂型的增粘成分的产品，或者通过调节非反应性粘合成分的添加量，非交联官能团的侧链长度以及末端官能团的种类等，显示出粘合性。当所述MQ树脂为固体的白色粉末，需要将其与端乙烯基硅油进行混合，混合后成为一种液体共混物，混合的比例为树脂：硅油为0.3∶0.7之间，有选择为0.4∶0.6之间。
1、上述方案中，含氢硅油的含氢量的测定方法参见《光谱实验室》第28卷第3期发表的文章：HNMR测定含氢硅油含氢量和分子量。
由于上述技术方案运用，本发明与现有技术相比具有下列优点和效果：
1、本发明为双组份加成型透明AB硅凝胶粘接剂(以下简称硅凝胶)，对玻璃、PC板、PMMA有很好的粘接性，而这些材料是触摸屏盖板的常用材料。硅凝胶具有低成本和工艺操作简单等特性。其折射率介于1.40～1.43，为无色透明凝胶体、光透过率在92％以上，具有一定的弹性和回复性，可以抵抗外部冲击，并且可以保持持久的粘合性。在室温或加温时，可完全固化，具有很好的经济性和可靠性。
2、本发明的粘接促进剂是一种性能优异的界面补强剂，可以提高硅凝胶与待黏贴表面之间的粘接能力。
附图说明
附图1为MT硅树脂的红外谱图。
附图2为MT硅树脂的核磁氢谱。
附图3为MT硅树脂的核磁硅谱。
具体实施方式
下面结合附图及实施例对本发明作进一步描述：
实施例一：一种透明有机硅凝胶粘接剂
一种透明有机硅凝胶粘接剂，所述透明有机硅凝胶粘接剂由A组分和B组分按照1∶1的质量比例混合后制得；所述A组分由下料重量份的材料组成：
基料    60重量份；
催化剂  0.1重量份；
辅料    5重量份；
所述催化剂为氯铂酸。
所述B组分由下料重量份的材料组成：
Figure PCTCN2014001069-appb-000009
其中，所述基料为符合通式(1)的化合物。
Figure PCTCN2014001069-appb-000010
式中，所述符合通式(1)的化合物中的R1和R2代表甲基，R3和R4代表乙烯基，且乙烯基含量为0.05wt％；所述符合通式(1)的化合物的粘度为10000厘泊。x＝10，y＝15。
所述交联剂符合通式(5)的化合物。
Figure PCTCN2014001069-appb-000011
式中，所述符合通式(5)的化合物中的R5和R8代表甲基，R6和R7代表氢基，且所述符合通式(5)的化合物的含氢量为0.05％；所述符合通式(5)的化合物的粘度为90厘泊；j＝10，k＝5。
所述辅料包含符合通式(6)的MQ树脂。
所述辅料还包含MT树脂。
(Me3SiO0.5)l(R9Me2SiO0.5)m(SiO2)     (6)；
式中，Me代表甲基；R9代表甲基；l＝1，m＝0.8，l+m＝1.8；所述MQ树脂的M/Q的比值为0.8。
所述辅料还包含粘结促进剂，该粘结促进剂由C组分和D组分混合后制得，所述C组分和D组分两者之间的质量比例为30∶70；所述C组分为符合通式(7)的化合物、符合通式(8)的化合物、符合通式(9)的化合物和符合通式(10)的化合物组成的混合物；所述B组分为符合通式(11)的化合物。
Figure PCTCN2014001069-appb-000012
式中，q＝3、r＝2、s＝6、t＝2、u＝3、v＝6、w＝3。
符合通式(7)的化合物、符合通式(8)的化合物、符合通式(9)的化合物和符合通式(10)的化合物四者之间的质量比例为1∶1∶1∶1。
粘结促进剂的制备方法：将C组分和D组分按照分量称量后混合均匀即得。
MT树脂的制备方法，包括下列步骤：
第一步：向反应容器中加入无水甲苯、无水乙醇和甲基三甲氧基硅烷，然后在50～70℃条件下，且在氮气保护下，具体是指反应容器置于氮气气氛下，温度条件和氮气保护条件缺一不可，然后向反应容器中先加入三氟甲磺酸作为催化剂，接着向所述反应容器中滴加醋酸使所述甲基三甲氧基硅烷与所述醋酸进行反应制得中间产物；其中，所述甲基三甲氧基硅烷与醋酸两者之间的摩尔比为1∶1。
第二步：脱除所述反应容器中的溶剂；脱除溶剂的方法具体是加热蒸发。
第三步：在80～100℃条件下，向所述反应容器中加入四甲基二氢基二硅氧烷，然后再向所述反应容器中滴加醋酸，醋酸和第一步制得的中间产物反应生成硅羟基，硅羟基 被四甲基二氢基二硅氧烷封端制得MT树脂；再经冷却、水洗、蒸馏后即得纯的MT有机硅树脂。其中，所述四甲基二氢基二硅氧烷与甲基三甲氧基硅烷两者之间的摩尔比为1∶0.5；所述醋酸与甲基三甲氧基硅烷两者之间的摩尔比为1∶1。
制得的MT树脂的简化平面结构式如下，未画出部分为重复硅氧结构单元。
Figure PCTCN2014001069-appb-000013
制得的MT树脂的简化立体图式如下：
Figure PCTCN2014001069-appb-000014
制得的MT树脂谱图如附图1～3所示。
图1中，2965cm-1是C-H的吸收峰，1268cm-1是Si-CH3的吸收峰，1018cm-1是Si-O-Si的吸收峰。
所述辅料中，符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为1∶1∶0.3。
透明有机硅凝胶粘接剂的制备方法为：分别称取上述重量范围内的各原料，加入搅拌机内，抽真空至真空度为-0.1～-0.05MPa，采用分散搅拌机50～500转/分搅拌0.5～3小时，搅拌均匀后，分别灌装并密封保存即得到所述AB组分硅凝胶。
制得的光学用透明有机硅凝胶粘接剂：外观无色透明，在400-700nm范围内，透光率达到97％(采用紫外分光光度计测得)。基本的颜色参数L为90.2，a为-2.01，b为0.62，经过双85实验(85℃和85％湿度条件)和冷热冲击试验后变化很小，不黄变。力学性能：拉伸强度0.3MPa；具有良好的粘合强度，针对玻璃的180°剥离强度为0.4KN/m，搭接剪切强度达到1.0MPa，阻燃性能好，达到UL94-V0。折射率1.42。
实施例二～八：一种透明有机硅凝胶粘接剂
一种透明有机硅凝胶粘接剂，所述透明有机硅凝胶粘接剂由A组分和B组分按照1 ∶1的质量比例混合后制得。
实施例二～六的A组分配料表如下：
  基料 催化剂 辅料
实施例二 85重量份 0.2重量份 25重量份
实施例三 95重量份 0.3重量份 15重量份
实施例四 90重量份 0.5重量份 20重量份
实施例五 67重量份 0.1重量份 5重量份
实施例六 85重量份 0.15重量份 30重量份
实施例二～六的B组分配料表如下：
  基料 交联剂 抑制剂 辅料
实施例二 65重量份 7重量份 0.1重量份 2重量份
实施例三 85重量份 13重量份 0.2重量份 5重量份
实施例四 70重量份 9重量份 0.1重量份 10重量份
实施例五 69重量份 5重量份 0.25重量份 8重量份
实施例六 90重量份 18重量份 0.5重量份 15重量份
1、实施例二～六的A组份使用的基料：
实施例二：符合通式(1)的化合物和符合通式(2)的化合物按照1∶1的质量比例混合。通式(1)中，R1代表甲基；R2、R3、R4代表乙烯基；x＝20，y＝20；所述符合通式(1)的化合物的粘度为7000厘泊；通式(2)中，a等于20，b等于30。
实施例三：符合通式(3)的化合物，通式(3)中，c等于20，d等于30，e等于10。
实施例四：符合通式(2)的化合物和符合通式(4)的化合物按照1∶1.5的质量比例混合。通式(2)中，a等于20，b等于35，通式(4)中，式中，f等于30，g等于10，h等于10，i等于10。
实施例五：符合通式(1)的化合物、符合通式(2)的化合物、符合通式(3)的化合物和符合通式(4)的化合物按照1∶0.5∶1.5∶1的质量比例组成的混合物。通式(1)中，R1、R2和R3代表甲基，R4代表乙烯基，且乙烯基含量为0.05％；所述符合通式(1)的化合物的粘度为6500厘泊。通式(2)中，a等于25，b等于30。通式(3)中，c等于22，d等于30，e等于15。通式(4)中，f等于30，g等于15，h等于10，i等于20。
实施例六：符合通式(2)的化合物、符合通式(3)的化合物和符合通式(4)的化合物按照0.8∶0.5∶1的质量比例组成的混合物。通式(2)中，a等于25，b等于30。通式(3)中，c等于22，d等于30，e等于15。通式(4)中，f等于30，g等于15，h等于10，i等于20。
2、实施例二～六的A组份使用的催化剂：
实施例二：醇改性的氯铂酸。
实施例三：铂-乙烯基硅氧烷配合物。
实施例四：氯铂酸。
实施例五：醇改性的氯铂酸与铂-乙烯基硅氧烷配合物按照1∶1的质量比例组成的混合物。
实施例六：氯铂酸。
3、实施例二～六的A组份使用的辅料：
实施例二：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为1∶1∶1。所述MQ树脂中，R9代表乙烯基，且乙烯基的含量4w％。a＝1、b＝0.6。M/Q比值为0.8。MT树脂的制备方法：第一步：向反应容器中加入无水甲苯、无水乙醇和二甲基二乙氧基硅烷，然后在50～70℃条件下，且在氮气保护下，具体是指反应容器置于氮气气氛下，温度条件和氮气保护条件缺一不可，然后向反应容器中先加入三氟甲磺酸锌作为催化剂，接着向所述反应容器中滴加醋酸使所述二甲基二乙氧基硅烷与所述醋酸进行反应制得中间产物；其中，所述二甲基二乙氧基硅烷与醋酸两者之间的摩尔比为1∶1.1。
第二步：脱除所述反应容器中的溶剂；脱除溶剂的方法具体是加热蒸发。
第三步：在80～100℃条件下，向所述反应容器中加入四甲基二氢基二硅氧烷，然后再向所述反应容器中滴加醋酸，醋酸和第一步制得的中间产物反应生成硅羟基，硅羟基被四甲基二氢基二硅氧烷封端制得MT树脂。向所述反应容器中加入与四甲基二氢基二硅氧烷等物质量的乙酸酐以吸收第三步中生成的水。再经冷却、水洗、蒸馏后即得纯的MT有机硅树脂。其中，所述四甲基二氢基二硅氧烷与二甲基二乙氧基硅烷两者之间的摩尔比为1∶0.52；所述醋酸与二甲基二乙氧基硅烷两者之间的摩尔比为1∶1.05。
实施例三：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为1∶0.5∶1。所述MQ树脂中，R9代表乙基。a＝0.6、b＝0.8。M/Q比值为0.7。MT树脂的制备方法同实施例一。
实施例四∶符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为0.5∶1∶1。所述MQ树脂中，R9代表环戊基。a＝0.3、b＝1。M/Q比值为0.9。MT树脂的制备方法：第一步：向反应容器中加入无水甲苯、无水乙醇、正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物，正丙基三甲氧基硅烷和甲基三丙氧基硅烷两者之间的质量比为1∶1。然后在50～70℃条件下，且在氮气保护下，具体是指反应容器置于氮气气氛下，温度条件和氮气保护条件缺一不可，然后向反应容器中先加入三氟甲磺酸镨作为 催化剂，接着向所述反应容器中滴加醋酸使所述正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物与所述醋酸进行反应制得中间产物；其中，所述正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物与醋酸两者之间的摩尔比为1∶1.1。
第二步：脱除所述反应容器中的溶剂；脱除溶剂的方法具体是加热蒸发。
第三步：在80～100℃条件下，向所述反应容器中加入四甲基二氢基二硅氧烷，然后再向所述反应容器中滴加醋酸，醋酸和第一步制得的中间产物反应生成硅羟基，硅羟基被四甲基二氢基二硅氧烷封端制得MT树脂。向所述反应容器中加入与四甲基二氢基二硅氧烷等物质量的乙酸酐以吸收第三步中生成的水。再经冷却、水洗、蒸馏后即得纯的MT有机硅树脂。其中，所述四甲基二氢基二硅氧烷与正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物两者之间的摩尔比为1∶0.5；所述醋酸与正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物两者之间的摩尔比为1∶1。
实施例五：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为0.5∶0.8∶1。所述MQ树脂中，R9代表丙烯基。a＝0.2、b＝1.1。M/Q比值为1.2。MT树脂的制备方法：第一步：向反应容器中加入无水甲苯、无水乙醇和三甲基乙氧基硅烷，然后在50～70℃条件下，且在氮气保护下，具体是指反应容器置于氮气气氛下，温度条件和氮气保护条件缺一不可，然后向反应容器中先加入三氟甲磺酸镱和三氟甲磺酸铜作为催化剂(三氟甲磺酸镱和三氟甲磺酸铜两者之间的质量比例为1∶1)，接着向所述反应容器中滴加醋酸使所述三甲基乙氧基硅烷与所述醋酸进行反应制得中间产物；其中，所述三甲基乙氧基硅烷与醋酸两者之间的摩尔比为1∶1.1。
第二步：脱除所述反应容器中的溶剂；脱除溶剂的方法具体是加热蒸发。
第三步：在80～100℃条件下，向所述反应容器中加入四甲基二氢基二硅氧烷，然后再向所述反应容器中滴加醋酸，醋酸和第一步制得的中间产物反应生成硅羟基，硅羟基被四甲基二氢基二硅氧烷封端制得MT树脂。向所述反应容器中加入与四甲基二氢基二硅氧烷等物质量的乙酸酐以吸收第三步中生成的水。再经冷却、水洗、蒸馏后即得纯的MT有机硅树脂。其中，所述四甲基二氢基二硅氧烷与三甲基乙氧基硅烷两者之间的摩尔比为1∶0.55；所述醋酸与三甲基乙氧基硅烷两者之间的摩尔比为1∶1。
实施例六：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为0.7∶0.8∶1。所述MQ树脂中，R9代表丁基。a＝1、b＝0.3。M/Q比值为0.9。MT树脂采用现有技术制作，具体为公布日为2013年1月16日，公布号为CN102875810A，名称为《一种含苯基MT型树脂及其制备方法》的中国发明专利公开的技术方案。
实施例二～六的A组份使用的辅料中的粘结促进剂，其原料配方见下表：
  q r s t u v w w w
              通式(2) 通式(3) 通式(4)
实施例二 4 3 7 3 4 8      
实施例三           6 3 5 7
实施例四           10 8   10
实施例五 3 6 10 6 5 7   12  
实施例六 6 2 9 4 6 12 1   9
注：实施例二：C组分和D组分两者之间的质量比例为90∶10。
实施例三：C组分和D组分两者之间的质量比例为40∶60。符合通式(2)的化合物、符合通式(3)的化合物、符合通式(4)的化合物三者之间的质量比例为1∶2∶1。
实施例四：C组分和D组分两者之间的质量比例为50∶50。符合通式(2)的化合物和符合通式(4)的化合物两者之间的质量比例为1∶2。
实施例五：C组分和D组分分两者之间的质量比例为45∶55。符合通式(1)的化合物和符合通式(3)的化合物两者之间的质量比例为1∶1。
实施例六：C组分和D组分两者之间的质量比例为20∶80。符合通式(1)的化合物、符合通式(2)的化合物符合通式(4)的化合物三者之间的质量比例为1∶1∶1。
4、实施例二～六的B组份使用的基料：
实施例二：符合通式(1)的化合物和符合通式(2)的化合物按照1∶1的质量比例混合。通式(1)中，R1代表甲基；R2、R3、R4代表乙烯基；x＝20，y＝20；所述符合通式(1)的化合物的粘度为7000厘泊；通式(2)中，a等于20，b等于30。
实施例三：符合通式(2)的化合物和符合通式(4)的化合物按照1∶1.5的质量比例混合。通式(2)中，a等于20，b等于35，通式(4)中，式中，f等于30，g等于10，h等于10，i等于10。
实施例四：符合通式(3)的化合物，通式(3)中，c等于20，d等于30，e等于10。
实施例五：符合通式(1)的化合物、符合通式(2)的化合物、符合通式(3)的化合物和符合通式(4)的化合物按照1∶0.5∶1.5∶1的质量比例组成的混合物。通式(1)中，R1、R2和R3代表甲基，R4代表乙烯基，且乙烯基含量为0.05％；所述符合通式(1)的化合物的粘度为6500厘泊。通式(2)中，a等于25，b等于30。通式(3)中，c等于22，d等于30，e等于15。通式(4)中，f等于30，g等于15，h等于10，i等于20。
实施例六：符合通式(2)的化合物、符合通式(3)的化合物和符合通式(4)的化合物按照0.8∶0.5∶1的质量比例组成的混合物。通式(2)中，a等于25，b等于30。通式(3)中，c等于22，d等于30，e等于15。通式(4)中，f等于30，g等于15，h等于10，i等于20。
5、实施例二～六的B组份使用的交联剂：
实施例二：所述符合通式(5)的化合物中的R5和R8代表甲基，R6和R7代表氢基，j＝12，k＝1。所述符合通式(5)的化合物的粘度为100厘泊。
实施例三：所述符合通式(5)的化合物中的R6、R7和R8代表甲基，R5代表氢基，j＝30，k＝10。所述符合通式(5)的化合物的粘度为80厘泊；
实施例四：所述符合通式(5)的化合物中的R8代表甲基，R5、R6和R7代表氢基，j＝15，k＝10。且所述符合通式(5)的化合物的含氢量为3％；所述符合通式(5)的化合物的粘度为200厘泊。
实施例五：同实施例四。
实施例六：同实施例三。
6、实施例二～六的B组份使用的抑制剂：
实施例二：四甲基四乙烯基环四硅氧烷。
实施例三：3-苯基-1-丁炔-3-醇。
实施例四：5-二甲基-1-己炔-3-醇。
实施例五：3-甲基-1-丁炔-3-醇和2-甲基-3-丁炔-2-醇按照1∶1的质量比例组成的混合物。
实施例六：3-甲基-1-戊炔-3-醇。
实施例二：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为1∶1∶1。所述MQ树脂中，R9代表乙烯基，且乙烯基的含量4w％。a＝1、b＝0.6。M/Q比值为0.8。MT树脂的制备方法：第一步：向反应容器中加入无水甲苯、无水乙醇和二甲基二乙氧基硅烷，然后在50～70℃条件下，且在氮气保护下，具体是指反应容器置于氮气气氛下，温度条件和氮气保护条件缺一不可，然后向反应容器中先加入三氟甲磺酸锌作为催化剂，接着向所述反应容器中滴加醋酸使所述二甲基二乙氧基硅烷与所述醋酸进行反应制得中间产物；其中，所述二甲基二乙氧基硅烷与醋酸两者之间的摩尔比为1∶1.1。
第二步：脱除所述反应容器中的溶剂；脱除溶剂的方法具体是加热蒸发。
第三步：在80～100℃条件下，向所述反应容器中加入四甲基二氢基二硅氧烷，然后再向所述反应容器中滴加醋酸，醋酸和第一步制得的中间产物反应生成硅羟基，硅羟基被四甲基二氢基二硅氧烷封端制得MT树脂。向所述反应容器中加入与四甲基二氢基二硅氧烷等物质量的乙酸酐以吸收第三步中生成的水。再经冷却、水洗、蒸馏后即得纯的MT有机硅树脂。其中，所述四甲基二氢基二硅氧烷与二甲基二乙氧基硅烷两者之间的摩尔比为1∶0.52；所述醋酸与二甲基二乙氧基硅烷两者之间的摩尔比为1∶1.05。
实施例三：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为0.7∶0.8∶1。所述MQ树脂中，R9代表丁基。a＝1、b＝0.3。M/Q比值为0.9。MT树脂采用现有技术制作，具体为公布日为2013年1月16日，公布号为CN102875810A，名称为《一种含苯基MT型树脂及其制备方法》的中国发明专利公开的技术方案。
实施例四：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为0.5∶1∶1。所述MQ树脂中，R9代表环戊基。a＝0.3、b＝1。M/Q比值为0.9。MT树脂的制备方法：第一步：向反应容器中加入无水甲苯、无水乙醇、正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物，正丙基三甲氧基硅烷和甲基三丙氧基硅烷两者之间的质量比为1∶1。然后在50～70℃条件下，且在氮气保护下，具体是指反应容器置于氮气气氛下，温度条件和氮气保护条件缺一不可，然后向反应容器中先加入三氟甲磺酸镨作为催化剂，接着向所述反应容器中滴加醋酸使所述正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物与所述醋酸进行反应制得中间产物；其中，所述正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物与醋酸两者之间的摩尔比为1∶1.1。
第二步：脱除所述反应容器中的溶剂；脱除溶剂的方法具体是加热蒸发。
第三步：在80～100℃条件下，向所述反应容器中加入四甲基二氢基二硅氧烷，然后再向所述反应容器中滴加醋酸，醋酸和第一步制得的中间产物反应生成硅羟基，硅羟基被四甲基二氢基二硅氧烷封端制得MT树脂。向所述反应容器中加入与四甲基二氢基二硅氧烷等物质量的乙酸酐以吸收第三步中生成的水。再经冷却、水洗、蒸馏后即得纯的MT有机硅树脂。其中，所述四甲基二氢基二硅氧烷与正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物两者之间的摩尔比为1∶0.5；所述醋酸与正丙基三甲氧基硅烷和甲基三丙氧基硅烷的混合物两者之间的摩尔比为1∶1。
实施例五：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为0.5∶0.8∶1。所述MQ树脂中，R9代表丙烯基。a＝0.2、b＝1.1。M/Q比值为1.2。MT树脂的制备方法：第一步：向反应容器中加入无水甲苯、无水乙醇和三甲基乙氧基硅烷，然后在50～70℃条件下，且在氮气保护下，具体是指反应容器置于氮气气氛下，温度条件和氮气保护条件缺一不可，然后向反应容器中先加入三氟甲磺酸镱和三氟甲磺酸铜作为催化剂(三氟甲磺酸镱和三氟甲磺酸铜两者之间的质量比例为1∶1)，接着向所述反应容器中滴加醋酸使所述三甲基乙氧基硅烷与所述醋酸进行反应制得中间产物；其中，所述三甲基乙氧基硅烷与醋酸两者之间的摩尔比为1∶1.1。
第二步：脱除所述反应容器中的溶剂；脱除溶剂的方法具体是加热蒸发。
第三步：在80～100℃条件下，向所述反应容器中加入四甲基二氢基二硅氧烷，然后再向所述反应容器中滴加醋酸，醋酸和第一步制得的中间产物反应生成硅羟基，硅羟基 被四甲基二氢基二硅氧烷封端制得MT树脂。向所述反应容器中加入与四甲基二氢基二硅氧烷等物质量的乙酸酐以吸收第三步中生成的水。再经冷却、水洗、蒸馏后即得纯的MT有机硅树脂。其中，所述四甲基二氢基二硅氧烷与三甲基乙氧基硅烷两者之间的摩尔比为1∶0.55；所述醋酸与三甲基乙氧基硅烷两者之间的摩尔比为1∶1。
实施例六：符合通式(6)的MQ树脂、MT树脂和粘结促进剂三者之间的质量比例为1∶0.5∶1。所述MQ树脂中，R9代表乙基。a＝0.6、b＝0.8。M/Q比值为0.7。MT树脂的制备方法同实施例一。
实施例二～六的B组份使用的辅料中的粘结促进剂，其原料配方见下表：
Figure PCTCN2014001069-appb-000015
注：实施例二：C组分和D组分两者之间的质量比例为90∶10。
实施例三：C组分和D组分两者之间的质量比例为40∶60。符合通式(2)的化合物、符合通式(3)的化合物、符合通式(4)的化合物三者之间的质量比例为1∶2∶1。
实施例四：C组分和D组分两者之间的质量比例为50∶50。符合通式(2)的化合物和符合通式(4)的化合物两者之间的质量比例为1∶2。
实施例五：C组分和D组分两者之间的质量比例为45∶55。符合通式(1)的化合物和符合通式(3)的化合物两者之间的质量比例为1∶1。
实施例六：C组分和D组分两者之间的质量比例为20∶80。符合通式(1)的化合物、符合通式(2)的化合物符合通式(4)的化合物三者之间的质量比例为1∶1∶1。
实施例二～六中的通式(1)～(11)同实施例一。
实施例二～六的透明有机硅凝胶粘接剂的制备方法同实施例一。
实施例二制得的光学用透明有机硅凝胶粘接剂的性质：外观无色透明，在400-700nm范围内，透光率达到98％(采用紫外分光光度计测得)。基本的颜色参数L为90.2，a为-2.01，b为0.62，经过双85实验(85℃和85％湿度条件)和冷热冲击试验后变化很小，不黄变。力学性能：拉伸强度0.25MPa；具有良好的粘合强度，针对玻璃的180°剥离强度为0.4KN/m，搭接剪切强度达到1.0MPa，阻燃性能好，达到UL94-V0。折射率1.43。
实施例三制得的光学用透明有机硅凝胶粘接剂的性质：外观无色透明，在400-700nm 范围内，透光率达到95％(采用紫外分光光度计测得)。基本的颜色参数L为90.2，a为-2.01，b为0.62，经过双85实验(85℃和85％湿度条件)和冷热冲击试验后变化很小，不黄变。力学性能：拉伸强度0.20MPa；具有良好的粘合强度，针对玻璃的180°剥离强度为0.4KN/m，搭接剪切强度达到1.0MPa，阻燃性能好，达到UL94-V0。折射率1.40。
实施例四制得的光学用透明有机硅凝胶粘接剂的性质·外观无色透明，在400-700nm范围内，透光率达到96.5％(采用紫外分光光度计测得)。基本的颜色参数L为90.2，a为-2.01，b为0.62，经过双85实验(85℃和85％湿度条件)和冷热冲击试验后变化很小，不黄变。力学性能：拉伸强度0.28MPa；具有良好的粘合强度，针对玻璃的180°剥离强度为0.4KN/m，搭接剪切强度达到1.0MPa，阻燃性能好，达到UL94-V0。折射率1.42。
实施例五制得的光学用透明有机硅凝胶粘接剂的性质：外观无色透明，在400-700nm范围内，透光率达到95％(采用紫外分光光度计测得)。基本的颜色参数L为90.2，a为-2.01，b为0.62，经过双85实验(85℃和85％湿度条件)和冷热冲击试验后变化很小，不黄变。力学性能：拉伸强度0.25MPa；具有良好的粘合强度，针对玻璃的180°剥离强度为0.41KN/m，搭接剪切强度达到1.0MPa，阻燃性能好，达到UL94-V0。折射率1.40。
实施例六制得的光学用透明有机硅凝胶粘接剂的性质：外观无色透明，在400-700nm范围内，透光率达到97％(采用紫外分光光度计测得)。基本的颜色参数L为90.2，a为-2.01，b为0.62，经过双85实验(85℃和85％湿度条件)和冷热冲击试验后变化很小，不黄变。力学性能：拉伸强度0.25MPa；具有良好的粘合强度，针对玻璃的180°剥离强度为0.4KN/m，搭接剪切强度达到1.0MPa，阻燃性能好，达到UL94-V0。折射率1.43。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (9)

  1. 一种透明有机硅凝胶粘接剂，其特征在于：所述透明有机硅凝胶粘接剂由A组分和B组分按照1∶1的质量比例混合后制得；所述A组分由下料重量份的材料组成：
    基料      60～95重量份；
    催化剂    0.1～0.5重量份；
    辅料      5～40重量份；
    所述催化剂为铂族金属催化剂；
    所述B组分由下料重量份的材料组成：
    Figure PCTCN2014001069-appb-100001
    其中，所述基料为符合通式(1)的化合物、符合通式(2)的化合物、符合通式(3)的化合物和符合通式(4)的化合物中的至少一种；
    Figure PCTCN2014001069-appb-100002
    式中，R1代表碳原子数为1～6的烷基；R2、R3、R4各自独立地代表碳原子数为1～6的烷基或者碳原子数为2～8的烯烃基；x＝5～40，y＝1～30；
    Figure PCTCN2014001069-appb-100003
    式中，a大于或等于20，b大于或等于30；
    Figure PCTCN2014001069-appb-100004
    式中，c大于或等于20，d大于或等于30，e大于或等于10；
    Figure PCTCN2014001069-appb-100005
    式中，f大于或等于30，g大于或等于10，h大于或等于10，i大于或等于10；
    所述交联剂为符合通式(5)的化合物中的至少一种；
    Figure PCTCN2014001069-appb-100006
    式中，R8代表碳原子数为1～6的烷基；R5、R6、R7各自独立地代表碳原子数为1～6的烷基或者氢基，且R5、R6和R7中的至少一个为氢基；j＝10～30，k＝1～10；
    所述辅料包含符合通式(6)的MQ树脂或者符合通式(6)的MQ树脂与端乙烯基硅油的混合物；其中，所述MQ树脂与端乙烯基硅油两者之间的质量比例为0.3～0.4∶0.6～0.7；
    所述辅料还包含MT树脂或者MT树脂与端乙烯基硅油的混合物；所述MT树脂与端乙烯基硅油两者之间的质量比例为0.3～0.4∶0.6～0.7；
    (Me3SiO0.5)1(R9Me2SiO0.5)m(SiO2)             (6)；
    式中，Me代表甲基；R9代表碳原子数为1～6的烷基、环丙基、环丁基、环戊基、环己基或者碳原子数为2～7的烯烃基；1＝0～1.5，m＝0～1.5，且1+m＝1.3～1.8；
    所述辅料还包含粘结促进剂，该粘结促进剂由C组分和D组分混合后制得，所述C组分和D组分两者之间的质量比例为10～90∶10～90；所述C组分为符合通式(7)的化合物、符合通式(8)的化合物、符合通式(9)的化合物和符合通式(10)的化合物中的至少一种；所述B组分为符合通式(11)的化合物中的至少一种；
    Figure PCTCN2014001069-appb-100007
    式中，q＝3～6、r＝2～6、s＝6～12、t＝2～6、u＝3～6、v＝6～12、w＝1～12。
    所述抑制剂为炔醇类化合物和含烯烃基环状硅氧烷低聚物中的至少一种。
  2. 根据权利要求1所述的透明有机硅凝胶粘接剂，其特征在于：所述铂族金属催化剂是氯铂酸、醇改性的氯铂酸、铂-乙烯基硅氧烷配合物、氯铂酸与烯烃络合物和铂-烯烃配合物中的至少一种。
  3. 根据权利要求2所述的透明有机硅凝胶粘接剂，其特征在于：所述铂族金属催化剂为铂-乙烯基硅氧烷配合物。
  4. 根据权利要求1所述的透明有机硅凝胶粘接剂，其特征在于：所述抑制剂选自3-甲基-1-丁炔-3-醇、3-甲基-1-戊炔-3-醇、3，5-二甲基-1-己炔-3-醇、1-己炔基-1-环己醇、3-苯基-1-丁炔-3-醇、2-甲基-3-丁炔-2-醇和四甲基四乙烯基环四硅氧烷、吡啶、不饱和酰胺。
  5. 根据权利要求1所述的透明有机硅凝胶粘接剂，其特征在于：所述符合通式(1)的化合物中的烯烃基为乙烯基、烯丙基、丁烯基、戊烯基、己烯基或庚烯基。
  6. 根据权利要求1所述的透明有机硅凝胶粘接剂，其特征在于：所述符合通式(1)的化合物中的R1和R2代表甲基，R3和R4代表乙烯基，且乙烯基含量为0.005～0.5wt％； 所述符合通式(1)的化合物的粘度为300～30000厘泊；
    或者，所述符合通式(1)的化合物中的R1代表甲基，R2、R3和R4代表乙烯基，且乙烯基含量为0.01～10％；所述符合通式(1)的化合物的粘度为50～10000厘泊；
    或者，所述符合通式(1)的化合物中的R1、R2和R3代表甲基，R4代表乙烯基，且乙烯基含量为0.001～0.5％；所述符合通式(1)的化合物的粘度为500～10000厘泊。
  7. 根据权利要求1所述的透明有机硅凝胶粘接剂，其特征在于：所述符合通式(5)的化合物中的R5和R8代表甲基，R6和R7代表氢基，且所述符合通式(5)的化合物的含氢量为0.005～1％；所述符合通式(5)的化合物的粘度为5～200厘泊；
    或者，所述符合通式(5)的化合物中的R6、R7和R8代表甲基，R5代表氢基，且所述符合通式(5)的化合物的含氢量为0.005～2％；所述符合通式(5)的化合物的粘度为10～100厘泊；
    或者，所述符合通式(5)的化合物中的R8代表甲基，R5、R6和R7代表氢基，且所述符合通式(5)的化合物的含氢量为0.001～10％；所述符合通式(5)的化合物的粘度为10～300厘泊。
  8. 根据权利要求1所述的透明有机硅凝胶粘接剂，其特征在于：所述MQ树脂中，R9代表甲基，所述MQ树脂的M/Q的比值为0.6～1.2；
    或者，所述MQ树脂中，R9代表乙烯基，且乙烯基的含量小于或等于10w％。
  9. 根据权利要求8所述的透明有机硅凝胶粘接剂，其特征在于：所述MQ树脂的M/Q的比值为0.8。
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