KR102099263B1 - Silicon Resin Coated Fabric Having Slip Property, and Method for Manufacturing the Same - Google Patents

Abstract

The present invention relates to a method for manufacturing a slip type silicone resin coated fabric which coats a fiber-based fabric with a curable silicone composition in a transfer method in order to apply slip properties to the fabric and prevent physical properties of the coated film during a coating process, and coated fabric manufactured by the same method. The slip type silicone resin coated fabric according to the present invention can prevent attachment of foreign materials since a surface of the coated film is not sticky, prevent physical properties of the film from being reduced, and minimize damage of the fabric since high temperature heat is not applied to the fabric during the coating process.

Description

Silicone Resin Coated Fabric Having Slip Property, and Method for Manufacturing the Same

The present invention is a method for producing a slip-resistant silicone resin-coated fabric and a method for producing a slip-resistant silicone resin-coated fabric to prevent the physical properties of the coating film from being deteriorated in the coating process while coating the curable silicone composition on a textile material fabric in a transfer manner to impart slip properties to the fabric. It relates to a coated fabric.

Silicone resin refers to an organosilicon polymer compound having a siloxane bond as a skeleton and an organic group bonded to a silicon atom, and is excellent in heat resistance, cold resistance, weather resistance, electrical insulation, release property, water repellency, etc., but has mechanical strength, abrasion resistance, acid / alkali safety, It is a material that has weak characteristics in oil / solvent safety, gas permeability, and other characteristics from general organic polymers.

These silicone resins are widely used in various fields as they are widely used in various industries such as oil (liquid), resin (solid), and rubber, and silicone rubbers are prepared in a certain form in advance or cured by curing the curable silicone composition. It is generally produced as.

The curable silicone composition is generally classified as a silicone rubber, and is typically prepared by curing organopolysiloxane with an organic peroxide or organohydrogenpolysiloxane and a platinum-based catalyst, and can be cured in a short time by heating or the like. Therefore, it is widely used in various fields.

However, the silicone composition in the form of oil or resin may have slip properties on its own, but the silicone cured product obtained from silicone rubber or curable silicone composition may have surface slip properties due to tacky and non-slip properties. It is difficult to use in areas where surface durability such as scratch resistance is required, and low mechanical strength or abrasion resistance has been pointed out as a disadvantage when these silicone resins are coated on fabrics for production.

Particularly, in recent years, as the human harmfulness to fine dust, ultrafine dust, and yellow sand is known, interest in fabric materials that can protect the human body from them is increasing, and the curable silicone composition has a sticky property and non-slip properties, which makes it difficult to Since foreign matter such as dust easily adheres and the foreign matter stuck to it does not easily fall off, it has been a limiting factor in the use of not only clothing materials, but also materials such as mats and sofa fabrics that come in contact with skin.

Accordingly, attempts have been made to improve the surface non-slip property by blending an organic or inorganic lubricant with the curable silicone composition, but if an appropriate amount of lubricant is used, sufficient slip properties cannot be achieved, and a lubricant is used to provide sufficient slip properties. When used in large quantities, a problem occurs in that the thermal and mechanical properties of the silicone resin product are deteriorated.

In order to improve such a problem, Korean Patent Publication No. 2001-0069854 proposed a method for mixing silicone and drying oil having an iodine value of 150 or more and curing to impart excellent slip properties without deteriorating physical properties.

Dry oils with iodine of 150 or more, such as linseed oil, perilla oil, tung oil, etc., have double bonds in the oil reacted and cured with oxygen in the air to form their own coating film on the silicon surface, and the coating film improves the slip property of the silicon surface. It will work.

However, since the coating film has improved slip properties, it is formed by oxidation of oil, so water resistance, solvent resistance, abrasion resistance, and mechanical strength are low, and thus the coating film is easily damaged depending on the use environment, and thus its application is very limited.

In addition, Korean Patent Publication No. 2016-0122309 proposed a method of forming a coating film by applying a resin composition obtained by mixing water-dispersed polyurethane resin and fumed silica on top of a base fabric, and hydrophilic silica particles of the coating film By forming a moisture-permeable tunnel in the thickness direction, it provides moisture-permeable performance, provides waterproof performance by a non-porous coating film, reduces stickiness on the surface of the coated film by silica particles, and is made of organic solvents by using water-dispersible polyurethane resin. It provides an effect that does not cause environmental problems.

However, the water-dispersible polyurethane has insufficient adhesion and mechanical properties, and the coating film is formed of a non-porous film, so it lacks elasticity. As the water evaporates by heat during drying, the water-dispersible polyurethane moves to the fabric surface, resulting in a difference in physical properties between the surface and the interior. It may cause appearance defects such as deformation.

The present invention is to solve the above problems, while providing a slip resistance to the silicone resin coating film coated on the surface of the fabric, the manufacturing method of the slip silicone resin coated fabric to prevent the physical properties of the coated coating film from deteriorating and manufactured by this method It is to provide a coated fabric.

In order to solve the above problems, the present invention is to prepare a primary silicone resin by mixing 10 to 30 parts by weight of calcium carbonate powder to 100 parts by weight of silicone resin; Curing the primary silicone resin by applying the primary silicone resin on release paper at 50-150 g / m 2 and heating at 160-180 ° C. for 1-3 minutes; Preparing a secondary silicone resin containing 1 to 5% by weight of expandable microcapsules containing gas inside the outer wall; Coating the secondary silicone resin at 100 to 300 g / m 2 on the cured primary silicone resin; Transferring the primary and secondary silicone resins to the fabric by combining the cotton coated with the secondary silicone resin with the fiber fabric and heating and pressing at 130 to 150 ° C. for 3 to 5 minutes; And peeling the release paper; provides a method for producing a slip-resistant silicone resin coated fabric comprising a.

At this time, it is preferable to add 0.5 to 5.0 parts by weight of the cream to 100 parts by weight of the primary silicone resin.

In addition, after the step of peeling off the release paper, it is preferable that a process of post-heating the coated fabric at 120 to 140 ° C. for 5 to 8 minutes is added.

In addition, the microcapsules preferably contain nitrogen inside the outer wall made of silicone resin and have an average particle diameter of 5 to 10 μm.

In addition, the step of transferring is preferably performed by heating and pressing for 2-3 minutes and then depressurizing while heating for 0.5 to 1.0 minutes, followed by heating and pressing for 0.5 to 1.0 minutes.

In addition, the present invention provides a slip-resistant silicone resin coated fabric produced by the above method.

The slippery silicone resin coated fabric according to the present invention can prevent the foreign matter from sticking because the surface of the coated coating film is not sticky, the physical properties of the coated coating film are not deteriorated, and high temperature heat is not applied to the fabric during the coating process. Minimize the damage.

In addition, the cream suppresses the generation of air bubbles to improve the surface properties, improve the slip properties, and the microcapsules give the elasticity and bulkiness, so that the manufactured coated fabric is not only used for contact with the skin, such as mats, sofas, clothing, curtains, covers, It can be widely used in various fields such as artificial leather.

The present invention is coated with a primary silicone resin on release paper, dried and cured, coated with a secondary silicone resin thereon, and then heated / pressurized and transferred to a textile material fabric to produce a slippery silicone resin coated fabric. To prepare.

Silicone resin is a thermosetting synthetic resin made by polymerization of an organic derivative of silicone, and has a molecular structure in the form of a siloxane bond (Si-O bond) in which silicon and oxygen alternate, and a curing agent in the main ingredient of such a curable silicone resin composition (hardener) can be added, and a curing coagent may be added thereto, and viscosity may be adjusted by adding a diluent in consideration of coating processing characteristics.

The curing of the silicone resin is crosslinked and cured by hydrolysis and condensation reaction in the presence of moisture. Additive curing property that is crosslinked and cured according to the addition reaction of a siloxane containing Si-H to an unsaturated group in the presence of a catalyst such as a condensation-curable silicone resin, platinum catalyst, etc. It can be classified into silicone resins, radical-type curable silicone resins that are crosslinked by recombination and heterogeneous reaction of generated radicals, and the like.

Therefore, the curing agent or curing aid means a curing catalyst, a curing accelerator, a condensing agent, a radical initiator, a crosslinking agent, and the like, and the type and mixing ratio of the curing agent, the curing aid, and the diluent are generally well-known technologies and can be selected according to needs. Detailed description or limitation will be omitted.

In addition, silicone solvents such as benzene, toluene, nucleic acid, ethylene dichloride, trichloroethylene, dimethyl ether, isopropyl alcohol, and methyl ethyl ketone can be mixed depending on the product characteristics to improve processability, and the mixing amount is also appropriate if necessary. Can be used.

Since the primary silicone resin is transferred to the fabric and forms the fabric surface, calcium carbonate powder is mixed with a silicone resin, preferably a thermosetting silicone resin, to impart slip properties without deteriorating the physical properties of the coated fabric surface. .

Calcium carbonate is non-toxic to the human body and has antibacterial and antibacterial properties against various harmful bacteria and microorganisms. It has excellent hydrophilicity, low oil absorption, and homogeneity as well as a function as an extender and reinforcement agent with excellent hardness, heat insulation, moisture absorption, and hiding. It has excellent properties.

This calcium carbonate has a property of smoothing the surface of the coated coating film, thereby reducing the sticky properties of the cured silicone, preventing foreign matter from sticking, and the calcium carbonate powder acts as a filler to improve the hardness of the coated coating film, thereby improving wear resistance and The effect of improving scratch resistance can also be obtained.

The smaller the particle size of the calcium carbonate powder is, the better the dispersibility in the silicone resin is, so the calcium carbonate particles are preferably nano-sized. Mixing 10 to 30 parts by weight of calcium carbonate with 100 parts by weight of the silicone resin and It is suitable for improving hardness.

The primary silicone resin may be applied to release paper, dried and cured by applying heat, and heated and dried for 1 to 3 minutes at a temperature of 50 to 150 g / m2 and 160 to 180 ° C.

However, when the primary silicone resin is cured, fine bubbles are generated, which may deteriorate the slip properties and physical properties of the coating film, and an antifoaming agent may be added to solve this, but the antifoaming agent breaks down the chemical balance of the silicone resin to produce carbonic acid. It can inhibit the dispersibility of calcium powder and interfere with curing, thereby adversely affecting the properties of the coating film.

In order to solve this problem, it is preferable to add a cream to the primary silicone resin, and the cream is a component of milk fat separated from milk and having a small specific gravity, so that the function of suppressing the generation of bubbles during curing of the primary silicone resin is provided. It also plays a role in increasing the slipping effect of calcium carbonate due to the nature of the cream.

It is preferable to add 0.5 to 5.0 parts by weight of the cream based on 100 parts by weight of the silicone resin, and the cream is first mixed with a silicone solvent and then added to the silicone resin so that the cream in the silicone resin is uniformly dispersed. More preferred.

Next, apply a general silicone resin, preferably a thermosetting silicone resin (secondary silicone resin) on the primary silicone resin coated coating film at 100 to 300 g / m 2, then apply the secondary silicone resin coating surface to the fiber material fabric and 130 Primary and secondary silicone resins are transferred to the fabric by heating and pressing for 3 to 5 minutes at a temperature of ~ 150 ° C.

As the fiber material fabric, there is no restriction of natural fibers and synthetic fibers such as cotton, hemp, nylon, polyester, polyurethane, and can be applied to various products such as artificial leather.

Thereafter, the release paper is peeled to prepare a slip silicone resin coated fabric in which a secondary silicone resin and a primary silicone resin are laminated on the fabric, and the silicone resin has a sticky characteristic, but the present invention is modified to slip on the surface of the coated fabric. Since the secondary silicone resin forms a coating film, it is not sticky and foreign matter does not easily adhere.

After the release paper is peeled off, the coated fabric may be post-heated at a temperature of 120 to 140 ° C for 5 to 8 minutes, and after heat treatment at a relatively low temperature for a long time compared to the previous heat treatment, the fabric, secondary silicone resin coating and primary silicone The resin coating film can be further bonded and the stress that may remain in the coated fabric can be relieved.

If the primary and secondary silicone resins are applied directly to the fabric material and cured, there is a risk of thermal damage depending on the type of fabric, but after the primary silicone resin is thermally cured at a high temperature as described above, the primary and secondary silicone resins Is transferred to the fabric at a medium temperature and post-heated at a low temperature, so that high-temperature heat is not applied to the fabric, thereby minimizing damage to the fabric and increasing the binding power of the coating film.

An expandable microcapsule may be added to the secondary silicone resin to impart elasticity and bulkiness to the slippery silicone resin coated fabric of the present invention.

The microcapsule is a thermally expandable polymer microparticle containing gas in the core of the outer shell, and when the heat is expanded, the size of the microcapsule increases as the gas expands, and is expanded by heat during transfer and post-heat treatment. By forming voids inside the secondary silicone resin coated coating film, it gives elasticity and bulkiness to the coated fabric.

The gas is preferably nitrogen that is safe and harmless to the human body in the working process, and the material forming the outer wall is preferably the same as the secondary silicone resin to increase compatibility with the secondary silicone resin. The invention is not limited to this, and can be used as long as it is a human-friendly material having thermoplasticity and elasticity.

The microcapsules may have an average particle diameter of 5 to 10 μm, and may contain 1 to 5% by weight of the secondary silicone resin, and the average particle diameter is limited to the above range in terms of preventing dispersibility and physical property degradation in the secondary silicone resin. Preferably, the content range is appropriate in the above range in view of imparting elasticity and bulkiness and preventing deterioration of physical properties.

However, when the release paper coated with the primary and secondary silicone resins is incorporated into the fabric and transferred by heating and pressing in the direction of the fabric from the release paper, heat is sequentially transferred through release paper, primary silicone resin, secondary silicone resin and fabric by conduction. As it is delivered, the primary silicone resin side microcapsule expands first, then the fabric side microcapsule expands later, and since the secondary silicone resin is pressurized, the primary silicone resin side microcapsules expand sufficiently, but the fabric side microcapsules expand. If not, or when the expanded / non-expanded state is mixed, the secondary silicone resin may be cured, resulting in a case where the expansion size of the microcapsules is not uniform throughout, and as a result, the shape of the secondary silicone resin coating coating is distorted and the shape is deformed. There is a problem that the physical properties of the coated fabric is lowered.

In order to prevent such a problem, it is preferable to release the pressure for a while during the transfer and then pressurize again, for example, heating and pressing for 2 to 3 minutes (step 1) and depressurization while heating for 0.5 to 1.0 minute (step 2). It can continue to be heated and pressed for 0.5 to 1.0 minutes (step 3). In step 1, the microcapsules on the primary silicone resin side expand, and in step 2, the heat is continuously transferred from the primary silicone resin side toward the fabric to release the pressure. Therefore, the microcapsules on the fabric side expand and the secondary silicone resin is completely cured in step 3 to firmly bond with the fabric.

As a result, all of the microcapsules expand sufficiently in the secondary silicone resin to make the expansion size uniform throughout, and the stress that may occur due to the difference in expansion order is resolved during the post-heat treatment process, so the physical properties of the coated coating film due to the addition of the microcapsules This deteriorating problem can be prevented.

Hereinafter, the present invention will be described in more detail based on the following examples, comparative examples and test examples.

However, the following examples are only for exemplifying the present invention, and the present invention is not limited by the following examples, and can be changed to other equivalents of substitution and equivalent within the scope not departing from the technical spirit of the present invention. It will be apparent to those skilled in the art to which the present invention pertains.

<Example 1>

A primary silicone resin was prepared by mixing 1 kg of a thermosetting silicone resin with 1 kg of isopropyl alcohol and 200 g of calcium carbonate powder, and then applying this to a release paper coated with polypropylene on paper in an amount of 100 g / m 2 and at 170 ° C. Cured by heating to temperature for 2 minutes.

A second silicone resin is prepared by mixing 1 kg of a thermosetting silicone resin with 1 kg of isopropyl alcohol, and then coating the cured primary silicone resin in an amount of 200 g / m 2 and then applying the second silicone resin. And the fabric fabric woven from polyurethane fiber, and passed between a heating roller and a rubber roller (so that the release paper comes into contact with the heating roller and the textile fabric comes into contact with the rubber roller) by heating and pressing at a temperature of 140 ° C. for 4 minutes 1 After transferring the secondary and secondary silicone resin to the fabric, the release paper was peeled to prepare a silicone resin coated fabric.

<Example 2>

A silicone resin coated fabric was prepared in the same manner as in Example 1, except that 30 g of the cream was added to the primary silicone resin of Example 1, mixed uniformly, and then applied to release paper.

<Example 3>

A silicone resin coated fabric was manufactured in the same manner as in Example 1, except that the coated fabric prepared in Example 1 was heat-treated at a temperature of 130 ° C. for 7 minutes.

<Example 4>

Except that 40 g of microcapsules containing nitrogen and having an average particle diameter of 8 µm inside the outer wall of the silicone resin were added to the secondary silicone resin of Example 1 and mixed uniformly, and then coated on the cured primary silicone resin. Then, a silicone resin coated fabric was prepared in the same manner as in Example 1.

<Example 5>

The transfer process of the above Example 4 is a release paper, a primary silicone resin, a secondary silicone resin, and three pairs of heating rollers and rubber rollers are installed along the traveling direction of the fabric fabric composite, and then heated at a temperature of 145 ° C. for 2 minutes. A silicone resin-coated fabric was prepared in the same manner as in Example 1, except that it was carried out by heating and pressing at a temperature of 145 ° C. for 1 minute at a temperature of 145 ° C. under pressure → depressurization. Did.

<Comparative Example>

In Example 1, silicone was applied in the same manner as in Example 1, except that the primary silicone resin was not applied to the release paper and the secondary silicone resin was applied to the release paper in an amount of 300 g / m 2 and transferred to the fabric. A resin coated fabric was prepared.

<Test Example 1> Measurement of physical properties of coated fabric

Each of the coated fabric samples prepared in Examples 1 to 5 and Comparative Examples was taken at 3 points, and the compression rate, recovery rate, abrasion resistance, slip property, and scratch generation were measured, and the average values are shown in Table 1 below.

Compression rate measurement was performed by applying a load of 900 gf / cm 2 to a circular indenter, maintaining it for 30 seconds, and then removing the load and measuring the maximum thickness (T1) of the artificial leather at a time point after 30 seconds.

After applying the load again for 30 seconds, the minimum thickness (T2) was measured, and after removing the load, the thickness of the artificial leather (T3) was measured 30 seconds after the load was removed, and the compressibility and recovery rate were calculated according to the following equation.

* Compression rate (%) = (T1-T2) / T1 × 100

* Recovery rate (%) = (T3-T2) / (T1-T2) × 100

The abrasion resistance was determined by the color abrasion method (Martindale method), the coated fabric sample was pressed with a load of 12 시킨, rotated 35000 cycles, and the color discoloration of the friction area was determined by gray scale (SRAY). It was measured in accordance with, and the degree of scratching was artificially generated and the degree was visually observed.

Property measurement result Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example Compression rate (%) 14.3 14.2 14.5 16.1 16.9 14.0 Restoration rate (%) 97.5 97.1 97.4 99.0 99.5 97.3 Abrasion resistance (grade) 4.2 4.5 4.3 4.0 4.1 3.5 Slip property ^{Note 1 )} 3.5 4.0 3.4 3.3 3.4 2.6 Scratch occurs ^{Note 2 )} 1.6 1.0 1.3 1.5 1.5 3.7 Note 1) 5: Very good, 4: Good, 3: Normal, 2: Bad, 1: Very bad
Note 2) 5: Very many, 4: Many, 3: Moderate, 2: Little, 1: Very little

Referring to Table 1, the compression ratio and the recovery rate are significantly larger in Examples 4 and 5 in which the microcapsules are mixed, and in Example 5 in which the pressure is released in the middle of the transfer process, the microcapsules are secondary silicon. It can be seen that when mixed with the resin coating film, the elasticity of the coated fabric is increased, and the elasticity is improved when the pressure is adjusted during the transfer process.

The wear resistance was the largest in Example 2 in which the cream was added to the primary silicone resin, and the comparative example in which the coating film did not contain calcium carbonate was the lowest. By further improving it, it can be seen that the durability of the silicone resin coated fabric is improved.

Slip resistance shows a similar tendency to abrasion resistance, and the degree of scratch occurrence tends to be opposite to slip property. Calcium carbonate and cream are judged to decrease the occurrence of scratches by increasing the slip resistance.

Therefore, it can be seen that in the production of the silicone resin coated fabric, the inclusion of calcium carbonate and cream components in the surface layer of the coated coating film improves elasticity and durability, thereby improving the quality of the coated fabric.

<Test Example> Measurement of fine dust adhesion

After exposing the coated fabrics of Examples and Comparative Examples to air containing fine dust for 10 minutes, the degree to which the fine dust adhered to the fabric was measured, and the fine dust adhesion rate was based on the weight of the fine dust attached to the comparative example. The relative weight of the fine dust attached to the fabric of the Example is calculated as a percentage and is shown in Table 2 below.

Measurement result of fine dust adhesion rate Example 1 Example 2 Example 3 Example 4 Example 5 Fine dust adhesion rate (%) 45.7 38.6 46.3 47.1 46.6

As shown in Table 2, when the adhesion rate of the fine dust of Examples 1 to 5 was measured to be less than 100%, and the calcium carbonate was included in the surface layer of the coated coating film, it could be confirmed that the fine dust did not adhere well to the surface of the coated fabric. , Among the examples, it can be seen that the adhesion rate of the fine dust in Example 2 was the lowest, so that the addition of the cream component reduced the adhesion rate of the fine dust.

These results are estimated to be closely related to the slip properties of Test Example 1, and the comparative example with the lowest fine dust adhesion rate of Example 2 with the highest slip property and the lowest slip property has a higher fine dust adhesion rate than the Example. From the results, it is judged that the larger the slip property, the fine dust does not adhere well to the surface of the coated fabric, and the attached fine dust easily falls from the fabric.

Therefore, in order to prevent the fine dust from adhering to the fabric by imparting slip properties to the silicone resin coated fabric and to prevent the physical properties of the coated fabric from deteriorating, coating the silicone resin on the fabric with a transfer method while coating the surface of the coated film It can be seen that it is preferable to include the calcium carbonate component, and it is more preferable to add the cream component.

Claims (7)

Preparing primary silicone resin by mixing 10-30 parts by weight of calcium carbonate powder with 100 parts by weight of silicone resin;
Curing the primary silicone resin by applying the primary silicone resin on release paper at 50-150 g / m 2 and heating at 160-180 ° C. for 1-3 minutes;
Preparing a secondary silicone resin containing 1 to 5% by weight of expandable microcapsules containing gas inside the outer wall;
Coating the secondary silicone resin at 100 to 300 g / m 2 on the cured primary silicone resin;
Transferring the primary and secondary silicone resins to the fabric by combining the cotton coated with the secondary silicone resin with the fiber fabric and heating and pressing at 130 to 150 ° C. for 3 to 5 minutes; And
Method of manufacturing a slip-type silicone resin coated fabric comprising; peeling off the release paper. The method according to claim 1,
A method of manufacturing a slippery silicone resin coated fabric, characterized in that 0.5 to 5.0 parts by weight of cream is added to 100 parts by weight of the primary silicone resin. The method according to claim 1,
After the step of peeling off the release paper, a method of manufacturing a slippery silicone resin coated fabric, characterized in that a process of post-heat treatment of the coated fabric at 120 to 140 ° C. for 5 to 8 minutes is added. delete The method according to claim 1,
The microcapsule is a method for producing a slip-resistant silicone resin coated fabric, characterized in that the inside of the outer wall made of silicone resin contains nitrogen and has an average particle diameter of 5 to 10 μm. The method according to claim 1,
The transferring step is a method of manufacturing a slip-resistant silicone resin coated fabric, characterized in that it is performed by heating and pressing for 2-3 minutes, releasing pressure while heating for 0.5 to 1.0 minutes, and then heating and pressing for 0.5 to 1.0 minutes. A slippery silicone resin coated fabric produced by the method of claim 1, 2, 3, 5 or 6.