# Patent

## Title
Resource utilization of paint slag-containing waste limestone powder and treatment process thereof

## Abstract

An asphalt damping sheet, which comprises the following components in indicated amounts based on the total mass of the asphalt damping sheet: a paint slag-containing waste limestone powder 20-50 parts; soft pitch 1-5 parts; hard pitch 11-15 parts; a non-metallic mineral 29-59 parts; PET short fiber 0.1-1.5 parts; and said non-metallic mineral is selected from the group consisting of quartz sand, pottery clay and mica powder. The technical process in the invention uses the paint slag-containing waste limestone powder generated in dry separation process of overspray adopted by vehicle manufacturer paint shops as filler in the asphalt damping sheets, such asphalt damping sheets can be used in the field of machine manufacturing such as automobiles and ships, and also can be used in the field of building waterproof materials, and the goal of resource recycling is achieved.

## Background
CROSS REFERENCE TO RELATED PATENT APPLICATIONS
The present application claims the priority of Chinese patent application No. 2013103799774 filed Aug. 27, 2013.
TECHNICAL FIELD
The invention relates to a process solution for resource utilization of paint slag-containing waste limestone powder, and particularly relates to the use of waste limestone powder in the filler of asphalt damper sheets and recycling in automobile manufacturing.
BACKGROUND OF THE INVENTION
Currently, a dry separation process of overspray is used in the paint workshops of major vehicle manufacturers for handling paint overspray, and such process enables the coating production to get closer to the goal of “green” since it not only reduces energy consumption by 60% and fresh water consumption by 44% but also reduces the carbon dioxide emission by about 33% as compared to the traditional painting workshops. Said technology utilizes a dry purification device to handle the paint mist, and one of the main features of this new technology is to use limestone powder as binding agents. Using limestone powder as a binding agent and the dry particles of overspray are taken away via the air circulation. Said dry separation treatment process of overspray uses tap water and water treatment chemicals no longer, and thus no wastewater is discharged. The limestone powder containing paint slag is the major waste from this process.
Currently, the saturated waste limestone powder after the usage is disposed by way of incineration. And this not only costs high disposal expenses annually but also brings about certain of environmental protection burden, and the incineration disposal process inevitably consumes a lot of energy and tends to cause a second pollution. If the waste limestone powder could be utilized as a feedstock or even be re-used in the automobile manufacturing, then the waste generated during the manufacturing process would be consumed in the automobile manufacturing links, and the environmental burden caused to the society is zero, which saves a lot of human and material resources.
An asphalt damping sheet is a damping sheet using asphalt and non-metallic minerals as raw materials. An asphalt damping sheet as a viscous-elastic material can be attached to the inner surface of vehicle body and can be glued tightly to the steel wall of the vehicle body mainly for reducing noise, reducing vibration and isolating the vibration transmission pathway, i.e. acts as a damper. At the present time, almost all domestic passenger cars are equipped with asphalt damping sheets.
SUMMARY OF THE INVENTION
The object of the invention is the resource utilization of a paint slag-containing waste limestone powder generated in the paint workshops of vehicle manufacturers, which is used as filler in the production of environmentally friendly asphalt damping sheets, so as to address the problems of energy waste and secondary pollution caused by the incineration treatment.
The paint slag-containing waste limestone powder used in the invention is the one generated by the dry separation process of overspray adopted in the dry spray booth of the vehicle manufacturer paint workshops. Wherein, the raw limestone powder is the raw limestone powder of 400 meshes according to KKS451 standard.
To that end, the following technical solutions are used in this invention:
an asphalt damping sheet, the raw material of which comprises the following components in indicated amounts relative to the total mass of the asphalt damping sheet:
a paint slag-containing waste limestone powder: 20-50 parts;
soft pitch: 1-5 parts;
hard pitch: 11-15 parts;
a non-metallic mineral: 29-59 parts;
PET short fiber: 0.1-1.5 parts;
said non-metallic mineral is selected from the group consisting of quartz sand, pottery clay and mica powder.
Said PET short fiber is polyethylene terephthalate short fiber.
Preferably, the amount of the paint slag-containing waste limestone powder in the raw material is 20-40 parts.
Preferably, the amount of PET short fiber in the raw material is 1-1.5 parts.
Preferably, said soft pitch is 30# GB according to GBT 494-2010 China national standard for asphalt.
Preferably, said hard pitch is non-standard asphalt with a melting point ranging from 100° C. to 130° C.; and more preferably, said hard pitch is non-standard asphalt with a melting point ranging from 110° C. to 120° C.
Preferably, the particle size of the said quartz sand is 100-300 meshes.
Preferably, the length of the said PET short fiber is 0.8-2 mm.
Preferably, the raw material of said asphalt damping sheet further comprises 6-15 parts of magnetic powder based on the total mass of the asphalt damping sheet.
Preferably, said asphalt damping sheet further comprises an adhesive layer on the surface of the asphalt damping sheet.
Preferably, the material of said adhesive layer is pressure-sensitive adhesive.
Also provided in the invention is a preparation process of the above asphalt damping sheet, which specifically comprises the steps of:
(1) proportioning: the proportioning is carried out according to the ratio of each component required in the asphalt damping sheet;
(2) mixing: the mixing is carried out in a mixing roll at the temperature of 100-160 for 40-80 minutes;
(3) calendering: the calendering is carried out in a calender in accordance with the desired thickness and width;
(4) cooling: spray cooling;
(5) molding;
(6) transfer coating of splitting;
(7) stamping;
(8) off-line, and packaging into finished product after passing inspection.
Further disclosed in the invention is the use of a paint slag-containing waste limestone powder in the preparation of asphalt damping sheets as raw material of the asphalt damping sheets.
The above use means that said paint slag-containing waste limestone powder is used as filler in the asphalt damping sheets.
Also disclosed in the invention is the use of said asphalt damping sheets in the fields of automobiles or ships and building waterproof materials.
The technical process in the invention uses the paint slag-containing waste limestone powder, which is generated in dry separation process of overspray adopted by vehicle manufacturers, as filler in the asphalt damping sheets, and thus the wastes produced in the automobile manufacturing are recycled, besides, the asphalt damping sheets obtained by this process have better damping effects than those available commercially, and moreover, the asphalt damping sheets obtained by this process are free from visible mildew, apparent musty and apparent odor.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the value of the damping factor tan δ of the sample of Embodiment 1 at different frequencies;
FIG. 2 shows the value of the damping factor tan δ of the sample of Embodiment 2 at different frequencies;
FIG. 3 shows the value of the damping factor tan δ of the sample of Embodiment 3 at different frequencies;
FIG. 4 shows the value of the damping factor tan δ of the sample of Embodiment 4 at different frequencies;
FIG. 5 shows the value of the damping factor tan δ of the sample of Embodiment 5 at different frequencies;
FIG. 6 shows the value of the damping factor tan δ of the sample of Embodiment 6 at different frequencies;
FIG. 7 shows the value of the damping factor tan δ of the sample of Embodiment 7 at different frequencies;



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention is described by way of the following specific embodiments, and it is understood that these embodiments are provided for illustrative purpose only and cannot be construed as limitation of the scope of the invention.
The waste limestone powder used in the embodiments was the paint slag-containing waste limestone powder generated by the dry separation process of overspray adopted in the dry spray booth of the vehicle manufacturer paint shops. Wherein the type of raw limestone powder used in the dry separation process of overspray met KKS451 standard and which was the raw limestone powder of 400 meshes. Such limestone powder transformed into the paint slag-containing waste limestone powder after being used in the dry separation process of overspray, and the content of the paint slag was 7-13% relative to the total mass of the paint slag-containing waste limestone powder. The asphalt damping sheets obtained in the embodiments were compared with the control sample which was high quality asphalt damping sheet available on the market.
Embodiment 1
Paint slag-containing waste limestone powder: 30 parts;
Soft pitch (30#): 1 part;
Hard pitch (melting point: 112V): 15 parts;
Quartz sand (200 meshes): 53 parts;
PET short fiber: 1 part;
The above components were added into a two roll mixing roll at 120° C. and mixed for 60 minutes, and calendered in a vulcanizer at a pressure of 4 MPa and at a temperature of 100° C., naturally cooled and molded; the sample was cut into strips with a length of 17.5 mm or more, a width of 13 mm or less and a thickness of 2 mm; and tested at a temperature of 30° C. in DMA Q-800 single cantilever frequency-conversion constant-temperature testing.
The damping value of the material of embodiment 1 partially overlaps with the control sample, and their damping performances are similar within the frequency range.
Embodiment 2
Paint slag-containing waste limestone powder: 30 parts;
Soft pitch (30#): 3 parts;
Hard pitch (melting point: 112V): 13 parts;
Quartz sand (200 meshes): 53 parts;
PET short fiber: 1 part;
The above components were added into a two roll mixing roll at 120° C. and mixed for 60 minutes, calendered in a vulcanizer at a pressure of 4 MPa and at a temperature of 100° C., naturally cooled and molded; the sample was cut into strips with a length of 17.5 mm or more, a width of 13 mm or less and a thickness of 2 mm; and tested at a temperature of 30° C. in DMA Q-800 single cantilever-thermostatic frequency testing.
The gasket material characters such as hardness and softness were maintained and the amount of soft pitch was increased, then the damping value was slightly higher than that of the control sample within the frequency range.
Embodiment 3
Paint slag-containing waste limestone powder: 50 parts;
Soft pitch (30#): 3 parts;
Hard pitch (melting point: 112V): 13 parts;
Quartz sand (200 meshes): 33 parts;
PET short fiber: 1 part;
The above components were added into a two roll mixing roll at 120° C. and mixed for 60 minutes, calendered in a vulcanizer at a pressure of 4 MPa and at a temperature of 100° C., naturally cooled and molded; the sample was cut into strips with a length of 17.5 mm or more, a width of 13 mm or less and a thickness of 2 mm; and tested at a temperature of 30° C. in DMA Q-800 single cantilever frequency-conversion constant-temperature testing.
The gasket material characters such as hardness and softness were maintained, the ratio of waste limestone powder was increased and the ratio of the quartz sand was decreased, then the damping value was lower than that of the control sample within the frequency range.
Embodiment 4
Paint slag-containing waste limestone powder: 50 parts;
Soft pitch (30#): 5 parts;
Hard pitch (melting point: 112° C.): 11 parts;
Quartz sand (300 meshes): 33 parts;
PET short fiber: 1 part;
The above components were added into a two roll mixing roll at 120° C. and mixed for 60 minutes, calendered in a vulcanizer at a pressure of 4 MPa and at a temperature of 100° C., naturally cooled and molded; the sample was cut into strips with a length of 17.5 mm or more, a width of 13 mm or less and a thickness of 2 mm; and tested at a temperature of 30° C. in DMA Q-800 single cantilever frequency-conversion constant-temperature testing.
The gasket material characters such as hardness and softness were maintained and the ratio of soft pitch was increased and the ratio of hard pitch was decreased, then the damping value was slightly higher than that of embodiment 3, but still slightly lower than that of control sample within the frequency range.
Embodiment 5
Paint slag-containing waste limestone powder: 50 parts;
Soft pitch (30#): 5 parts;
Hard pitch (melting point: 112 V): 15 parts;
Quartz sand (300 meshes): 29 parts;
PET short fiber: 1 part;
The above components were added into a two roll mixing roll at 120° C. and mixed for 60 minutes, calendered in a vulcanizer at a pressure of 4 MPa and at a temperature of 100° C., naturally cooled and molded; the sample was cut into strips with a length of 17.5 mm or more, a width of 13 mm or less and a thickness of 2 mm; and tested at a temperature of 30° C. in DMA Q-800 single cantilever frequency-conversion constant-temperature testing.
The gasket material characters such as hardness and softness were maintained and the ratio of total pitch was increased, then the damping value was slightly higher than that of embodiment 3 and slightly higher than that of control sample within the frequency range, but the total cost would be increased.
Embodiment 6
Paint slag-containing waste limestone powder: 20 parts;
Soft pitch (30#): 5 parts;
Hard pitch (melting point: 112° C.): 15 parts;
Quartz sand (300 meshes): 59 parts;
PET short fiber: 1 part;
The above components were added into a two roll mixing roll at 120° C. and mixed for 60 minutes, calendered in a vulcanizer at a pressure of 4 MPa and at a temperature of 100° C., naturally cooled and molded; the sample was cut into strips with a length of 17.5 mm or more, a width of 13 mm or less and a thickness of 2 mm; and tested at a temperature of 30° C. in DMA Q-800 single cantilever frequency-conversion constant-temperature testing.
The gasket material characters such as hardness and softness were maintained and the ratio of quartz sand was increased, then the damping value was greatly increased compared to that of control sample, but the utilization of limestone powder would be decreased to some extent.
Embodiment 7
Paint slag-containing waste limestone powder: 40 parts;
Soft pitch (30#): 4 parts;
Hard pitch (melting point: 112 V): 12 parts;
Mica: 42.5 parts;
PET short fiber: 1.5 part;
The above components were added into a two roll mixing roll at 150° C. and mixed for 80 minutes, calendered in a vulcanizer at a pressure of 4 MPa and at a temperature of 100° C., naturally cooled and molded; the sample was cut into strips with a length of 17.5 mm or more, a width of 13 mm or less and a thickness of 2 mm; and tested at a temperature of 30° C. in DMA Q-800 single cantilever frequency-conversion constant-temperature testing.
The value of damping factor tan δ of the sample of each embodiment at different frequencies was shown in table 1 and FIG. 1. It can be seen from FIG. 1 and table 1 that, the damping performance of the sample of embodiment 2 exceeded that of the control sample, moreover, the raw material cost was optimal.







TABLE 1







The damping value of each embodiment









Frequency
Control sample
tanδ value of each embodiment















(Hz)
(tanδ)
Embodiment 1
Embodiment 2
Embodiment 3
Embodiment 4
Embodiment 5
Embodiment 6
Embodiment 7


















55
0.8294
0.8114
0.8487
0.7232
0.8114
0.8421
0.8873
0.8387


65
0.8307
0.8255
0.8674
0.7234
0.8076
0.8405
0.902
0.8576


70
0.7988
0.8011
0.8498
0.73
0.7751
0.8123
0.8778
0.8588


75
0.8061
0.8101
0.8528
0.7311
0.7844
0.8233
0.9122
0.86


80
0.8256
0.8289
0.87
0.7332
0.7949
0.8381
0.9218
0.8633


85
0.7997
0.81
0.8683
0.742
0.7715
0.8232
0.9328
0.8751


90
0.7872
0.7691
0.843
0.7038
0.7597
0.79
0.9124
0.823


100
0.7818
0.7625
0.831
0.7121
0.7494
0.7912
0.9032
0.8212









The sample of embodiment 2 was tested for the following performances and the results were shown in table 2:







TABLE 2







Performances of the sample











Name of
HG/T





experimental
4384-2012 trade

Individual



item
standard
Test result
conclusion
Remarks





Weight
—
The side of A4 paper
—
—




weighed 460 g




Thickness
measured after
after the gasket was
qualified
Thinner gaskets could



the gasket and
bonded to the steel

be obtained by



steel being
plate, 2.80 mm

adjusting the



baked


thickness of the mold


Density/
Should be
2.4
qualified
Density depends on


(mg/m3)
within 2.0-2.8


calendering






conditions


tensile
Minimum
The minimal value in
qualified
Dumbbell ASTM


strength/MPa
tensile strength
the test curve of the

D412 Die C



value should be
standard strip being

6 * 115 mm



0.6 MPa
tested was 1.2 MPa




Tear
Tearing Ts
Calculated minimum
qualified
Angle tear ASTM


strength
minimum value
value of the standard

D624 Die C



should be
strip tested was 9 KN/m





5 KN/m





Flexibility
Diameter 10 cm
No cracks
qualified
—



axis curl, no






cracks





Blocking
stacking under
Some gaskets blocked,
qualified
Standards could be


resistance
standard
and some not

met via the use of



conditions, no


release paper



blocking






occurs; release






paper could be






used





Baking
The
No cracking, good
qualified
—


conditions
adhesiveness
adhesion




and
was good after





properties
baked around





after
165° C., no





being
cracking





baked






Consistency
Being
The shape was
qualified
—



consistent with
consistent, and was





the surface
consistent with the





shape of
shape of cross-convex





ladder-type steel
steel





plate





Cold
After baking the
Comparative
qualified
—


punching
bonding, chilled
experiment, cold punch





at minus 20° C.
phenomenon were





prior to cold
similar between sample





punching
and control sample




Vibration
Comparative
Loss value was high
qualified
Higher than the


damping
experiments;


control sample


properties



(30° C.)


Shrinkage
Drying method,
Percentage of change
qualified
—


ratio/%
the dimensional
was 0.4%





change should






be less than






2.0%





High
Attached to
no-slip
qualified
—


temperature
horseshoe-shaped





resistance
steel plates






after being






baked, no-slip









The above performance tests were in accordance with the specification standards regarding asphalt damping sheets of certain auto parts factory.
The sample of embodiment 2 of the present invention was submitted to a third-party testing organization for testing other performances and the results were shown in table 3, wherein the performance test specifications and standards in table 3 were as follows:
Mildew performance was tested according to GMW3259 standards and no apparent mildew or musty should be occurred;
Atomization performance was tested according to GMW3235 standards, and the atomization amount should be greater than or equal to 80;
Odor test was performed according to GMW3205, and the odor level should be greater than or equal to 6 (level 10=odorless; level 8=perceivable odor; 6=tolerable odor; 4=disgusting odor; 2=very disgusting odor; 1=intolerable odor);
Flame retardancy was tested according to GMW323, and the combustion rate should not exceed 100 mm/min.







TABLE 3







The test results of other performances of sample of embodiment 2











Sample 1
Sample 2
Sample 3





Mildew
no visible
no visible
no visible


performance
mildew
mildew
mildew



no apparent
no apparent
no apparent



musty
musty
musty


Atomization
88.67
89.33
88.00


amount





Odor level
6.3 (wet
6.0 (dry
—



method, 24
method, 24




hours@70° C. ±
h@70° C. ±




2° C. &50 ml
2° C.)




deionized water)




Flame
non-
non-
non-


retardancy
combustible
combustible
combustible

## Claims

1. An asphalt damping sheet comprising the following components in indicated amounts based on the total mass of the asphalt damping sheet:
20-50 parts of a paint slag containing waste limestone powder collected from a dry separation process of overspray;
1-5 parts of soft pitch;
11-15 parts of hard pitch;
29-59 parts of a non-metallic mineral;
0.1-1.5 parts of polyethylene terephthalate short fibers;
said non-metallic mineral is one or more selected from the group consisting of quartz sand, pottery clay and mica powder;
said soft pitch is 30# pitch according to GB/T 494-2010 China national standard for asphalt;
a melting point of the hard pitch is ranging from 100° C. to 130° C.;
said polyethylene terephthalate short fibers have a length of 0.8-2 mm.

2. The asphalt damping sheet according to claim 1, characterized in that the particle size of the quartz sand is in the range of 100-300 mesh.

3. The asphalt damping sheet according to claim 1, further comprises 6-15 parts of magnetic powder.

4. The asphalt damping sheet according to claim 1, characterized in that said asphalt damping sheet further comprises an adhesive layer on the surface of the asphalt damping sheet.

5. The asphalt damping sheet according to claim 1, characterized in that a content of the paint slag is 7-13% relative to the total mass of the paint slag containing waste limestone powder.