KR100640293B1 - Molding product from siloxane polymer compound with adhesion layer thereon, and formation method thereof - Google Patents

Abstract

Provided are a method for forming an adhesive layer on the surface of a molded product comprising a siloxane polymer at a room temperature without a curing process at a high temperature for a long time, and a molded product comprising a siloxane polymer. The method comprises the steps of diluting a one-pack type sealant and coating it on the surface of a molded product comprising a siloxane polymer; drying the solvent contained in the coated diluted sealant, and crosslinking and curing it for 30-60 min; and forming an adhesive layer of an acrylic adhesive during the crosslinking process. Preferably the diluted sealant is coated by using a brush or a spray, and the sealant is diluted with 200-1,200 parts by weight of a thinner based on 100 parts by weight of the sealant.

Description

MOLDING PRODUCT FROM SILOXANE POLYMER COMPOUND WITH ADHESION LAYER THEREON, AND FORMATION METHOD THEREOF}

1 is a photograph showing a state in which a dilution sealant is applied with a brush on a molding made of a siloxane polymer compound according to the present invention.

Figure 2 is a photograph showing the appearance of spray coating on a molding made of a siloxane polymer compound diluted sealant according to the present invention.

3 is an acrylic transfer tape having an acrylic pressure-sensitive adhesive layer formed on one surface of a double-sided release paper.

Figure 4 is a photograph showing the appearance of the roller pressing the acrylic transfer tape after the sealant coating.

5 is a photograph showing a state of cutting a molding made of a siloxane polymer compound in which an acrylic pressure-sensitive adhesive layer is formed.

The present invention relates to a method for forming an adhesive layer on the surface of a molded article made of a siloxane polymer compound and to a molded article made of a siloxane polymer compound in which an adhesive layer is formed.

Recently, with the rapid development of the industry, the industry is developing a variety of new materials and demanding materials having excellent chemical properties. Among the high-tech materials, siloxane polymer compound is also called silicone compound, which is a compound composed of polymer containing siloxane bond, and has stable chemical structure that cannot be compared with any other elastic material, and it is not corrosive and oxidized. As a non-compound compound, it has various properties such as heat resistance, cold resistance, electrical insulation, chemical safety, abrasion resistance, glossiness, and abundant elasticity.

However, the completed siloxane polymer compound is very stable chemically and physically because the structure of the basic polymer bond is composed of siloxane bonds. Therefore, once crosslinking / molding is performed, adhesion, deposition and painting on the surface thereof are performed. It is very difficult to carry out further work. Therefore, in order to solve this problem, efforts to add adhesiveness in various ways continue.

In order to provide adhesion to the surface of the polymer or nitride, the target polymer or nitride is placed in a vacuum state, and an ion particle having energy is irradiated to the surface of the polymer or nitride while blowing a reactive gas directly onto the surface. The surface modification method of the polymer consisting of reducing the contact angle or increasing the adhesion of the polymer surface is disclosed in Korean Patent Application No. 1996-11996.

In addition, Korean Patent Application No. 1999-40418 discloses activating a surface of the silicone rubber by applying ions accelerated by applying energy to the silicone rubber under vacuum to activate the surface of the silicone rubber, and then blowing a reactive gas into the surface of the activated silicone rubber. By reacting, the method of providing hydrophilicity and adhesive force to the silicone rubber surface is disclosed.

These methods are methods of imparting adhesiveness to the surface thereof while maintaining the basic physical properties of the silicone rubber itself, and these ion irradiation methods have been used as a method of forming an adhesive layer on the surface of the silicone rubber in the entire industry. .

However, these methods using ion irradiation are currently used as the most effective technology for modifying the surface of polymers, but all require high vacuum environment, process time, and expensive equipment due to the characteristics of surface treatment. It is pointed out that the disadvantage.

In addition, in Korean Patent Application No. 2001-30841, a pressure-sensitive adhesive layer is first formed on two release treatment surfaces, and a silicone adhesive primer is applied to the surface of the pressure-sensitive adhesive layer, respectively, and then contacted with the primer. A method for producing a silicone heat dissipating sheet having adhesiveness is disclosed by sandwiching liquid silicone between mold release surfaces and heat-crosslinking them all together at a high temperature. However, this method is a method of inserting a liquid heat-dissipating silicone between two release papers and thermally crosslinking the sheet to form a sheet, and not a method of forming an adhesive layer on the surface of the completed siloxane compound.

In addition, this method requires a specially prepared silicone primer when the adhesive is applied to form the pressure-sensitive adhesive layer, and must be accompanied by a silicone crosslinking process of heating at least 200 ° C. for at least 2 hours. As a result, the price of the final product is increased and the time required for the process is long, and it must be included in the process of crosslinking the silicone, and it is a fundamental limitation that cannot give adhesion to the surface of the silicone rubber product that has been formed. There is.

An object of the present invention is to provide a method for forming an adhesive layer on the surface of a completed siloxane polymer compound.

In another aspect, the present invention is to provide a molded article made of a siloxane polymer compound, the adhesive layer formed on the surface in a simpler method.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, as a result, after diluting and apply | coating general purpose 1-component silicone sealant which attribute-cures at room temperature to the surface of the siloxane compound which completed crosslinking / molding with the ratio of thinner, By forming the adhesive layer coated with the acrylic pressure-sensitive adhesive on the above, the present invention has been completed by focusing on the fact that the adhesive layer can be formed on the surface of the siloxane polymer compound in a simple and low-cost process.

That is, the present invention is a method of forming an adhesive layer on the surface of the molded article made of the siloxane polymer compound, the first step of diluting and applying the one-component sealant on the surface of the molded article, the applied dilution sealant layer is dried, crosslinked and cured A siloxane polymer compound comprising a second step of proceeding the process for 30 to 60 minutes, and a third step of completing crosslinking by forming an adhesive layer coated with an acrylic pressure-sensitive adhesive on the surface where the sealant is applied and crosslinking curing is performed. Provided is a method for forming an adhesive layer on a formed article surface. At the time of dilution of the sealant in the first step, it is preferable to dilute 200 to 1200 parts by weight of the thinner based on 100 parts by weight of the sealant, and the application of the diluted sealant may be performed using a brush or a spray. In addition, the adhesion of the acrylic pressure-sensitive adhesive layer in the third step, it is more preferable to apply an acrylic pressure-sensitive adhesive on a double-sided release paper to form a transfer adhesive layer by applying a cross-linking, and then attach it to the sealant layer surface by pressing. .

The present invention also provides a molded article made of the siloxane polymer compound, including an adhesive layer made of a one-component sealant dilution layer formed on the surface of the molded article made of the siloxane polymer compound, and an acrylic pressure-sensitive adhesive layer applied on the sealant dilution layer. . The sealant dilution layer preferably contains 200 to 1200 parts by weight of thinner based on 100 parts by weight of the sealant, and the thickness of the sealant dilution layer is preferably 5 to 50 microns.

Hereinafter, a method of forming an adhesive layer on the surface of a molding made of the siloxane polymer compound and a siloxane polymer compound in which the adhesive layer is formed will be described in detail with reference to the accompanying drawings showing an embodiment of the present invention. The following drawings and description do not limit the invention, and the invention may be appropriately modified and modified based on the details set forth in the claims.

1 and 2 are photographs showing the method of applying the diluted sealant on the surface of the molded product made of the siloxane polymer compound in the first step of the method for forming an adhesive layer on the surface of the molded product made of the siloxane polymer compound according to the present invention. The sealant used in the present invention is a one-component silicone sealant (at room temperature hardening type), and can be easily purchased and used from commercial products such as acetic acid type, non-acetic acid type, and mixed type of acetic acid type and non-acetic acid type. The thinner, which is a diluent diluting the sealant, is preferably mixed with the sealant at a ratio of 200 to 1200 parts by weight based on 100 parts by weight of the sealant. At this time, when mixing more than 1200 parts by weight, the coating thickness is too thin when applied to the surface of the molded article made of the siloxane polymer compound and is naturally dried due to the property, effective bonding when forming the acrylic pressure-sensitive adhesive layer in the third step according to the present invention This is not desirable because it becomes impossible. On the other hand, when the thinner is mixed in an amount of less than 200 parts by weight, the viscosity of the diluted sealant becomes high, so that the coating operation is not easy, and the thickness of the sealant layer for forming the acrylic pressure-sensitive adhesive layer in the third step according to the present invention is increased. It is not preferable because it becomes difficult to control. The sealant diluted in an appropriate ratio may be easily applied to the surface of the siloxane polymer compound which has been molded by using a brush as shown in FIG. 1 or spray method as shown in FIG. 2, and the diluted sealant is At the same time of application, it is naturally dried at room temperature. At this time, the coating thickness is preferably such that the thickness is 5 to 50 microns after drying.

On the other hand, the acrylic pressure-sensitive adhesive layer coated with an acrylic pressure-sensitive adhesive can be produced by applying a wet acrylic pressure-sensitive adhesive to the surface less releasing using a release paper coated on both sides, the degree of release of both sides. At this time, the acrylic pressure-sensitive adhesive to be applied can be used by commercially available various kinds of acrylic pressure-sensitive adhesives having various functions and adhesive strength, and if necessary, a foaming agent, a flame retardant, a thermal conductive material, an electrically conductive material, etc. Appropriate additives of may also be added. Since the adhesive strength of the finished product is dependent on the acrylic pressure-sensitive adhesive applied to the secondary, the weak adhesive strength when the weak adhesive is applied, the strong adhesive strength when the strong adhesive is applied, and the thicker the coating thickness of the acrylic adhesive, the stronger the adhesive strength. Application | coating of the acrylic adhesive of the said release paper can be performed by a general method, and an acrylic adhesive layer of fixed thickness is formed by vulcanization. As described above, the acrylic pressure-sensitive adhesive layer thus prepared may be wound and stored in a roll so that the sides of the mold release better touch each other, and may be used whenever necessary.

As mentioned above, after applying the diluted sealant on the molding made of the siloxane polymer compound according to the present invention, within about 30 to 60 minutes after the thinner is dried, the acrylic pressure-sensitive adhesive layer prepared in advance as described above It can be crosslinked with each other by applying on the diluted sealant and pressing them together with a roller at room temperature (see FIG. 4). As a result, the adhesive silicone rubber having the acrylic pressure-sensitive adhesive layer formed on the surface of the molded article made of the siloxane polymer compound may be cut into a suitable standard and then commercialized as shown in FIG. 5.

Example  One

1. Using a release paper coated on both sides with a different degree of release, and having a low release degree, an acrylic pressure-sensitive adhesive was applied to a thickness of 30 microns.

2. A solution diluted with thinner 4000 g to 400 g of a non-acetic acid one-component sealant (sealant-OK, manufactured by Shinwol Chemical Co., Ltd.) was applied to the surface of a foam sponge siloxane polymer compound using a spray coating method.

3. After drying the solvent of the diluent sealant layer applied to the surface of the siloxane polymer compound, crosslinking and curing were performed at room temperature for 30 minutes.

4. The thickness of the applied diluent sealant layer after drying was 10 microns.

5. The acrylic pressure-sensitive adhesive layer prepared as described above was applied to the diluent sealant layer and pressed together with a roller at room temperature to crosslink each other.

6. It was cut to 40 × 55mm size and commercialized.

Example  2

1. Using a release paper coated on both sides with a different degree of release, and having a low release degree, an acrylic pressure-sensitive adhesive was applied to a thickness of 50 microns.

2. A solution diluted with thinner 4800 g to 400 g of acetic acid sealant (SE 1886A / B, manufactured by Dow Corning Toray Silicone Co., Ltd.) was applied to the sheet-type siloxane polymer compound surface using a spray coating method.

3. After drying the solvent of the diluent sealant layer applied to the surface of the siloxane polymer compound, a crosslinking and curing process was performed at room temperature for 60 minutes.

4. The thickness of the applied diluent sealant layer after drying was 10 microns.

5. Crosslinked with each other in the same manner as in Example 1.

6. The product was cut to 40 × 55mm size.

Example  3

1. Using a release paper coated on both sides with a different degree of release, and having a low release degree, an acrylic pressure-sensitive adhesive was applied to a thickness of 70 microns.

2. A solution diluted with thinner 800 g to 400 g of a one-component sealant (K-104Gel, manufactured by Shinwol Chemical Co., Ltd.) was applied to the surface of the sheet-type siloxane polymer compound using a spray coating method.

3. After drying the solvent of the diluent sealant layer applied to the surface of the siloxane polymer compound, a crosslinking and curing process was performed at room temperature for 60 minutes.

4. The thickness of the applied diluent sealant layer after drying was 10 microns.

5. Crosslinked with each other in the same manner as in Example 1.

6. It was cut to 40 × 55mm size and commercialized.

Comparative example  One

1. Using a release paper coated on both sides with a different degree of release, and having a low release degree, an acrylic pressure-sensitive adhesive was applied to a thickness of 10 microns.

2. A solution of 200 g of one-component sealant (YE5818, manufactured by Toshiba Silicone Co., Ltd.) and 200 g of non-acetic acid sealant (Sealant-OK, manufactured by Shinwol Chemical Co., Ltd.) with thinner 5200 g was applied to the surface of the sheet-type siloxane polymer compound using a spray coating method. Applied.

3. After drying the solvent of the diluent sealant layer applied to the surface of the siloxane polymer compound, crosslinking and curing were performed at room temperature for 15 minutes.

4. The thickness of the applied diluent sealant layer after drying was 30 microns.

5. Crosslinked with each other in the same manner as in Example 1.

6. It was cut to 40 × 55mm size and commercialized.

Comparative example  2

1. Using a release paper coated on both sides with a different degree of release, and having a low release degree, an acrylic pressure-sensitive adhesive was applied to a thickness of 50 microns.

2. A solution diluted with 600 g of thinner to 400 g of non-acetic acid one-component sealant (sealant-OK, manufactured by Shinwol Chemical Co., Ltd.) was applied to the surface of a block-type siloxane polymer compound using a spray coating method.

3. After drying the solvent of the diluent sealant layer applied to the surface of the siloxane polymer compound, crosslinking and curing were performed at room temperature for 5 minutes.

4. The thickness of the applied diluent sealant layer after drying was 10 microns.

5. Crosslinked with each other in the same manner as in Example 1.

6. It was cut to 40 × 55mm size and commercialized.

Test Example  One

In order to compare the characteristics of the siloxane polymer compound with the adhesive layer prepared in Examples 1 and 2, respectively, according to the thickness of the pressure-sensitive adhesive, the adhesion test and the holding force by KS A 1107-2002 (adhesive tape and sheet test method) The test was carried out and the tensile strength (adhesive strength) test was performed according to ASTM D 1002. The test plate (adhesive) was used STS 304 of 1.5 to 2.0 mm thick and 125 × 50 mm in size, and kept uniformly using abrasive paper (No. 280) before each test. In addition, the test was conducted by the Korea Living Environment Testing Institute, the results are shown in Table 1 below.

Test Items unit Test result Example 1 Example 2  Adhesive force (180 ° peeling) Steady state   N / cm 0.81 2.14 After heat test (80 ± 2 ℃, 12hrs) 1.82 Support rupture After cold resistance test (-40 ± 2 ℃, 12hrs) 1.62 Support rupture After accelerated light resistance test (Sunshine Carbon Arc Lamp, 24hrs) 2.27 Support rupture   Holding force (deviated distance) Steady state   mm 0.1 or less 0.1 or less After heat test (80 ± 2 ℃, 12hrs) 0.1 or less 0.1 or less After cold resistance test (-40 ± 2 ℃, 12hrs) 0.1 or less 0.1 or less After accelerated light resistance test (Sunshine Carbon Arc Lamp, 24hrs) 0.1 or less 0.1 or less   Tensile strength adhesive strength Steady state N / mm ² 0.30 1.14 After heat test (80 ± 2 ℃, 12hrs) 0.52 1.80 After cold resistance test (-40 ± 2 ℃, 12hrs) 0.32 1.29 After accelerated light resistance test (Sunshine Carbon Arc Lamp, 24hrs) 0.36 1.48

As shown in Table 1, the siloxane polymer compound having an adhesive layer prepared in Example 1 and Example 2 according to the present invention was applied well even if the thickness of the applied acrylic adhesive was different, and the acrylic adhesive was a siloxane. It adhered well to the surface of the polymer compound.

Test Example  2

In order to measure the adhesive force over time of the siloxane polymer compound having an adhesive layer prepared in Example 2, the adhesion test was performed by KS A 1107-20002 (adhesive tape and sheet test method). The test was performed after peeling off the release paper on one side of the siloxane polymer compound having the adhesive layer prepared in Example 2 and exposing the adhesive surface in a standard chamber (20 ± 2 ° C., 65 ± 5% RH). Adhesion was measured respectively. The test plate used the same thing as Test Example 1 above. In addition, the test was performed by the Korea Living Environment Testing Institute, the results are shown in Table 2 below.

Test Items unit Test result       Adhesion (180 ° peeling) 1 day       N / cm 2.29 2 days 1.72 3 days 1.59 4 days 1.46 5 days 1.39 6 days 1.31 7 days 1.24 8th 1.19 9th 1.13 10 days 1.08 11th 0.99 12 days 0.93 13th 0.81 14 days 0.75 15th 0.65

As shown in Table 2, the adhesive layer formed in the adhesive layer prepared in Example 2 according to the present invention, the adhesive strength gradually decreased over time after exposure in the standard room, even after 15 days 0.65N / cm The adhesive force of was maintained.

Test Example  3

In order to measure the adhesive force according to the repeated adhesion of the siloxane polymer compound having the adhesive layer prepared in Example 3, the adhesion test was performed by KS A 1107-2002 (adhesive tape and sheet test method). The test is a step of adhering the siloxane polymer compound on which the adhesive layer is formed to the test plate and then left for 30 minutes, forcibly detaching and exposing the adhesive surface at room temperature for 30 minutes, and re-adhesive the adhesive surface to the test plate again. The procedure made was defined as one cycle. The test plate was an aluminum plate. In addition, the test was performed by the Korea Living Environment Testing Institute, the results are shown in Table 3 below.

Test Items unit Test result Before cycle 3 cycles 5 cycles 7 cycles 10 cycles Adhesion (180 ° peeling)  N / cm  2.54  1.62  2.52  1.68  2.33

As shown in Table 3, the siloxane polymer compound formed with the adhesive layer prepared in Example 3 according to the present invention maintained the initial adhesive strength to some extent even after repeating the cycle several times, and the dilution sealant layer regardless of the environment change. It had a constant binding force between the siloxane polymer and the acrylic pressure-sensitive adhesive applied.

Unlike the products of the above examples, the silonic acid polymer compound having the adhesive layers prepared in Comparative Examples 1 and 2 was weak enough to be able to perform the adhesion and retention test.

According to the present invention, the adhesive force can be artificially imparted simply to the siloxane polymer compound in which the molding is completed, without the need for a high heat / long time vulcanization step at room temperature and not in a vacuum environment. Since the method of the present invention is aimed at a finished product, no special manufacturing line is required, and therefore, the place is not restricted in the production of the intended product. In addition, unlike conventional methods, it is not required to purchase a high-priced silicon-only product such as a device for vacuum surface treatment or a silicone-specific adhesive agent or a primer, so that process time and material costs are saved, resulting in a cheaper final product. You can implement the price of.

Such a method of the present invention can be applied to all products based on the molded elastomer, such as general rubber, foam rubber, general silicone, sponge-type foam silicone, heat-dissipating silicone, and according to the selection of an acrylic pressure-sensitive adhesive and an additive It is also possible to diversify the use of the finished silicone adhesive rubber.

Claims (7)

A method of forming an adhesive layer on a surface of a molded article made of a siloxane polymer compound, A first step of diluting and applying a one-part sealant to the surface of the molding; A second step of performing a crosslinking and curing process for 30 to 60 minutes after the solvent of the applied dilution sealant layer is dried; And And a third step of forming an adhesive layer coated with an acrylic pressure-sensitive adhesive on the surface where the sealant is applied to crosslinking curing, thereby completing the crosslinking. A method of forming an adhesive layer on the surface of a molding made of a siloxane polymer compound. The method of claim 1, When diluting the sealant, the diluent includes 200 to 1200 parts by weight of thinner based on 100 parts by weight of the sealant. A method of forming an adhesive layer on the surface of a molding made of a siloxane polymer compound. The method of claim 1, Application of the diluted sealant is characterized in that using a brush or spray A method of forming an adhesive layer on the surface of a molding made of a siloxane polymer compound. The method of claim 1, The acrylic pressure-sensitive adhesive layer is formed by coating and crosslinking an acrylic pressure-sensitive adhesive on a double-sided release paper to form a transfer pressure-sensitive adhesive layer, and then pressing the acrylic pressure-sensitive adhesive on the sealant layer surface. A method of forming an adhesive layer on the surface of a molding made of a siloxane polymer compound. A one-component sealant dilution layer formed on the surface of the molding made of the siloxane polymer compound, and an acrylic adhesive layer applied on the sealant dilution layer A molded article made of the siloxane polymer compound, comprising an adhesive layer. The method of claim 5, The sealant dilution layer is characterized in that it comprises 200 to 1200 parts by weight of thinner based on 100 parts by weight of the sealant A molded article made of the siloxane polymer compound, comprising an adhesive layer. The method of claim 5, The thickness of the sealant dilution layer after drying is characterized in that 5 to 50 microns A molded article made of the siloxane polymer compound, comprising an adhesive layer.

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