CN102618201A - A kind of reinforced anti-vibration glue with followability and preparation method thereof - Google Patents

Abstract

The invention provides an enhanced anti-vibration adhesive with follow-up property and a preparation method thereof, and the enhanced anti-vibration adhesive mainly comprises the following components: 20-35% of modified vinyl resin; 10-30% of thermoplastic resin; 1-12% of a toughening agent; 0.5-6% of a diluent; 4-35% of a plasticizer; 0.4-5.5% of a coupling agent; 2-6% of a curing agent; 1-5% of an accelerant; 15-35% of a filler; 1-6% of a heat stabilizer; 0.5-5% of a foaming agent; 0.2 to 2.5 percent of pigment. The product has the characteristics of simple preparation, environmental protection, good follow-up property, proper construction viscosity, strong oil surface adhesive force, spraying resistance, good matching property with the electrophoretic primer, capability of curing in a wider temperature range, improvement on the integral strength of parts and the like.

Description

A kind of reinforced anti-vibration glue with followability and preparation method thereof

technical field

The invention relates to the field of chemical materials, in particular to a reinforced anti-vibration glue with followability and a preparation method thereof.

Background technique

1. Reinforced anti-vibration adhesive is mainly used for the isolation and bonding between the outer panels of automobile doors, engine hoods, and trunk lids and the reinforcing ribs. It plays a special role in the structural enhancement of the car, sealing and antirust, vibration and noise reduction, heat insulation and noise reduction, firmness and anti-loosening, interior and exterior decoration, as well as simplifying the manufacturing process and reducing the weight of the car body. The anti-vibration adhesive has good adhesion to the oil-faced steel plate. The anti-vibration adhesive can fully extend and be elastic when pasted. heat curing in a paint drying oven). After the door reinforcement is glued, after cleaning, phosphating, electrophoresis and other painting processes, the anti-vibration glue will be deformed as the door is squeezed and deformed by water entering and exiting, and the glue point will not flow out or slip. After baking, the anti-vibration glue has no cracks and has a good bonding effect. Domestic products of the same kind are less adaptable to painting processes such as cleaning, phosphating, and electrophoresis, and are prone to degumming.

2. With the development of automobile products in the direction of environmental protection and energy saving, safety and comfort, lightweight, low cost, long life and pollution-free, the demand for high-quality anti-vibration rubber will increase. Volatile organic compounds, plasticizers, diluents and other additives, harmful fillers, etc. all have potential factors that may pollute the human body or the environment to varying degrees, and these harmful substances must be avoided during product production. Some well-known foreign automobile manufacturers have clear regulations on hazardous materials that cannot be used, such as plasticizer dioctyl phthalate and heat stabilizer lead salt stabilizer. However, most domestic enterprises that produce adhesives still use dioctyl phthalate and lead salt stabilizers. For example, the plasticizer used in the patent No. 200710072656.4 formula is dioctyl phthalate, and the heat stabilizer is two Lead stearate monobasic or lead maleate tribasic.

3. The filler used by most domestic production enterprises is ordinary calcium carbonate with low cost. Compared with modified nano-calcium carbonate, it is much inferior in terms of hydrophobicity, fluidity, dispersibility and oil absorption value. There will be obvious differences in the products prepared by applying ordinary calcium carbonate and nano-calcium carbonate. The high viscosity of the products containing ordinary calcium carbonate will affect the workability and poor storage stability (solvent precipitation). Adding fillers with calcium sulfate whiskers can significantly improve the strength and high temperature resistance of the product. For example, a filler used in the formula of patent No. 200710072656.4 is ordinary calcium carbonate, and calcium sulfate whiskers are not used.

Contents of the invention

The present invention improves on the defects of the above-mentioned background technology, and provides an environment-friendly reinforced anti-vibration rubber with followability and a preparation method thereof.

For this reason, the technical solution of the present invention is a kind of reinforced anti-vibration glue with followability, which is characterized in that: its composition includes:

Modified vinyl resin 20～35%

thermoplastic resin 10～30%

Toughener 1～12%

Thinner 0.5～6%

plasticizer 4～35%

coupling agent 0.4～5.5%

Hardener 2～6%

Accelerator 1～5%

filler 15～35%

Heat stabilizers 1～6%

Foaming agent 0.5～5%

paint 0.2～2.5%

Wherein the modified vinyl resin is bisphenol type vinyl resin or novolac epoxy type vinyl ester resin.

The thermoplastic resin is polyethylene resin or polyvinyl chloride resin.

The toughening agent is unsaturated end-group reactive liquid nitrile rubber, and its model is ETBN-EP.

The thinner is a-methyl styrene or hydroxypropyl methacrylate.

Plasticizers are epoxy esters, alkyl sulfonates, such as epoxy soybean oil.

The coupling agent is r-aminopropyltriethoxysilane.

The curing agent is methyl ethyl ketone peroxide.

The accelerator is cobalt naphthenate.

The filler is modified nano-calcium carbonate, active silicon micropowder, calcium sulfate whisker, calcium oxide or a combination thereof.

Heat stabilizers are mixed metal stabilizers and organotin stabilizers.

Foaming agent is azo compound, sulfonyl hydrazide compound, such as AC foaming agent and so on.

The pigment is pigmented carbon black.

A method for preparing a reinforced anti-vibration glue with followability, characterized in that the method comprises the following steps:

1) Stir 20-35% modified vinyl resin, 10-30% thermoplastic resin, 4-35% plasticizer, 0.5-6% diluent and 1-12% toughening agent in a high-speed mixer for 30min-60min , until the materials are evenly mixed and set aside.

2) Add 2~6% curing agent, 1~5% accelerator, 0.4~5.5% coupling agent, 1~6% heat stabilizer, 0.5~5% foaming agent, Add 15-35% filler and 0.2-2.5% pigment into the high-speed mixer and stir for 30-90 minutes until the materials are evenly mixed.

3) Pass the uniformly mixed material in the above 2) through the three-roll mill for two or three times, discharge and pack.

Beneficial effect:

The enhanced anti-vibration adhesive with followability of the present invention has good construction performance, and can be used for mechanical pump transportation on the automobile welding line. Set up heating and curing equipment (heating and curing in electrophoresis and other paint drying furnaces), which will not have any adverse effects on cleaning, phosphating, electrophoresis and other painting processes, and the integrity rate of the glued parts of the door and reinforcement is above 98%. The storage period at room temperature can reach more than half a year. After long-term storage or long-term transportation, even if the parts coated with anti-vibration adhesive are baked, the adhesive on the outer panel of the body will not peel off, the adhesive force will be significantly reduced and deformation will occur, and the surface will not be damaged. No deformation will occur.

The enhanced anti-vibration adhesive with followability of the present invention is environmentally friendly, has no peculiar smell and toxicity, and generally does not irritate or irritate the skin if the adhesive contacts the skin, and strictly controls prohibited substances in industrial products.

Description of drawings

Fig. 1 is a reference schematic diagram of the use state of the present invention.

Fig. 2 is a schematic diagram of a qualified sample of the present invention.

Fig. 3 is a schematic diagram of an unqualified sample of the present invention.

Fig. 4 is a schematic diagram of an unqualified sample of the present invention.

Fig. 5 is a flow diagram of the present invention.

Fig. 6 is a schematic diagram of the liquid resistance test of the present invention.

Fig. 7 is a schematic diagram of the glue-coated lap joint of the shear strength test piece of the present invention.

In the figure, 1 is the muzzle of the glue coating, 2 is the test plate, 3 is the sample, 4 is the cushion block, and 5 is the glue coating area.

Detailed ways

The following examples illustrate the present invention in detail, but the present invention is not limited thereto.

Example 1:

Proportion:

(a) Bisphenol type vinyl resin 29%

(b) Polyethylene resin 10%

(c) Reactive liquid nitrile rubber 6%

(d) Hydroxypropyl methacrylate 2.4%

(e) Epoxidized soybean oil 10%

(f) r-Aminopropyltriethoxysilane 1.1%

(g) methyl ethyl ketone peroxide 2%

(h) Cobalt naphthenate 1%

(i) filler 34%

(J) Organotin stabilizer 3%

(K) AC blowing agent 0.5%

(l) Pigment carbon black 1%

Proportion of filler (composition):

Modified Nano Calcium Carbonate 21%, Active Silica Powder 8%, Calcium Sulfate Whiskers 5%.

Example 2:

Proportion:

(a) Novolak epoxy vinyl ester resin 30%

(b) Polyethylene resin 11%

(c) Reactive liquid nitrile rubber 6%

(d) Hydroxypropyl methacrylate 2.4%

(e) Epoxidized soybean oil 10%

(f) r-Aminopropyltriethoxysilane 1.1%

(g) methyl ethyl ketone peroxide 2%

(h) Cobalt naphthenate 1%

(i) filler 32%

(j) Organotin stabilizer 3%

(k) AC blowing agent 0.5%

(l) Pigment carbon black 1%

Proportion of filler (composition):

Modified nano-calcium carbonate 18%, activated silica powder 8%, calcium sulfate whiskers 5%, calcium oxide 1%.

Example 3:

Proportion:

(a) Bisphenol type vinyl resin 30%

(b) Polyethylene resin 10%

(c) Reactive liquid nitrile rubber 6%

(d) Hydroxypropyl methacrylate 2.4%

(e) Epoxidized soybean oil 10%

(f) r-Aminopropyltriethoxysilane 1%

(g) methyl ethyl ketone peroxide 2.1%

(h) Cobalt naphthenate 1%

(i) filler 33%

(j) Organotin stabilizer 3%

(k) AC blowing agent 0.5%

(l) Pigment carbon black 1%

Proportion of filler (composition):

Modified nano-calcium carbonate 20%, active silica powder 6%, calcium sulfate whiskers 5%, calcium oxide 2%.

preparation:

Embodiments 1, 2, and 3 were all prepared as follows.

1) Stir 20~35% modified vinyl resin, 10~30% thermoplastic resin, 4~35% plasticizer, 0.5~6% diluent and 1~12% toughening agent in a high-speed mixer for 30min~1h , until the material is evenly mixed and set aside.

2) Add 2~6% curing agent, 1~5% accelerator, 0.4~5.5% coupling agent, 1~6% heat stabilizer, 0.5~5% foaming agent, Add 15~35% filler and 0.2~2.5% pigment into the high-speed mixer and stir for 30~60min until the materials are evenly mixed.

3) Pass the uniformly mixed material in the above 2) through the three-roll mill for two or three times, discharge and pack.

Performance test: (see Table 1, Table 2)

Embodiment 1, 2, 3 all carry out performance testing by following method.

A.1 Test room requirements: Unless otherwise specified, the test environment is specified as 23±2°C, 50%±5RH.

A.2 Preparation of samples and test panels: after 24 hours in the specified test state, start the test.

A.3 Test plate material and surface treatment: The test plate material is 08AL steel plate for body manufacturing, with a thickness of 0.8-1.6mm. After standing for 24 hours, it is used as an oil surface steel plate.

1) Appearance: visual inspection.

2) Viscosity: Put an appropriate amount of rubber into the cup of the pressure flow viscometer, and measure the time it takes for the rubber to flow out of 20g through the Ø3.0mm aperture at (23±2)°C and a pressure of 0.5MPa, and calculate it 3 times The average value of the measured values, retaining 2 decimal places. Right now:

ŋ = 20×(t/G)

In the formula: ŋ—viscosity of rubber material, s;

t—the time it takes for the rubber material to flow out through the Ф3.0mm aperture, s;

G—the weight of rubber compound, g.

3) Oil surface adhesion

Place the specified oil-coated steel plate horizontally, place the glue gun mouth vertically, 6mm away from the test plate surface, squeeze the sample at 3 places every 80mm, then immediately raise the glue gun at a speed of 180mm/s, and observe the glue. Whether the material is detached from the test plate or drawn. (As shown in Figures 1, 2, 3, and 4).

4) Liquidity

4.1 On the specified oil-faced steel plate (thickness 0.8mm, width 75mm, length 300mm), with the aid of a mold, evenly coat the horizontal dimension (40mm×10mm×5mm) and the longitudinal dimension (100mm×10mm×5mm) perpendicular to each other. Rubber strips (as shown in Figure 5).

4.2 Place the prepared sample plate vertically at room temperature for 10 minutes, observe the flow distance and sliding state of the rubber material, and record it.

4.3 Bake the 4.2 sample plate vertically in an oven at 170°C for 20 minutes, take it out and cool it to room temperature, observe the flow distance and sliding state of the rubber material, and record it.

5) Liquid resistance

5.1 Preparation of the sample: Apply rubber compound with a size of 100mm in length, 10mm in width and 5mm in thickness on the specified oil surface steel plate (the specification is 1.6mm in thickness, 25mm in width and 150mm in length).

5.2 Treatment of the sample: place the prepared sample at room temperature for 1 hour, and vertically soak it in the test medium according to the following procedure (as shown in Figure 6).

5.3 Determination of liquid resistance: take the sample out of the medium, visually inspect the appearance, whether there is any abnormal phenomenon such as dissolution, separation, deformation, etc., then place the sample vertically at room temperature for 5 minutes, and then put it in an oven at 170 ° C for 20 minutes , After taking it out and cooling, visually inspect the appearance for abnormal phenomena such as separation, softening, embrittlement, and deformation.

6) Follow-up

6.1 Purpose: To detect whether the cracking of the adhesive separation is caused by the deflection and warpage of the outer panel of the body.

6.2 Treatment of the sample: use a barrel spray gun (for storing adhesives) to smear about 3g of the sample in the center of the test piece material, add partitions with a thickness of about 5mm at both ends, place and use another test piece material on the partition The board separates the test panel and the adhesive to form a sandwich-like structure. Press the central part of the above-mentioned test piece material by hand until there is a gap of 1 mm before letting go.

6.3 Determination of followability: If the outer panel of the body is restored to its original state and the sealant is not cracked, it is qualified; if the sealant is cracked, it is unqualified.

7) Volume change rate

Take a 30mm×30mm blank aluminum test panel, weigh its mass in the air and pure water, apply about 1.5g of rubber on the test panel, accurately weigh the mass in the air and pure water, and then send it into the oven Curing at 170°C for 20 minutes, after airing at room temperature, weigh the mass of the rubber material and the test panel in air and pure water again, and calculate the volume change rate according to the following formula.

In the formula: S ₁ — volume change rate, %;

W ₁ — the mass of the aluminum plate in the air, g;

W ₂ — the mass of pure water on the aluminum plate, g;

W ₃ - the mass of the aluminum plate and rubber in the air before curing, g;

W ₄ — the mass of aluminum plate and glue in pure water before curing, g;

W ₅ — the mass of the aluminum plate and rubber in the air after curing, g;

W ₆ - the mass of aluminum plate and glue in pure water after curing, g;

8) Normal shear strength

8.1 Preparation of sample: Apply rubber compound with dimensions of 3mm in thickness, 25mm in width and 25mm in length on the specified oil surface steel plate (1.6mm in thickness, 25mm in width and 150mm in length). Lap the oil-faced steel plate of the same specification with the rubber of the same size based on one side. Immediately clamp the pads so that the centerlines of the test pieces are in a straight line, and adjust with the clamps. At the same time, clean up all the overflowing glue on the bonding surface before curing (as shown in Figure 7).

8.2 Treatment of the sample: place the prepared sample at room temperature for 1 hour, then bake it in an oven at 170°C for 20 minutes, take it out and let it cool at room temperature for 24 hours, then remove the clamp and use it as a test piece .

8.3 Determination of shear strength:

Fix the test piece with the fixture of the testing machine so that the long axis of the test piece is consistent with the centerline of the testing machine, and the load passes through the centerline of the testing machine correctly. Then stretch at a speed of 50mm/min, draw the shear load curve at the same time, and pay attention to the form of destruction, and determine the maximum load (N) at which the test piece is destroyed. Result calculation: divide the maximum load by the bonding area (mm ² ), and calculate the shear strength (MPa). Right now:

In the formula: P—the maximum load of specimen shear failure, N;

B—the width of the lap joint of the sample, mm;

L—the length of the overlapping surface of the sample, mm;

τ—normal shear strength of the test piece, MPa.

9) Low temperature bakeability

9.1 Preparation of sample: prepare the sample according to 8.1.

9.2 Treatment of the sample: place the prepared sample at room temperature for 1 hour, then bake it in an oven at 160°C for 20 minutes, take it out and cool it to room temperature for 1 hour, then put it in an oven at 140°C and bake it for 20 minutes. After taking it out and cooling it to room temperature for 24 hours, remove the clamp and use it as a test piece.

9.3 Determination of low temperature bakeability:

Carry out the shear strength test and calculate the shear strength according to 8.3 and 8.4. Result calculation: compare the measured shear strength with the 8 measured shear strength, and calculate the decrease rate of strength. Right now:

In the formula: M—represents the decrease rate of shear strength, %;

τ—normal shear strength of the test piece, MPa;

τ ₁ —the shear strength of the test piece when it is cured at low temperature, MPa.

10) High temperature bakeability

10.1 Preparation of sample: prepare sample according to 8.1.

10.2 Treatment of the sample: place the prepared sample at room temperature for 1 hour, then bake it in an oven at 210°C for 20 minutes, take it out and cool it to room temperature for 24 hours, then remove the clip and use it as a test piece .

10.3 Determination of high temperature bakeability:

Carry out the shear test according to 8.3 and 8.4 and calculate the shear strength. Result calculation: compare the measured shear strength with the shear strength measured in 8, and calculate the decrease rate of the strength. Right now:

In the formula: M—represents the decrease rate of shear strength, %;

τ—normal shear strength of the test piece, MPa;

τ ₁ —the shear strength of the test piece when it is cured at high temperature, MPa.

11) Shelf life

11.1 Appearance: Cover about 50g of the sample in the container, place it in a thermostat at 40°C for 168 hours, take it out, cool it down to room temperature, and visually observe whether there are any abnormal phenomena such as gelation and delamination.

。

.

Table 2

Claims (10)

1. A kind of reinforced anti-vibration glue with followability, is characterized in that, it is made up of following components: (a) Modified vinyl resin 20~35% (b) Thermoplastic resin 10~30% (c) toughening agent 1~12% (d) Thinner 0.5~6% (e) Plasticizer 4~35% (f) Coupling agent 0.4~5.5% (g) curing agent 2~6% (h) Accelerator 1~5% (i) filler 15~35% (j) heat stabilizer 1~6% (k) Blowing agent 0.5~5% (l) Pigment 0.2~2.5%. 2. A kind of follow-up reinforced anti-vibration glue according to claim 1, characterized in that: said modified vinyl resin is bisphenol type vinyl resin or novolak epoxy type vinyl ester resin . 3. A reinforced anti-vibration glue with followability according to claim 1, characterized in that: said thermoplastic resin is polyethylene resin or polyvinyl chloride resin. 4. A reinforced anti-vibration rubber with followability according to claim 1, characterized in that: the toughening agent is modified liquid nitrile rubber, and its model is ETBN-EP. 5. A kind of follow-up anti-vibration glue according to claim 1, characterized in that: the diluent is a-methylstyrene or hydroxypropyl methacrylate; the plasticizer is Epoxy esters or alkyl sulfonates. 6. A reinforced anti-vibration adhesive with followability according to claim 1, characterized in that: said coupling agent is r-aminopropyltriethoxysilane. 7. A reinforced anti-vibration adhesive with followability according to claim 1, characterized in that: the curing agent is methyl ethyl ketone peroxide; the accelerator is cobalt naphthenate. 8. A kind of follow-up anti-vibration rubber according to claim 1, characterized in that: the filler is modified nano-calcium carbonate or active silica powder, calcium sulfate whiskers, calcium oxide or its combination. 9. A kind of follow-up anti-vibration adhesive according to claim 1, characterized in that: the heat stabilizer is a mixed metal stabilizer or an organotin stabilizer; the foaming agent is an azo compound , Sulfonylhydrazine compounds. 10. A preparation method for preparing a kind of follow-up reinforced anti-vibration glue according to claim 1, characterized in that: the method comprises the following steps: 1) Stir 20~35% modified vinyl resin, 10~30% thermoplastic resin, 4~35% plasticizer, 0.5~6% diluent and 1~12% toughening agent in a high-speed mixer for 30min~1h , until the materials are evenly mixed and set aside; 2) Add 2~6% curing agent, 1~5% accelerator, 0.4~5.5% coupling agent, 1~6% heat stabilizer, 0.5~5% foaming agent, Add 15~35% filler and 0.2~2.5% pigment into the high-speed mixer and stir for 30~60min until the materials are evenly mixed; 3) Pass the uniformly mixed material in the above 2) through the three-roll mill for two or three times, discharge and pack.

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