KR20110108893A - Aramid complex product and method for manufacturing the same - Google Patents

Abstract

The present invention relates to an aramid composite and a method for producing the same, which have various levels of bulletproof performance required in the industry, and are excellent in light weight and adhesive strength. The aramid composite material of the present invention is a composite material comprising an aramid fabric, an adhesive layer and a metal base material, characterized in that the surface of any one of the aramid fabric and the metal base material is modified.

Description

Aramid complex product and method for manufacturing the same

The present invention relates to an aramid composite and a method for producing the same, having excellent adhesive strength and light weight while satisfying the level of antiballistic performance required by the industry.

Bulletproof products are products for protecting the human body from bullets and shells, and the bulletproof performance of bulletproof products depends greatly on the materials used.

In particular, bulletproof products used in vehicles require materials having better bulletproof performance in order to protect the human body from great dangers such as external shells.

Accordingly, conventionally, steel sheets have been mainly used as ballistic materials.

 However, the steel sheet has excellent ballistic performance, but the specific gravity is very high to increase the weight of the vehicle, the mobility is very low, the probability of exposure to danger increases, the amount of fuel used is difficult to operate efficiently.

On the other hand, bulletproof products using high-strength plastic or high-strength fiber is very lightweight, but bulletproof performance is less than the steel sheet is not enough to protect the human body from external dangers.

Therefore, in order to lighten the bulletproof product, a dissimilar material composite material composed of a metal base material such as a steel sheet on the front side and a fiber reinforced composite is used on the rear side.

However, since the dissimilar material composite material has a weak adhesive strength by compounding materials having different properties, there is a problem in that the anti-ballistic performance is deteriorated due to a significant decrease in adhesive strength when exposed to an external environment for a long time or when subjected to a large physical shock.

Accordingly, in order to improve adhesion between the metal base material and the fiber reinforced composite, a method of physically and chemically treating the surface of the metal base material has been proposed. However, the conventional method alone has a limit in improving adhesion between different materials having different properties.

Accordingly, an object of the present invention relates to an aramid composite and a method for manufacturing the same, which can be used in various anti-ballistic products as it has a level of antiballistic performance required in the industry, and excellent light weight and adhesive strength.

One aspect of the present invention to achieve the above object, in the composite material including the aramid fabric, the adhesive layer and the metal base material, the surface of any one of the aramid fabric and the metal base material provides an aramid composite characterized in that the modified do.

Another aspect of the invention, to prepare aramid fabric; Preparing a metal base material; Modifying the surface of any one of the aramid fabric and the metal base material; And it provides a method for producing an aramid composite comprising the step of adhering the aramid fabric and the metal base material.

The present invention has the following effects.

First, the aramid composite according to the present invention has a high ballistic performance of the level required in the industry.

Second, the aramid composite according to the present invention has excellent light weight as the aramid fabric and the metal base material is made of an optimal combination.

Third, the aramid composite according to the present invention has excellent adhesive strength as the surface of at least one of the aramid fabric and the metal base material is modified.

As such, the aramid composite having excellent anti-ballistic performance, light weight and adhesive strength can be used in various anti-ballistic products.

1 is a schematic cross-sectional view of an aramid composite according to an embodiment of the present invention.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. Therefore, the present invention encompasses all changes and modifications that come within the scope of the invention as defined in the appended claims and equivalents thereof.

As used herein, the term 'aramid fabric' refers to all molded articles in which aramid fibers are entangled with each other. Examples of the aramid fabric include aramid prepregs and aramid prepres in which a polymer resin is impregnated into the fabric. They include aramid laminates in which several layers are laminated.

As used herein, the term 'aramid fiber' refers to all types of fibers made from aramid polymers, for example aramid filaments or aramid yarns.

As used herein, the term 'aramid prepreg' refers to all molded articles impregnated with a resin that is not fully cured, such as aramid fabrics.

Hereinafter, an embodiment of the aramid composite of the present invention and a method for manufacturing the same will be described in detail with reference to the accompanying drawings.

1 schematically shows a cross section of an aramid composite according to an embodiment of the present invention.

As shown in FIG. 1, the aramid composite of the present invention includes an aramid fabric 30, an adhesive layer 20, and a metal base 10.

The aramid fabric 30 contains aramid fibers and a resin. Optionally, a coupling agent may be included to enhance the adhesive strength.

The aramid fibers can be used as filament, yarn, etc. as defined above, but it may be preferable to use aramid filament to express excellent ballistic performance.

Such aramid filaments may have a total fineness in the range of 500 to 4,000 deier (deier) in consideration of bulletproof performance, productivity and economy.

In addition, the aramid filament may have a tensile strength of 20 g / d or more in order to express the level of ballistic performance required by the industry.

The resin may be a thermoplastic or thermosetting resin, it may be preferable to use a thermosetting resin excellent in impregnation.

The thermosetting resin may be an epoxy resin, a vinyl ester resin, a phenol resin, a cyanate resin, or the like. A phenol resin or an epoxy resin having a low shrinkage rate and excellent processability in the curing process may be used. Can be used. In particular, a phenol resin excellent in flame retardancy and impact resistance can be used.

The phenol resin may have a content of 10 to 30% by weight compared to the aramid fabric 30 in consideration of both adhesive strength, light weight and ballistic resistance.

The aramid fabric 30 can be used in a variety of fabrics, such as woven fabrics, knitted fabrics, one-way sheets, non-woven fabrics, as defined above, to use aramid fabrics to obtain excellent ballistic performance.

The aramid fabric 30 may be an aramid laminated material cured by laminating aramid prepreg in several layers, the aramid laminated material is laminated in 15 to 45 sheets when considering both sufficient ballistic performance, light weight and economic efficiency Can be done.

The adhesive layer 20 may include polyvinyl alcohol (polyvinylalcohol, PVA) or polysulfide. Since the polyvinyl alcohol or polysulfide adhesive has good affinity with the metal base material 10 and the aramid fabric 30, the aramid composite prepared therefrom may have excellent adhesive strength.

The adhesive layer 20 may include a binder, and the binder may play a role of further improving the adhesive strength between the metal base material 10 and the aramid fabric 30. The binder may include a silane-based, titanium-based or zirconium-based binder.

The metal base material 10 includes at least one of iron, aluminum, titanium, and magnesium. The metal base material 10 mainly made of iron has an advantage of excellent bulletproof performance because of its high strength, and the metal base material 10 mainly made of aluminum may be used in a field requiring lightness because it is light, and includes titanium. The metal base material 10 may be used in special fields such as armored vehicles because of its high price but high strength.

The surface of any one of the aramid fabric 30 and the metal base material 10 of the present invention is modified. That is, the surface of any one of the aramid fabric 30 and the metal base material 10 is in an activated state.

The surface of the modified aramid fabric 30 and the metal base material 10 may include a binder. The binder may be a silane compound of Formula 1 or a metal oxide represented by Formula 2.

[Formula 1]

Y- (R) n-SiX ₃ (Y is one functional group selected from halogen atom, epoxy group, amino group, mercapto group, vinyl group, acryloyl group, R is a hydrocarbon group, X is the same or different alkoxy group , n is 0 or 1)

[Formula 2]

M (OR ') m, where m is 3 or 4, R' is a linear or branched alkyl group of 1 to 8 carbon atoms, M is titanium (Ti) or zirconium (Zr)

Since the silane-based binder represented by Chemical Formula 1 has various functional groups, the silane-based binder may easily form various bonds with the bonding surface, thereby improving adhesion strength between the metal base material 10 and the aramid fabric 30.

As the metal oxide-based binder represented by Chemical Formula 2 contains a metal such as titanium or zirconium, adjacent atoms may be easily charged, thereby forming a bonding force between the metal base material 10 and the aramid fabric 30. Since it can increase, it serves to improve the adhesive strength.

The modified aramid fabric 30 surface may have an oxygen content of 105 to 155% compared to the surface of the unmodified aramid fabric 30.

When oxygen is used as a reactive gas to modify the surface of the aramid fabric 30 through the plasma treatment process, the oxygen content of the aramid fabric 30 surface gradually increases and the carbon content decreases as the plasma treatment time increases. . That is, as the plasma treatment time increases, the hydroxyl group (-OH) and the ester group (-COO-) gradually increase on the surface of the aramid fabric 30. This phenomenon is caused by the hydrolysis of the amide bond of the aramid fabric or the benzene ring. It happens to be hydroxylated. Aramid fabric 30 having a large number of such hydroxyl groups and ester groups on the surface greatly improves the adhesive performance with the resin.

If the oxygen content rate is less than 105%, satisfactory adhesive strength cannot be obtained. On the other hand, if the oxygen content rate is more than 155%, the aramid fabric 30 may be damaged to degrade physical properties.

The surface of the modified aramid fabric 30 may have a contact angle with respect to water 35 to 78 °.

In general, the contact angle can be defined as the angle at which the liquid and solid surfaces are thermodynamically balanced. If the contact angle is large, the contact angle has a low surface energy and the contact angle has a high surface energy. For example, when the surface of the aramid prepreg is modified through a plasma treatment process, as the plasma treatment time increases, the contact angle of the aramid prepreg surface decreases, which means that an active functional group is added to the aramid prepreg surface. A large number is generated to increase the surface energy, thereby improving the adhesion performance of the aramid prepreg.

If the contact angle exceeds 78 °, the improvement of the adhesive strength cannot be expected, whereas if the contact angle is less than 35 °, the physical properties of the aramid fabric 30 may be degraded due to excessive surface modification.

The aramid composite of the present invention consisting of the aramid fabric 30 or the metal base material 10 having the modified surface as described above is between the metal base material 10 and the aramid fabric 30 measured by a peel test (peel test) May have a strength of at least 2.6 kgf / 5 cm.

On the other hand, the composite surface-modified aramid fabric 30 or the aramid composite prepared from the metal base material 10 is the adhesive strength between the metal base material 10 and the aramid fabric 30 measured by a peel test (peel test) May have at least 3.0 kgf / 5 cm.

The aramid composite material may satisfy the V50 standard according to the Military Standard 662F specification using M80 having a bullet diameter of 7.62 mm based on the NIJ standard grade 3 when the metal base material 10 is a steel sheet.

Next, the method for producing an aramid composite according to an embodiment of the present invention will be described in detail.

First, aramid fabric 30, which is one component of the aramid composite, is manufactured. The aramid fabric 30 may use a variety of fabrics as described above, in consideration of excellent ballistic performance and economical efficiency can be used aramid fabric. In addition, the aramid fabric 30 may include an impregnated resin, it may be a multi-ply laminated form.

The laminated aramid fabric 30 is impregnated with a resin such as aramid fabric using a dipping process and then semi-cured to produce aramid prepreg, the aramid prepreg is laminated in an appropriate number of high-pressure state It can be prepared by curing.

Next, the metal base material 10 which is one structure of an aramid composite material is prepared. The metal base material 10 may remove foreign substances and the like through a pretreatment process including a pickling process.

Then, the surface of any one of the aramid fabric 30 and the metal base material 10 is modified. The reforming process can be carried out through various methods.

Among them, the surface of any one of the aramid fabric 30 and the metal base material 10 may be modified through a binder treatment. The binder treatment process may be performed through a drying and heat treatment process after imparting a binder through dipping, spraying, or coating. The binder may be a silane compound or a titanium metal oxide as described above.

In addition, the surface of any one of the aramid fabric 30 and the metal base material 10 may be modified through a friction treatment. The friction treatment process may be performed through a sand paper, sand blast, metal brush or shot blast process.

In addition, the surface of any one of the aramid fabric 30 and the metal base material 10 may be modified through a plasma (plasma) treatment. In the plasma treatment process, when the surface of the aramid fabric 30 is treated with oxygen as a reaction gas, the surface of the aramid fabric 30 may generate a large amount of oxygen reactor, and the oxygen reactor has a high affinity. Therefore, adhesive strength can be improved significantly.

The plasma treatment process may be carried out under a nitrogen atmosphere and a reduced pressure of 100 to 3000 watts and irradiation time of 5 to 30 minutes. If the work rate is too low or the irradiation time is too short, less reactors may be generated, while if the work rate is too high or the irradiation time is too long, the aramid fabric 30 may be damaged. Meanwhile, the plasma treatment process may be performed in a nitrogen atmosphere to prevent a decrease in the reactor generated on the aramid fabric 30 surface after the plasma treatment, and the plasma treatment process may be performed under reduced pressure to prevent the introduction of moisture.

In addition, the surface of any one of the aramid fabric 30 and the metal base material 10 may be modified through a corona discharge treatment or a flame treatment. That is, the surface of the aramid fabric 30 and the metal base material 10 may be activated using a corona discharged light source or a flame. In particular, the surface of the activated aramid fabric 30 can greatly improve the adhesive strength as a large number of carboxyl groups, amine groups, or hydroxyl groups are produced.

In the corona discharge treatment process, a high AC voltage is applied between two electrodes while maintaining room temperature and normal pressure to induce a corona discharge, and after placing a sample between the two electrodes, a voltage of 1,000 to 50,000 V and It may be carried out through a process of corona treatment of the surface of the sample at an irradiation time of 1 to 60 minutes.

In the flame treatment process, a mixed gas of natural gas and air is introduced through a flame nozzle to make a flame, and a flame treatment is performed on the surface of a sample at a sample distance of 1 to 10 mm and a treatment time of 0.1 to 30 minutes. Can be performed.

Subsequently, the at least one surface-modified metal base material 10 and the aramid fabric 30 are bonded using a polysulfide or polyvinyl alcohol adhesive.

The process of adhering the aramid fabric 30 and the metal base material 10 may be carried out by inserting an adhesive between the metal base material 10 and the aramid composite material, and then bonding under pressure of 800 psi or more. have.

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the following examples are only intended to help the understanding of the present invention, and the scope of the present invention should not be limited.

1) Surface modification by friction treatment

Example  One

Para-phenylenediamine, an aromatic diamine, and terephthaloyl dichloride, an aromatic dieside chloride, were polymerized in an N-methyl-2-pyrrolidone polymerization solvent to prepare a poly paraphenylene terephthalamide polymer. Was dissolved in a concentrated sulfuric acid solvent to prepare a spinning dope, and the spinning dope was spun through a spinneret and solidified to prepare a wholly aromatic aramid filament of 1,000 denier. Subsequently, the wholly aromatic aramid filaments were applied to warp and weft yarns to weave into plain weave to produce aramid fabrics having a density of 450 g / m 2. Subsequently, the phenol resin was dissolved in a methanol solvent to impregnate the aramid fabric in an impregnation composition having a phenol resin content of 56% by weight, and then the methanol solvent was removed by drying to obtain an aramid prepreg having a phenol resin content of 20%. Got. Subsequently, the aramid prepreg was laminated with 28 sheets, and heated and cured at 150 ° C. while applying pressure to prepare an aramid laminate.

Next, the surface of the steel plate (AR 500) having a thickness of 3.2 mm was rubbed using sandblasting, and then the surface of the rubbed steel sheet was washed using acetone to prepare a surface-modified steel sheet.

Next, the surface of the aramid laminate was modified using sandpaper.

Next, a polysulfide-based adhesive was applied on the aramid laminate having the surface modified, and the steel sheet having the surface modified thereon was brought into close contact and left at room temperature for one day to obtain an aramid composite.

The antiballistic performance of the aramid composites prepared in Example 1 was measured by the following method and shown in Table 1 below.

Bulletproof performance measurement

Bulletproof performance of each aramid composite prepared using M80 having a bullet diameter of 7.62 mm based on the National Institute of Justice (NIJ) standard grade 3 was measured. On the other hand, the bullet-proof performance was measured according to the Military Standard 662F rule whether bullet speed at a distance of 50 m from the muzzle satisfies the V50 standard of 801 ± 9.1 kPa.

division Example 1 Bulletproof performance satisfied

2) surface modification by binder treatment

Example  2

Para-phenylenediamine, an aromatic diamine, and terephthaloyl dichloride, an aromatic dieside chloride, were polymerized in an N-methyl-2-pyrrolidone polymerization solvent to prepare a poly paraphenylene terephthalamide polymer. Was dissolved in a concentrated sulfuric acid solvent to prepare a spinning dope, and the spinning dope was spun through a spinneret and solidified to prepare a wholly aromatic aramid filament of 3,000 denier. Subsequently, the wholly aromatic aramid filaments were applied to warp and weft yarns to weave into plain weave to produce aramid fabrics having a density of 450 g / m 2. Subsequently, the phenol resin was dissolved in a methanol solvent to immerse the aramid fabric in an impregnation composition having a phenol resin content of 56% by weight, followed by drying to remove the methanol solvent to remove the aramid prep having a phenol resin content of 20%. Got a leg. Subsequently, the aramid prepreg was laminated with 28 sheets, and cured at a pressure of 150 ° C. to prepare an aramid laminate.

Next, a steel sheet having a thickness of 3.2 mm and a surface roughness of 30 μm was prepared.

Next, 3-glycidoxylpropyltrimethoxysilane, which is a silane-based binder, is added to an aqueous solution of ethanol at a concentration of 1% by weight to prepare a binder composition, and then the steel sheet and the aramid laminate in the binder composition. After immersing for 30 minutes and heat-treated for 24 hours at a temperature of 100 ℃ to obtain a surface-modified aramid laminate and steel sheet.

Next, after applying the polysulfide-based adhesive to the steel sheet, the aramid laminate was placed thereon, and bonded for 1 hour at a temperature of 50 ℃ and a pressure of 1000 psi to prepare an aramid composite.

Comparative example  One

In Example 2 described above, an aramid composite was prepared in the same manner as in Example 2, except that the binder composition was not treated with the steel sheet and the aramid laminate.

Example  3 to 8

In Example 2 described above, an aramid composite was prepared in the same manner as in Example 2, except that steel sheets having surface roughnesses of 0.5, 2, 10, 50, 70, and 80 μm were used.

Example  9 to 12

In Example 2 described above, an aramid composite was prepared in the same manner as in Example 2 except that the adhesion process was performed at pressures of 700, 2000, 3000, and 4000 psi, respectively.

Example  13 to 16

In Example 2 described above, an aramid composite was prepared in the same manner as in Example 2 except for using a binder composition having a binder concentration of 0.1, 2.0, 3.0 and 4.0 wt%.

Example  17

In Example 2 described above, instead of using the polysulfide adhesive, an aramid composite was prepared in the same manner as in Example 2 except that the polyvinyl alcohol film was bonded for 1 hour at a temperature of 140 ° C. .

Example  18

In Example 2 described above, an aramid composite was prepared in the same manner as in Example 2, except that a titanium ethoxide (Ti (OEt) ₄ ) binder was used instead of the silane-based binder. .

Example  19

In Example 2 described above, an aramid composite was prepared in the same manner as in Example 2, except that a zirconium ethoxide (Zr (OEt) ₄ ) binder was used instead of the silane-based binder. .

The adhesive strength of each of the aramid composites prepared by Examples 2 to 19 and Comparative Example 1 was measured by the following method, and the results are shown in Table 2.

Adhesion Strength of Aramid Composites

The adhesive strength (kgf / 5 cm) between the steel sheet and the aramid fabric 30 was measured by a peel test in accordance with ASTM D903. At this time, the peel test was performed under a load cell of 100 kgf and a speed condition of 300 mm / min.

division Binder glue Surface roughness
(Μm) Adhesive pressure
(psi) Binder concentration
(weight%) Adhesive strength
(Kgf / 5cm) Example 2 Silane system polysufide 30 1000 One 4.6 Comparative Example 1 - polysufide 30 1000 0 2.1 Example 3 Silane system polysufide 0.5 1000 One 2.8 Example 4 Silane system polysufide 2 1000 One 3.0 Example 5 Silane system polysufide 10 1000 One 3.5 Example 6 Silane system polysufide 50 1000 One 5.1 Example 7 Silane system polysufide 70 1000 One 5.7 Example 8 Silane system polysufide 80 1000 One 3.1 Example 9 Silane system polysufide 30 700 One 2.9 Example 10 Silane system polysufide 30 2000 One 4.8 Example 11 Silane system polysufide 30 3000 One 5.0 Example 12 Silane system polysufide 30 4000 One 5.2 Example 13 Silane system polysufide 30 1000 0.1 2.6 Example 14 Silane system polysufide 30 1000 2 5.0 Example 15 Silane system polysufide 30 1000 3 5.3 Example 16 Silane system polysufide 30 1000 4 5.6 Example 17 Silane system PVA 30 1000 One 3.2 Example 18 Titanium polysufide 30 1000 One 5.5 Example 19 Zirconium polysufide 30 1000 One 5.6

3) surface modification by plasma treatment

Example  20

An aramid fabric was obtained by the same method as in Example 2 described above.

Next, the aramid fabric was immersed in a resin composition prepared by dissolving the phenol resin in a methanol solvent, followed by drying to remove the methanol solvent to obtain a preliminary aramid prepreg having a phenol resin content of 20%.

Subsequently, the pre-aramid prepreg was subjected to a plasma treatment process using oxygen as a reactor and a irradiation time of 1500 watts power and 15 minutes to obtain a surface-modified aramid prepreg.

Comparative example  2

In Example 20 described above, an aramid prepreg with an unmodified surface that was not plasma treated was used.

Example  21 to 24

In Example 20, the aramid prepreg was prepared in the same manner as in Example 20, except that the irradiation time was changed to 3, 7, 15, and 35 minutes, respectively.

Example  25 to 29

In Example 20, the aramid prepreg was prepared in the same manner as in Example 20, except that the power was changed to 50, 200, 1000, 2500, and 3500 watts, respectively.

The contact angle, oxygen content rate, and adhesive strength with respect to water of each aramid prepreg prepared in Examples 20 to 29 and Comparative Example 2 were measured by the following method, and the results are shown in Table 3.

About water Contact angle  Measure

The contact angle (°) with respect to water indirectly indicating the degree of surface modification of the aramid prepreg was measured from the sessile drop method using a static contact angle meter (Phoenix 300 Co.) equipped with a CCD (Charge Coupled Device). At this time, the contact angle was obtained by averaging five times or more for each specimen at a temperature of 20 ℃ and a relative humidity of 65%.

Oxygen Content rate  Measure

Using an x-ray photoelectron spectroscopy (XPS) instrument, the oxygen content (C1) of the modified aramid prepreg surface and the oxygen content (C2) of the unmodified aramid prepreg surface are measured, respectively. The oxygen content rate (%) was calculated | required from the formula of [C1 / C2] x100 using these measured values.

Adhesive strength gf / 5 cm) measurement

First, two prepared aramid prepregs were laminated and then bonded and cured at a pressure of 1200 psi and a temperature of 150 ° C. to prepare a sample. Using the sample, the adhesive strength (gf / 5 cm) was measured by a peel test under a load cell of 1 kgf and a speed condition of 300 mm / min according to ASTM D903.

division Survey time (minutes) Power (watts) Contact angle (°) Oxygen content rate (%) Adhesive strength
gf / 5 cm) Example 20 15 1500 47.1 137 221 Comparative Example 2 - - 80.4 - 48 Example 21 3 1500 72.5 110 114 Example 22 7 1500 63.4 128 173 Example 23 25 1500 40.7 143 265 Example 24 35 1500 36.2 150 311 Example 25 15 50 76.2 106 96 Example 26 15 200 71.4 114 121 Example 27 15 1000 63.3 122 117 Example 28 15 2500 45.2 140 213 Example 29 15 3500 37.1 146 297

Example  30

The aramid prepreg prepared in Example 20 described above was laminated to 28 sheets, and then cured at a pressure of 1200 psi and a temperature of 150 ° C. to prepare a preliminary aramid laminate. Subsequently, the aramid laminate was prepared by plasma treatment of the preliminary aramid laminate at a power of 1500 watts and an irradiation time of 10 minutes using oxygen as the reactor.

Next, a 3.2 mm thick steel sheet having a sandblasted 30 μm surface roughness was prepared.

Next, after applying the polysulfide adhesive to the steel sheet, the aramid laminate was placed thereon and bonded for 1 hour at a temperature of 50 ℃ and a pressure of 1000 psi to prepare an aramid composite.

Comparative example  3

In Example 30 described above, an aramid composite was prepared in the same manner as in Example 30 except that the pre-aramid laminate not subjected to plasma treatment was used.

Example  31

In Example 30 described above, an aramid composite was prepared in the same manner as in Example 30, except that a steel plate plasma-treated at a power of 2000 Watts and an irradiation time of 10 minutes using oxygen as a reactive gas was used.

Example  32

In Example 30 described above, except using a pre-aramid laminate not subjected to plasma treatment, and using a steel plate subjected to plasma treatment at a uniform power of 2000 watts and an irradiation time of 10 minutes using oxygen as a reactive gas. An aramid composite was prepared in the same manner as in 30.

The adhesive strength of each aramid composite prepared by Examples 30 to 32 and Comparative Example 3 was measured by the following method, and the results are shown in Table 4.

Measurement of Adhesive Strength (kgf / 5cm) of Aramid Composites

Adhesive strength (kgf / 5cm) was measured by a peel test at a load cell of 100 kgf and a speed of 300 mm / min according to ASTM D903.

division
Plasma treatment Adhesive strength
(Kgf / 5cm) Aramid Composite Steel plate Example 30 ○ × 5.3 Comparative Example 3 × × 2.2 Example 31 ○ ○ 7.0 Example 32 × ○ 4.7

4) Surface modification through corona discharge treatment

Example  33

An aramid fabric was obtained by the same method as in Example 2 described above.

Next, the aramid fabric was immersed in a resin composition prepared by dissolving the phenol resin in a methanol solvent, followed by drying to remove the methanol solvent to obtain a preliminary aramid prepreg having a content of 20% of the phenol resin.

Subsequently, the aramid prepreg was prepared by corona discharge treatment of the preliminary aramid prepreg at room temperature, atmospheric pressure, a voltage of 10,000 V, a frequency of 60 Hz, and a treatment time of 20 minutes.

Example  34

In Example 33 described above, instead of corona discharge treatment of the preliminary aramid prepreg, a mixed gas having a volume ratio of natural gas and air of 1: 1 is used, and the distance from the flame end to the sample is 5 mm and the processing time is Aramid prepreg was prepared in the same manner as in Example 33, except that the preliminary aramid prepreg was flame treated at 5 minutes.

Comparative example  4

In Example 33 described above, the preliminary aramid prepreg without corona discharge treatment was used as the aramid prepreg.

The adhesive strength of each aramid prepreg prepared by Examples 33 to 34 and Comparative Example 4 was measured by the following method, the results are shown in Table 5.

Aramid Prepreg  Adhesive strength measurement

Each prepared aramid prepreg was laminated and then bonded at a pressure of 1200 psi and a temperature of 150 ℃ to make a sample. Using the sample, the adhesive strength (gf / 5 cm) was measured through a peel test at a speed of 300 mm / min with a 1 kgf load cell according to ASTM D903.

division Adhesive strength (gf / 5 cm) Example 33 350 Example 34 320 Comparative Example 4 150

Example  35

The aramid prepreg prepared in Example 33 described above was laminated in 28 sheets so that the modified surface was in the same direction, and then cured at a pressure of 1200 psi and a temperature of 150 ° C. to prepare an aramid laminate.

Next, a 3.2 mm thick steel sheet having a surface roughness of 30 μm was prepared. Subsequently, a polysulfide adhesive was applied to the steel sheet, and then the aramid laminate was placed thereon and adhered at a temperature of 50 ° C. and a pressure of 1000 psi for 1 hour to prepare an aramid composite.

Example  36

In Example 35, the aramid composite was prepared in the same manner as in Example 35, except that the aramid prepreg prepared in Example 34 was used.

Example  37

Preliminary aramid laminates were prepared by stacking 15 preliminary aramid prepregs with no surface modification in Example 33 and molding at a pressure of 1200 psi and a temperature of 150 ° C. Next, the aramid laminate was manufactured by corona discharge treatment on the surface of the preliminary aramid laminate under the same conditions as in Example 33 described above. In Example 35 described above, an aramid composite was prepared in the same manner as in Example 35, except that the aramid laminate was used.

Example  38

In Example 36 described above, the aramid laminate by the same method as in Example 35, except that the surface of the aramid laminate is flame-treated under the same conditions as in Example 34, instead of corona discharge treatment of the surface of the aramid laminate. Composites were prepared.

Example  39

In Example 35 described above, an aramid composite was prepared in the same manner as in Example 35, except that the corona discharge-treated steel sheet was used under the same conditions as described in Example 33.

Example  40

In Example 35 described above, an aramid composite was prepared in the same manner as in Example 35, except that the steel plate treated with flame under the same conditions as described in Example 34 was used.

Comparative example  5

In Example 35 described above, an aramid composite was prepared in the same manner as in Example 35, except that the surface prepared by Comparative Example 4 described above used a pre-modified aramid prepreg.

The adhesive strength of each aramid composite prepared by Examples 35 to 40 and Comparative Example 5 was measured by the following method, and the results are shown in Table 6.

Measurement of Adhesive Strength (kgf / 5cm) of Aramid Composites

The adhesive strength (kgf / 5cm) between the steel sheet and the aramid laminate was measured by a peel test at 100 kgf load cell and 300 mm / min speed according to ASTM D903.

division Aramid prepreg reforming Aramid Laminate Modification Whether to modify the steel sheet Adhesive strength (kgf / 5cm) Example 35 O × × 3.0 Example 36 O × × 3.1 Example 37 × O × 4.5 Example 38 × O × 4.3 Example 39 O × O 3.9 Example 40 O × O 3.7 Comparative Example 5 × × × 2.0

10: metal base material 20: adhesive layer
30: aramid fabric

Claims (7)

In a composite material comprising an aramid fabric, an adhesive layer and a metal base material,
The aramid composite, characterized in that the surface of any one of the aramid fabric and the metal base material is modified. The method of claim 1,
The surface of any one of the modified aramid fabric and the metal base material aramid composite characterized in that it comprises a silane compound represented by the formula (1) or a coupling agent (coupling agent) comprising a metal oxide represented by the formula (2). The method of claim 1,
The surface of the modified aramid fabric is an aramid composite, characterized in that it has an oxygen content of 105 ~ 155% of the surface of the unmodified aramid fabric. The method of claim 1,
The metal base material is an aramid composite containing at least one of iron, aluminum, titanium, and magnesium. The method of claim 1,
The aramid composite is an aramid composite, characterized in that the adhesive strength between the metal base material and the aramid fabric measured by a peel test (2.6 kgf / 5 cm or more). Preparing an aramid fabric;
Preparing a metal base material;
Modifying the surface of any one of the aramid fabric and the metal base material; And
Method for producing an aramid composite comprising the step of adhering the aramid fabric and the metal base material. The method of claim 6,
The step of modifying the surface of any one of the aramid fabric and the metal base material, the step of treating a silane-based compound, or a binder containing a titanium-based metal oxide, 0 to 3000 Watt power and 5 to 30 under a nitrogen atmosphere and reduced pressure A method for producing an aramid composite comprising a plasma treatment step at the irradiation time of minutes, or a corona discharge treatment step at a voltage of 1000 to 50000 V and an irradiation time of 1 to 60 minutes.

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