High-performance environment-friendly polyurethane adhesive and preparation method thereof

Abstract

The invention provides a high-performance environment-friendly polyurethane adhesive and a preparation method thereof, and belongs to the technical field of adhesives. Wherein the high-performance environment-friendly polyurethane adhesive is prepared from the following raw materials in parts by mass: the component A is prepared from 60 to 80 parts of polyester type polyol dispersion, 1 to 2 parts of an emulsifier, 0.05 to 0.5 part of a de-foaming agent, 5 to 8 parts of zinc borate and 20 to 30 parts of de-ionized water; the component B comprises the following raw materials in parts by weight: 30-50 parts of a polyisocyanate curing agent, 3-8 parts of modified silicon dioxide, 0.1-0.2 part of a catalyst and 10-15 parts of ethyl acetate; the modified silicon dioxide is modified by an amino silane coupling agent. According to the high-performance environment-friendly polyurethane adhesive provided by the invention, the modified silicon dioxide is added into the component B, and the dispersity of the component B in a water phase is improved by utilizing the synergistic effect after the modified silicon dioxide is combined with the polyisocyanate, so that the structural defect of excessive or insufficient local crosslinking is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and particularly relates to a high-performance environmental protection polyurethane adhesive and a preparation method thereof. Background Art

[0002] With the rapid development of new energy vehicles, the automotive industry has an increasing demand for lightweight, environmental protection and intelligentization. Polyurethane materials, due to their excellent physical properties, lightweight potential and environmental protection characteristics, conform to the concept of new energy vehicles and have become a class of emerging materials widely used in the field of new energy vehicles. Especially in automotive interiors, polyurethane adhesives can meet the various functional requirements of bonding, sealing, shock absorption and sound insulation of automotive interior parts.

[0003] Polyurethane adhesives can be mainly divided into solvent-based, solvent-free and waterborne polyurethane adhesives. Compared with traditional solvent-based polyurethane adhesives, waterborne polyurethane adhesives use water as a solvent and have extremely low volatile organic compound (VOC) content, making them more suitable for use in automotive interiors.

[0004] Currently, common waterborne polyurethane adhesives are mainly composed of a hydroxyl-containing waterborne polyol component (Component A) and an isocyanate group-containing polyisocyanate component (Component B) used together. However, polyisocyanates are extremely prone to react with water and can form a coating, making it difficult for polyisocyanates to be dispersed in the water phase. In some cases, polyisocyanates can even form a complete phase separation phenomenon with water, and it is impossible to form a relatively stable system. Therefore, if polyisocyanates are directly used as the curing agent for two-component waterborne polyurethane adhesives, there are easily structural defects such as excessive or insufficient local cross-linking. Summary of the Invention

[0005] To solve the problems mentioned in the background art, the present invention provides a high-performance environmental protection polyurethane adhesive, in which modified silica is added to Component B. By utilizing the synergistic effect after the combination of modified silica and polyisocyanate, the dispersibility of Component B in the water phase is improved, so that Components A and B are uniformly dispersed, and the structural defects of excessive or insufficient local cross-linking are reduced.

[0006] Specifically:

[0007] A high-performance environmental protection polyurethane adhesive, comprising Component A and Component B;

[0008] By mass, wherein:

[0009] The raw material composition of Component A includes 60 - 80 parts of polyester polyol dispersion, 1 - 2 parts of emulsifier, 0.05 - 0.5 parts of defoamer, 5 - 8 parts of zinc borate, and 20 - 30 parts of deionized water;

[0010] The composition of component B includes 30-50 parts of polyisocyanate curing agent, 3-8 parts of modified silica, 0.1-0.2 parts of catalyst, and 10-15 parts of ethyl acetate;

[0011] The modified silica is silica modified by an amino silane coupling agent.

[0012] Further, the polyester polyol dispersion is selected from polycaprolactone polyol, polycarbonate polyol or polyadipate polyol.

[0013] Further, the emulsifier is selected from glycerol monostearate, glycerol distearate, polyethylene glycol stearate or polyethylene glycol oleate.

[0014] Further, the defoaming agent is selected from silicone defoaming agents.

[0015] Further, the polyisocyanate curing agent is selected from diphenylmethane diisocyanate, toluene diisocyanate or isophorone diisocyanate.

[0016] Further, the catalyst is selected from organotin or organobismuth catalysts.

[0017] Further, the amino silane coupling agent is selected from γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane or γ-aminopropyltrimethoxysilane.

[0018] Further, the silica is selected as nano-silica.

[0019] In addition, the present invention also provides a preparation method of the above-mentioned high-performance environmental protection polyurethane adhesive, including the preparation steps of component A and component B;

[0020] Among them, the preparation steps of component A include: mixing the polyester polyol dispersion, deionized water and emulsifier, and dispersing at high speed; adding zinc borate and continuing to disperse; finally adding a defoaming agent, stirring at low speed, and filtering and packaging to obtain component A;

[0021] The preparation steps of component B include: mixing the polyisocyanate curing agent and ethyl acetate, adding modified silica during stirring, continuing to stir evenly after adding, and packaging to obtain component B.

[0022] Further, the preparation steps of the modified silica in component B include: dispersing silica in anhydrous ethanol, and ultrasonically dispersing to form a suspension; adding an amino silane coupling agent to the suspension, and refluxing and reacting at 75-80 °C for 5-6 h; after the reaction, centrifuging and washing with anhydrous ethanol for several times, and drying in vacuum to obtain modified silica; the mass ratio of silica to amino silane coupling agent is 9-10:1.

[0023] Compared with the prior art, the beneficial features of the present invention are as follows:

[0024] 1. For the high-performance environmentally friendly polyurethane adhesive of the present invention, an amino-silane coupling agent is used to modify nano-silica in component B. There are a large number of silanol groups on the surface of nano-silica itself, and its chemical properties are relatively active. However, its compatibility with polyisocyanate materials is poor and it is difficult to be uniformly dispersed therein. One end of the amino-silane coupling agent molecule contains a group (such as a silane oxy group) that can chemically react with the silanol groups on the surface of silica, and the other end contains an amino group. When the two react, the silane oxy group hydrolyzes to form silanol, which undergoes dehydration condensation with the silanol groups on the surface of silica, so that the amino-silane coupling agent is grafted onto the silica surface to form amino-modified silica. After the amino-modified silica is added to component B, on the one hand, a chemical reaction can occur between the amino group on the surface of the amino-modified silica and the isocyanate group of the polyisocyanate curing agent to form a chemical bond, enhancing the interaction between the two, enabling the silica to be stably dispersed in the polyisocyanate and avoiding the aggregation of silica. On the other hand, when component B is mixed with component A, the polyisocyanate will undergo a polymerization reaction with the hydroxyl groups in the polyester polyol dispersion to form a polyurethane network. The modified silica is introduced into the polyurethane network structure through chemical bonding with the polyisocyanate, and due to the hydrophilicity of the amino group on its surface, the affinity of the entire component B in the aqueous system is improved, thereby enhancing the dispersibility of the polyisocyanate in the aqueous phase.

[0025] 2. For the high-performance environmentally friendly polyurethane adhesive of the present invention, zinc borate is introduced into component A. When component A and component B are mixed, during the curing process, zinc borate will release borate ions, which further react with the residual hydroxyl groups or siloxane groups on the surface of the modified silica in component B to form borosilicate bonds (B-O-Si), forming a three-dimensional heat-resistant skeleton, thereby improving the heat resistance of the adhesive. In addition, the aspect ratio of borate whiskers is relatively large, and it is easy to agglomerate in the adhesive system. The whiskers may be entangled with each other and it is difficult to be uniformly dispersed. The silica particles can adsorb on the surface of the borate whiskers to prevent the agglomeration between the whiskers, enabling the whiskers to be evenly distributed in the adhesive matrix. A stable heat-resistant system is constructed by utilizing the synergistic effect of the two. When applied to automotive interiors, it solves the defect that the service life of the adhesive is shortened due to the high-temperature environment enclosed in the vehicle when the car is parked outdoors in summer.

[0026] 3. For the high-performance environmentally friendly polyurethane adhesive of the present invention, nano-silica is introduced. Nano-silica can absorb and scatter ultraviolet light, improving the weather resistance of the adhesive and extending its service life; at the same time, the presence of nano-silica can also promote the reaction between the polyester polyol dispersion and the polyisocyanate curing agent, shortening the curing time and improving production efficiency. Detailed implementation mode

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0028] To facilitate the implementation of the present invention by those skilled in the art, some of the reagents used in the examples and comparative examples are described below:

[0029] Polyester polyol dispersion: Neopentyl glycol adipate, Hubei Xinyuhong;

[0030] Emulsifier: Glycerol monostearate, Wuhan Xindongyi Chemical Industry;

[0031] Defoamer: Organosilicon defoamer, Weifang Dakang Chemical Industry;

[0032] Zinc borate: Henan Wanshan New Materials;

[0033] Polyisocyanate curing agent: Isophorone diisocyanate, Shanghai Hongzhuang Chemical Industry;

[0034] Aminosilane coupling agent: γ-Aminopropyltriethoxysilane, Wuhan Shuer Biotechnology;

[0035] Silica: Nano-silica, Lingshou County Baiyi Mineral Products Processing Factory;

[0036] Catalyst: Dibutyltin dilaurate, Shandong Qiyun Chemical Industry;

[0037] Ethyl acetate: Jinan Deying Chemical Industry.

[0038] To prove the beneficial effects of the present invention, several groups of examples and comparative examples were designed respectively for comparative experiments to verify.

[0039] Example 1

[0040] A high-performance environmentally friendly polyurethane adhesive, comprising component A and component B; by mass parts, wherein:

[0041] The raw material composition of component A includes 60 parts of polyester polyol dispersion, 1 part of emulsifier, 0.5 part of defoamer, 8 parts of zinc borate, and 30 parts of deionized water;

[0042] The raw material composition of component B includes 30 parts of polyisocyanate curing agent, 3 parts of modified silica, 0.2 part of catalyst, and 15 parts of ethyl acetate;

[0043] The modified silica is silica modified by an amino-silane coupling agent.

[0044] Among them, according to the above ratio, the preparation steps of component A include: mixing the polyester polyol dispersion, deionized water, and emulsifier, maintaining a rotation speed of 1800 rpm, and dispersing at high speed for 20 min; adding zinc borate and continuing to disperse for 30 min; finally adding an antifoaming agent, reducing the rotation speed to 500 rpm, stirring at low speed for 10 min, and filtering and packaging to obtain component A.

[0045] According to the above ratio, the preparation steps of component B include: mixing the polyisocyanate curing agent and ethyl acetate, maintaining a stirring speed of 500 rpm, adding the modified silica during the stirring process, and continuing to stir for 1 h after adding, and packaging to obtain component B.

[0046] The preparation steps of the modified silica in component B include: dispersing silica in absolute ethanol, and ultrasonically dispersing to form a suspension; adding an amino-silane coupling agent to the suspension, and refluxing and reacting at 75 °C for 5 h; after the reaction is completed, centrifuging and washing with absolute ethanol several times, and drying in vacuum to obtain the modified silica; the mass ratio of silica to the amino-silane coupling agent is 9:1.

[0047] Example 2

[0048] A high-performance environmentally friendly polyurethane adhesive, comprising component A and component B; by mass, among them:

[0049] The raw material composition of component A includes 80 parts of polyester polyol dispersion, 2 parts of emulsifier, 0.05 part of antifoaming agent, 5 parts of zinc borate, and 30 parts of deionized water;

[0050] The raw material composition of component B includes 50 parts of polyisocyanate curing agent, 8 parts of modified silica, 0.1 part of catalyst, and 15 parts of ethyl acetate;

[0051] The modified silica is silica modified by an amino-silane coupling agent.

[0052] Among them, according to the above ratio, the preparation steps of component A include: mixing the polyester polyol dispersion, deionized water, and emulsifier, maintaining a rotation speed of 2000 rpm, and dispersing at high speed for 25 min; adding zinc borate and continuing to disperse for 35 min; finally adding an antifoaming agent, reducing the rotation speed to 600 rpm, stirring at low speed for 15 min, and filtering and packaging to obtain component A.

[0053] According to the above ratio, the preparation steps of component B include: mixing the polyisocyanate curing agent and ethyl acetate, maintaining a stirring speed of 600 rpm, adding the modified silica during the stirring process, and continuing to stir for 2 h after adding, and packaging to obtain component B.

[0054] The preparation steps of the modified silica in Component B include: dispersing silica in absolute ethanol and ultrasonically dispersing to form a suspension; adding an amino-silane coupling agent to the suspension and refluxing at 80 °C for 6 h; after the reaction, centrifuging, washing with absolute ethanol several times, and drying in vacuum to obtain the modified silica; the mass ratio of silica to the amino-silane coupling agent is 10:1.

[0055] Example 3

[0056] A high-performance environmentally friendly polyurethane adhesive, comprising Component A and Component B; by mass, where:

[0057] The raw material composition of Component A includes 80 parts of a polyester polyol dispersion, 2 parts of an emulsifier, 0.5 part of an antifoaming agent, 8 parts of zinc borate, and 20 parts of deionized water;

[0058] The raw material composition of Component B includes 50 parts of a polyisocyanate curing agent, 3 parts of modified silica, 0.2 part of a catalyst, and 10 parts of ethyl acetate;

[0059] The modified silica is silica modified by an amino-silane coupling agent.

[0060] Among them, according to the above ratio, the preparation steps of Component A include: mixing the polyester polyol dispersion, deionized water, and emulsifier, maintaining a rotation speed of 2000 rpm, and dispersing at high speed for 20 min; adding zinc borate and continuing to disperse for 35 min; finally adding the antifoaming agent, reducing the rotation speed to 500 rpm, stirring at low speed for 15 min, and filtering and packaging to obtain Component A.

[0061] According to the above ratio, the preparation steps of Component B include: mixing the polyisocyanate curing agent and ethyl acetate, maintaining a stirring speed of 500 rpm, adding the modified silica during the stirring process, and continuing to stir for 2 h after adding, and packaging to obtain Component B.

[0062] The preparation steps of the modified silica in Component B include: dispersing silica in absolute ethanol and ultrasonically dispersing to form a suspension; adding an amino-silane coupling agent to the suspension and refluxing at 80 °C for 5 h; after the reaction, centrifuging, washing with absolute ethanol several times, and drying in vacuum to obtain the modified silica; the mass ratio of silica to the amino-silane coupling agent is 9:1.

[0063] Comparative Example 1

[0064] A polyurethane adhesive, comprising Component A and Component B; by mass, where:

[0065] The raw material composition of Component A includes 60 parts of a polyester polyol dispersion, 1 part of an emulsifier, 0.5 part of an antifoaming agent, 8 parts of zinc borate, and 30 parts of deionized water;

[0066] The raw material composition of Component B includes 30 parts of polyisocyanate curing agent, 0.2 part of catalyst, and 15 parts of ethyl acetate.

[0067] Among them, according to the above ratio, the preparation steps of Component A include: mixing the polyester polyol dispersion, deionized water, and emulsifier, maintaining a rotation speed of 1800 rpm, and dispersing at high speed for 20 min; adding zinc borate and continuing to disperse for 30 min; finally adding an antifoaming agent, reducing the rotation speed to 500 rpm, stirring at low speed for 10 min, and filtering and packaging to obtain Component A.

[0068] According to the above ratio, the preparation steps of Component B include: mixing the polyisocyanate curing agent and ethyl acetate, maintaining a stirring speed of 500 rpm, stirring for 1 h, and packaging to obtain Component B.

[0069] Comparative Example 2

[0070] A polyurethane adhesive, comprising Component A and Component B; by mass parts, wherein:

[0071] The raw material composition of Component A includes 60 parts of polyester polyol dispersion, 1 part of emulsifier, 0.5 part of antifoaming agent, 8 parts of zinc borate, and 30 parts of deionized water;

[0072] The raw material composition of Component B includes 30 parts of polyisocyanate curing agent, 3 parts of silicon dioxide, 0.2 part of catalyst, and 15 parts of ethyl acetate.

[0073] Among them, according to the above ratio, the preparation steps of Component A include: mixing the polyester polyol dispersion, deionized water, and emulsifier, maintaining a rotation speed of 1800 rpm, and dispersing at high speed for 20 min; adding zinc borate and continuing to disperse for 30 min; finally adding an antifoaming agent, reducing the rotation speed to 500 rpm, stirring at low speed for 10 min, and filtering and packaging to obtain Component A.

[0074] According to the above ratio, the preparation steps of Component B include: mixing the polyisocyanate curing agent and ethyl acetate, maintaining a stirring speed of 500 rpm, adding silicon dioxide during the stirring process, and continuing to stir for 1 h after adding, and packaging to obtain Component B.

[0075] Comparative Example 3

[0076] A polyurethane adhesive, comprising Component A and Component B; by mass parts, wherein:

[0077] The raw material composition of Component A includes 60 parts of polyester polyol dispersion, 1 part of emulsifier, 0.5 part of antifoaming agent, and 30 parts of deionized water;

[0078] The raw material composition of Component B includes 30 parts of polyisocyanate curing agent, 3 parts of modified silicon dioxide, 0.2 part of catalyst, and 15 parts of ethyl acetate;

[0079] The modified silica is silica modified by an amino-silane coupling agent.

[0080] Among them, according to the above ratio, the preparation steps of component A include: dispersing the polyester-based polyol dispersion, deionized water, and emulsifier, maintaining a rotation speed of 1800 rpm, and dispersing at high speed for 20 min; adding an antifoaming agent, reducing the rotation speed to 500 rpm, stirring at low speed for 10 min, and filtering and packaging to obtain component A.

[0081] According to the above ratio, the preparation steps of component B include: mixing the polyisocyanate curing agent and ethyl acetate, maintaining a stirring speed of 500 rpm, adding the modified silica during the stirring process, and continuing to stir for 1 h after the addition, and packaging to obtain component B.

[0082] The preparation steps of the modified silica in component B include: dispersing silica in absolute ethanol, and ultrasonically dispersing to form a suspension; adding an amino-silane coupling agent to the suspension, and refluxing and reacting at 75 °C for 5 h; after the reaction, centrifuging and washing with absolute ethanol several times, and drying in vacuum to obtain the modified silica; the mass ratio of silica to the amino-silane coupling agent is 9:1.

[0083] 1. Heat aging performance test: After mixing components A and B of Examples 1-3 and Comparative Examples 1-3 in a mass ratio of 4:1, uniformly coat them on the surface of clean 200 mm × 25 mm sheep leather, brush glue on one side, bond after an open time of 20 s, place for 8 h after bonding, and then keep warm at 70 °C for 10 h to obtain specimen strips;

[0084] Each test group was tested according to the method described in the HG / T 2815-1996 standard. Specifically: the specimen strips were stored under the conditions of a temperature of 25 °C and a relative humidity of 50 parts for 7 days, then stored at 85 °C and a relative humidity of 85 parts for 7 days, and then placed at room temperature for 24 hours, and the T-peel strength was tested. The test results are shown in Table 1:

[0085] Table 1

[0086]

[0087] From the above test results, it can be seen that the heat aging test results of Examples 1-3 are better than those of Comparative Examples 1-3. Compared with Examples 1-3, Comparative Example 1 lacks modified silica in its components, so borosilicate bonds cannot be formed; compared with Examples 1-3, the silica in the components of Comparative Example 2 is not modified, and it is speculated that the heat-resistant system is unstable, resulting in a weakened peel strength; compared with Examples 1-3, Comparative Example 3 lacks zinc borate, resulting in a decrease in the heat-resistant performance of the finishing.

[0088] 2. Aqueous phase dispersibility test:

[0089] Considering that if component B cannot be uniformly dispersed in the aqueous phase system of component A, the difference in local interfacial bonding strength will be reflected in the peel strength, and the dispersion uniformity can be evaluated through multi-point testing.

[0090] Coat the adhesive product on the surface of 200mm×200mm sheepskin, use a wire bar coater to control the wet film thickness at 300μm, cure at 40℃ / 30%RH for 24h, cut 25mm×25mm squares according to the checkerboard pattern using a laser, take 9 cut samples at fixed positions, and refer to ASTM D903 for peel strength testing at an angle of 180° and a rate of 100mm / min.

[0091] After mixing components A and B of Examples 1-3 and Comparative Examples 1-3 in a mass ratio of 4:1, the testing was carried out according to the above method, and the test results are shown in Table 2:

[0092]

[0093] From the above test results, it can be seen that the peel strength of the 9 samples taken in Examples 1-3 is stable. However, in Comparative Example 1, there are obvious drops in the peel strength of samples 4#, 6#, and 7#, and its components lack modified silica, resulting in non-uniform dispersion of component B in the aqueous phase system; similarly, the overall deviation in Comparative Example 2 is more obvious, and the silica in its components is not modified, resulting in non-uniform dispersion of component B in the aqueous phase system; although Comparative Example 3 lacks zinc borate, the peel strength of the 9 samples tested is stable.

[0094] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-performance environmental protection polyurethane adhesive, characterized in that, It contains Component A and Component B; By mass parts, wherein: The raw material composition of Component A includes 60 - 80 parts of polyester polyol dispersion, 1 - 2 parts of emulsifier, 0.05 - 0.5 parts of defoamer, 5 - 8 parts of zinc borate, and 20 - 30 parts of deionized water; The raw material composition of Component B includes 30 - 50 parts of polyisocyanate curing agent, 3 - 8 parts of modified silica, 0.1 - 0.2 parts of catalyst, and 10 - 15 parts of ethyl acetate; The said modified silica is silica modified by amino silane coupling agent.

2. The high-performance environmentally friendly polyurethane adhesive according to claim 1, characterized in that, The said polyester polyol dispersion is selected from polycaprolactone polyol, polycarbonate polyol or polyadipate polyol.

3. The high-performance environmentally friendly polyurethane adhesive according to claim 1, characterized in that The said emulsifier is selected from glycerol monostearate, glycerol distearate, polyethylene glycol stearate or polyethylene glycol oleate.

4. The high-performance environmental protection polyurethane adhesive according to claim 1, characterized in that, The said defoamer is selected from silicone defoamers.

5. The high-performance environmental protection polyurethane adhesive according to claim 1, characterized in that, The said polyisocyanate curing agent is selected from diphenylmethane diisocyanate, toluene diisocyanate or isophorone diisocyanate.

6. The high-performance environmentally friendly polyurethane adhesive according to claim 1, characterized in that, The said catalyst is selected from organotin or organobismuth catalysts.

7. The high-performance environmentally friendly polyurethane adhesive according to claim 1, wherein, The said amino silane coupling agent is selected from γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane or γ-aminopropyltrimethoxysilane.

8. The high-performance environmentally friendly polyurethane adhesive according to claim 1, characterized in that, The said silica is nano-silica.

9. A preparation method of a high-performance environmental protection polyurethane adhesive according to any one of claims 1 to 8, characterized in that, It includes the preparation steps of Component A and the preparation steps of Component B; Among them, the preparation steps of Component A include: mixing polyester polyol dispersion, deionized water and emulsifier, and dispersing at high speed; adding zinc borate and continuing to disperse; finally adding defoamer, stirring at low speed, filtering and packaging to obtain Component A; The preparation steps of Component B include: mixing polyisocyanate curing agent and ethyl acetate, adding modified silica during stirring, continuing to stir evenly after adding, and packaging to obtain Component B.

10. The preparation method of the high-performance environmental protection polyurethane adhesive according to claim 9, characterized in that, The preparation steps of the modified silica in Component B include: dispersing silica in absolute ethanol, ultrasonic dispersing to form a suspension; adding amino silane coupling agent to the suspension, refluxing and reacting at 75 - 80 °C for 5 - 6 h; after the reaction, centrifuging, washing with absolute ethanol for several times, and drying in vacuum to obtain modified silica; the mass parts ratio of silica to amino silane coupling agent is 9 - 10:1.

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