KR20170026073A - Coating Product and Method Manufacturing Thereof - Google Patents

Abstract

The present invention relates to a coating product and a manufacturing method thereof. The present invention comprises the following steps: forming a hard coating layer, by coating a coating material which is an ingredient for hard coating, inside an injection mold, wherein a product having a predetermined shape is manufactured; integrating a certain ingredient with a material for forming the hard coating layer by injecting the certain ingredient into the injection mold and, at the same time, forming the hard coating layer on one side or both sides of the product having a predetermined shape by injection molding. Furthermore, the coated product can be shaped by various molding processes even after hardening the coating layer.

Description

COATING PRODUCT AND METHOD FOR MANUFACTURING THE SAME

The present invention relates to a coating product and a method of manufacturing the same, and more particularly, to a coating product and a method of manufacturing the same, which are coated with a coating composition containing a silsesquioxane polymer on one side or both sides of a product to prevent cracks, peeling, Coating products and methods of manufacture.

In recent years, exterior materials for household appliances such as refrigerators and washing machines are rapidly replacing metal materials such as ABS with plastics.

A plastic, glass, or metal product forms a hard coating layer on the surface thereof, so that physical properties such as impact resistance and scratch resistance are excellent.

After the injection molding of the product, a separate coating is applied to impart the functionality.

However, when hard coating is performed on a curved shape or a shape having a bending angle by unevenness after product injection molding, there is a disadvantage that roll coating is not possible or coating property is poor in flow coating.

Further, in the case of a molded article having a curved surface or concavo-convex shape, when a hard plate is coated on the original plate, there is a problem that cracks occur in a bent portion at the time of molding.

In order to solve these problems, when the product is injected after coating the molded product, hot melt material such as PC material is molded at about 200. When a general coating material is used, it is difficult to apply to the injection process .

In order to solve such problems, the present invention relates to a coating product for coating a coating composition containing a silsesquioxane polymer on one side or both sides of a product to prevent problems such as cracking and peeling of a curved part during molding, And a manufacturing method thereof.

According to another aspect of the present invention, there is provided a method of manufacturing a coated product,

Forming a coating layer by coating a coating material inside an injection mold having a predetermined shape; And

Injecting an injection material into the injection mold and integrating the injection material with the material forming the coating layer and injecting the injection material to form the coating layer on one side or both sides of the product.

According to an aspect of the present invention, there is provided a method of manufacturing a coated product, comprising: coating a coating material on one or both sides of a substrate to form a coating layer on the substrate; And

And forming the substrate on which the coating layer is formed through a rolling process.

Further, the method may further include the step of embodying the shape by inserting the substrate having the coating layer formed thereon into a stamp device having a shape formed on one surface thereof, and pressing the substrate.

According to an aspect of the present invention, there is provided a method of manufacturing a coated product, comprising: coating a coating material on one or both sides of a substrate to form a coating layer on the substrate; And

And embossing the substrate by inserting the substrate having the coating layer formed thereon into a stamp device having a shape formed on one surface thereof, and pressing the substrate.

A method of manufacturing a coating product according to an aspect of the present invention includes: coating a coating material on an inner surface of a stamp device having a certain shape to form a coating layer; And

And pressing the substrate on the stamp device to form a shape on the substrate while coating the coating material.

A method of manufacturing a coating product according to an aspect of the present invention includes: coating a coating material on one side or both sides of a substrate to form a coating layer on the substrate; And

And passing the substrate having the coating layer formed therebetween through a roll having a predetermined shape to form a shape on the substrate on which the coating layer is formed.

A method of manufacturing a coating product according to an aspect of the present invention includes: coating a coating material on one side or both sides of a substrate to form a coating layer on the substrate; And

The coating layer of the substrate on which the coating layer is formed is hardened, and then inserted into a stamp device having a shape formed on one surface thereof, and press-processed to realize a shape.

A method of manufacturing a coating product according to an aspect of the present invention includes: coating a coating material on one side or both sides of a substrate to form a coating layer on the substrate; And

The coating layer of the substrate on which the coating layer is formed is hardened, and then inserted into a stamp device having a shape formed on one surface thereof, and press-processed to realize a shape.

The material forming the coating layer is formed of a coating composition comprising a silsesquioxane polymer represented by any one of the following general formulas (1) to (9).

     [Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 1 to 9,

A is

And B is

And D is

And E is

Lt;

Y are each independently O, NR ²¹ or _{[(SiO 3/2 R)} 4 + 2 n O] , and at least one of _{[(SiO 3/2 R) 4 +} 2n O],

X is each independently R ²² or _{[(SiO 3/2 R)} 4 + 2 n R] , and at least one of _{[(SiO 3/2 R) 4 +} 2n R],

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently hydrogen; heavy hydrogen; halogen; An amine group; An epoxy group; Cyclohexyl epoxy group; (Meth) acrylic group; A diazo group; Isocyanate group; A nitrile group; A nitro group; A phenyl group; A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a halogen atom, an amino group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group; A C ₂ to C ₄₀ alkenyl group; A C ₁ to C ₄₀ alkoxy group; A C ₃ to C ₄₀ cycloalkyl group; A C ₃ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₃ to C ₄₀ heteroaryl group; A C ₃ to C ₄₀ aralkyl group; A C ₃ to C ₄₀ aryloxy group; Or a C ₃ to C ₄₀ arylcyclic group which is specifically substituted by a substituent selected from the group consisting of deuterium, halogen, an amine group, a (meth) acryl group, a silyl group, an isocyanate group, a nitrile group, a nitro group, a phenyl group, a cyclohexyl- It is included, and C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, an amine group, an epoxy group, cyclohexyl epoxy groups, (meth) acrylic group, between olgi, a phenyl group or isocyanate,

a and d are each independently an integer of 1 to 100,000, specifically a is 3 to 1000, d is 1 to 500, more specifically a is 5 to 300, d is 2 to 100,

b is independently an integer of 1 to 500,

e is independently 1 or 2, specifically 1,

n is independently an integer of 1 to 20, specifically 3 to 10;

The coating product according to the present invention is coated on one surface or both surfaces of the product with a coating composition comprising a silsesquioxane polymer represented by any one of the above Chemical Formulas 1 to 9.

According to the above-described construction, the present invention has an effect of preventing the occurrence of cracks and peeling of a bent portion in a molding process by coating a coating composition containing a silsesquioxane polymer on one surface or both surfaces of a product.

The present invention has the effect of improving coating methods for existing coating products to obtain coating quality superior to spray and dipping coatings.

The present invention relates to a process for coating a surface of a product with a coating composition comprising a silsesquioxane polymer to prevent cracking, pinhole phenomenon and shine, thereby reducing process cost, improving stain resistance and heat resistance, Moisture shielding property, life scratch resistance, less birefringence, less image distortion due to coating, and excellent thermal properties, so that the coating composition can be simultaneously applied to an injection or molding process.

1 is a view illustrating a method of manufacturing a coated product using a silsesquioxane polymer according to a first embodiment of the present invention.
FIG. 2 is a view illustrating a method for producing a coated product using a silsesquioxane polymer according to a second embodiment of the present invention.
3 is a view illustrating a method of manufacturing a coated product using a silsesquioxane polymer according to a third embodiment of the present invention.
4 is a view illustrating a method of manufacturing a coated product using a silsesquioxane polymer according to a fourth embodiment of the present invention.
5 is a view illustrating a method of manufacturing a coated product using a silsesquioxane polymer according to a fifth embodiment of the present invention.
6 is a view illustrating a method of manufacturing a coated product using a silsesquioxane polymer according to a sixth embodiment of the present invention.
Fig. 7 is a photographic view of a molded product obtained through the fifth embodiment of the present invention. Fig.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.

1 is a view illustrating a method of manufacturing a coated product using a silsesquioxane polymer according to a first embodiment of the present invention.

The method for manufacturing a coated product using the silsesquioxane polymer according to the first embodiment of the present invention includes the steps of forming a coating layer 100 by applying a coating material 110 to one surface of a base film 120, Forming a coating layer 100 in the mold 200 by injecting a hot melt material 130 as an injection material into the injection mold 200 and injecting the injection molding; (100), which is an injection-molded product integrated with the coating material (100).

Here, the coating layer 100 of the present invention is not limited to the coating film. However, the present invention is not limited thereto, and the coating material 110, which is a coating material, may be applied to the injection mold 200 without using the base film 120 May be coated on one side or on both sides.

The coated products 100 and 130 may have various shapes such as a bending angle of the concave and convex portions of the injection mold 200.

Typical coating materials have a disadvantage in that injection molding is difficult because of the low thermal properties of the hot melt material 130, for example in the case of PC materials, at 200.

Since the coating material 110 of the present invention is composed of a coating composition containing a silsesquioxane polymer and has a heat resistance of about 400, it can be simultaneously applied to an injection process.

The step of forming the coating layer 100 includes the steps of preparing the coating material 110 formed of the coating composition described above and applying the coating material 110 to the base material film 120 as a substrate.

The method of applying the coating material 110 on the base film 120 includes various methods such as a bar coating method, a knife coating method, a gravure coating method, a micro gravure coating method and a slot die coating method.

The substrate film 120 as a substrate is not particularly limited and specifically includes polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and the like.

The coating layer 100 is formed by applying the coating material 110 on the base film 120 using the coating method described above and then curing the coating layer by ultraviolet rays irradiated by the ultraviolet curing unit.

Ultraviolet rays are irradiated using ultraviolet lamps such as a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a microwave type electrodeless lamp. The wavelength range of UV required for curing the coating layer is not limited. 320-400 nm), the curing light amount required is 10 mJ / m ² or more.

The coating material 110 of the present invention exemplifies a coating composition comprising a silsesquioxane polymer. However, the coating material 110 is not limited to a silsesquioxane polymer alone, but may be a fluorine-based, acrylate-based, epoxy-based, urethane- Organic copolymers. ≪ / RTI >

The silsesquioxane polymer includes a cage-type silsesquioxane polymer having a cage structure or a ladder-type silsesquioxane polymer, and a mixed type of a cage-type silsesquioxane polymer and a ladder-type silsesquioxane polymer is also possible .

The silsesquioxane polymer of the present invention is a mixture of a cage type and a ladder type and is represented by any one of the following formulas (1) to (9).

The injection mold 200 may be formed into a convex shape and a concave shape to form a product having a bending angle.

The hot melt material 130 is injected into the space between the injection molds 200. Here, the hot-melt material 130 includes PC, PET, acrylic resin, and the like, but not limited thereto, and includes hot-melt polymer materials or hot-melt composite materials.

The specific material to be injected into the injection mold 200 may be not only the hot melt material 130 described in the present invention but also a solid phase plate including solid metal, solid plastic, and solid composite material.

The hot melt material 130 is integrated with the silsesquioxane polymer of the coating layer 100 so as not to separate the interface when injected into the injection mold 200.

When the injection mold 200 is removed and cooled, the coated products 100 and 130 having the bent angle formed with the coating layer 100, which is an injection molded product integrated with the coating layer 100, are manufactured.

The silsesquioxane polymer of the coating layer 100 has a releasing property, which helps to separate in the injection mold 200. Of course, the injection mold 200 may be coated with a release agent on the surface.

The coating layer 100 integrated with the hot melt material 130 is removed by cooling the injection mold 200 so that the coated product 100 or 130 having a desired shape such as a bending angle formed on both sides of the coating layer 100 is manufactured do.

FIG. 2 is a view illustrating a method for producing a coated product using a silsesquioxane polymer according to a second embodiment of the present invention. FIG. 3 is a schematic view illustrating a coating product using a silsesquioxane polymer according to a third embodiment of the present invention 4 is a view illustrating a method for producing a coated product using the silsesquioxane polymer according to the fourth embodiment of the present invention.

2, a method of manufacturing a coated product using a silsesquioxane polymer according to a second embodiment of the present invention includes coating a coating material 110 on one side or both sides of a substrate 140 And the substrates 110 and 140 are manufactured through a post-rolling process (rolling process). The rolling process is a method in which a metal material having a high temperature or a normal temperature is passed through two rotating rolls 150 and processed into a plate, rod, or tube shape. At this time, it is possible to obtain the desired result by selectively using the process of rolling the uncured coating product first or the hardened coating product.

3, a method of manufacturing a coated product using a silsesquioxane polymer according to a third embodiment of the present invention includes coating a coating material 110 on one side or both sides of a substrate 140 The substrate 140 coated with the coating material 110 is inserted into the stamp devices 152 and 154 having a shape formed on one surface thereof, and stamped and pressed to form a shape. At this time, a desired product can be obtained by selectively using a process of forming a hardened coating product first, followed by hardening a hardened coating product, or molding a hardened coating product.

As shown in FIG. 4, the method for producing a coated product using the silsesquioxane polymer according to the fourth embodiment of the present invention includes the steps of forming a hard coating material on the inner surface of the stamp devices 152 and 154, The coating material 110 is coated while the substrate 140 is formed into a shape by stamping and pressing the substrate 140 between the stamp devices 152 and 154 after coating the coating material 110 .

The fourth embodiment exemplifies coating the coating material 110 on the stamp devices 152 and 154 but is not limited thereto and may be applied to one surface of the base film 120 on the inner surface of the stamp devices 152 and 154 The material 110 may be applied to attach the coating layer 100.

FIG. 5 is a view illustrating a method for producing a coated product using the silsesquioxane polymer according to a fifth embodiment of the present invention. FIG. 6 is a graph showing a coating product using a silsesquioxane polymer according to a sixth embodiment of the present invention Fig.

5, a method of manufacturing a coated product using a silsesquioxane polymer according to a fifth embodiment of the present invention includes coating a coating material 110 on one side or both sides of a substrate 140 And the substrates 110 and 140 are manufactured through a post-rolling process (rolling process). A coating material 110 as a coating material is coated on one side or both sides of the substrate 140 passing between the two rolls 150 and then inserted into stamp devices 152 and 154 having a shape formed on one side thereof, To form a shape. At this time, a desired product can be obtained by selectively using a process of forming a hardened coating product first, followed by hardening a hardened coating product, or molding a hardened coating product.

6, a method for manufacturing a coated product using a silsesquioxane polymer according to a sixth embodiment of the present invention includes coating a coating material 110 on one side or both sides of a substrate 140 The substrate 140 on which the coating material 110 is coated is passed between two rolls 160 on which the shape is implemented to form a shape on the substrate 140. At this time, a desired product can be obtained by selectively using a process of forming a hardened coating product first, followed by hardening a hardened coating product, or molding a hardened coating product.

Embodiments 1, 2, 3, 4, 5, and 6 of the present invention are coated with a coating composition comprising a silsesquioxane polymer as a coating material 110 on one side or both sides of a product. For example, the product may have a rectangular-shaped concave-convex portion or a predetermined angle-shaped bending angle. Also, depending on the selection of the process, a desired result can be obtained by selectively using a process of forming a hardened coating product first and then curing the hardened coating product.

The above-mentioned coating material 110 is formed from a coating composition comprising a silsesquioxane polymer represented by any of the following formulas (1) to (9).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 1 to 9,

A is

And B is

And D is

And E is

Lt;

Y are each independently O, NR ²¹ or _{[(SiO 3/2 R)} 4 + 2 n O] , and at least one of _{[(SiO 3/2 R) 4 +} 2n O],

X is each independently R ²² or _{[(SiO 3/2 R)} 4 + 2 n R] , and at least one of _{[(SiO 3/2 R) 4 +} 2n R],

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently hydrogen; heavy hydrogen; halogen; An amine group; An epoxy group; Cyclohexyl epoxy group; (Meth) acrylic group; A diazo group; Isocyanate group; A nitrile group; A nitro group; A phenyl group; A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a halogen atom, an amino group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group; A C ₂ to C ₄₀ alkenyl group; A C ₁ to C ₄₀ alkoxy group; A C ₃ to C ₄₀ cycloalkyl group; A C ₃ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₃ to C ₄₀ heteroaryl group; A C ₃ to C ₄₀ aralkyl group; A C ₃ to C ₄₀ aryloxy group; Or a C ₃ to C ₄₀ arylcyclic group which is specifically substituted by a substituent selected from the group consisting of deuterium, halogen, an amine group, a (meth) acryl group, a silyl group, an isocyanate group, a nitrile group, a nitro group, a phenyl group, a cyclohexyl- It is included, and C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, an amine group, an epoxy group, cyclohexyl epoxy groups, (meth) acrylic group, between olgi, a phenyl group or isocyanate,

a and d are each independently an integer of 1 to 100,000, specifically a is 3 to 1000, d is 1 to 500, more specifically a is 5 to 300, d is 2 to 100,

b is independently an integer of 1 to 500,

e is independently 1 or 2, specifically 1,

n is independently an integer of 1 to 20, specifically 3 to 10;

The coating composition of the present invention can have adhesiveness and insulation by forming a single coating layer by coating and curing the silsesquioxane polymer having a specific structure having repeating units of Aa and Dd on the surface of the base film.

The silsesquioxane polymer represented by Formula 1 is prepared by mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ₁ ) ₂ structure into the formula (10) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; And a third step of adding a basic catalyst to the reactor after the second step and converting the reaction solution to basicity to carry out a condensation reaction.

[Chemical formula 10]

Wherein R, R ₁ , a are as defined in formulas (1) to (9).

The silsesquioxane polymer represented by Formula 2 may be prepared by mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the siloxane polymer to prepare a compound of Formula 10; And after the first step, an excess amount of an organosilane compound is added to introduce the Dd (OR ₁ ) ₂ structure into the general formula (10) as shown in general formula (2), an acidic catalyst is added to the reactor to adjust the reaction solution acidic, A second step of stirring; A third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of removing the single cage generating structure through a recrystallization and a filtering process after the third step.

The silsesquioxane polymer represented by Formula 3 may be prepared by mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And a second step in which an acidic catalyst is added to the reactor to introduce the Dd (OR ₁ ) ₂ structure into the formula (10) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added and stirred; A third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of introducing an EeX ₂ structure into the end of the composite polymer after the third step and introducing an acidic catalyst into the reactor to convert the reaction solution into an acidic atmosphere and mixing and stirring the organosilane compound .

The silsesquioxane polymer represented by Formula 4 is prepared by mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound, and controlling the degree of condensation to prepare the compound of Formula 10; And an acidic catalyst is added to the reactor to introduce the Bb structure and the Dd (OR ₁ ) ₂ structure into the chemical formula (10) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added, step; And a third step of adding a basic catalyst to the reactor after the second step and converting the reaction solution to basicity to carry out a condensation reaction.

The silsesquioxane polymer represented by Formula 5 may be prepared by mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the siloxane polymer to prepare a compound of Formula 10; And that the first Bb structure in formula (10) after the step 1 and Dd (OR ₁₎ followed by the addition of an acid catalyst to the reactor by adjusting the reaction solution to acidity in order to introduce the _second structure, the addition of an excess of an organic silane compound and stirring A second step; And a third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to a basic state to perform a condensation reaction; And a fourth step of removing the single cage generating structure through a recrystallization and a filtering process after the third step.

The silsesquioxane polymer represented by Formula 6 is prepared by mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound and condensing the mixture, And an acidic catalyst is added to the reactor to introduce the Bb structure and the Dd (OR ₁ ) ₂ structure into the chemical formula (10) after the first step, the reaction liquid is adjusted to be acidic, and then the organosilane compound is added, step; A third step of adding a basic catalyst to the reactor after the second step to convert the reaction solution to basicity to effect a condensation reaction; And a fourth step of introducing an EeX ₂ structure into the end of the composite polymer after the third step and introducing an acidic catalyst into the reactor to convert the reaction solution into an acidic atmosphere and mixing and stirring the organosilane compound .

The silsesquioxane polymer represented by Formula 7 is prepared by mixing a basic catalyst and an organic solvent in a reactor and then adding an organosilane compound to prepare two types of condensation-controlled compounds of Formula 4: A second step of adding an acidic catalyst to the reactor to adjust the acidity of the reaction solution, and then adding and stirring the organosilane compound in order to introduce the Bb structure and the Dd (OR ₁ ) ₂ structure into the formula 4 obtained in the above step ₁ ; A third step of adding a basic catalyst to the reactor after each of the two-step reactions to convert the reaction solution to basicity to effect a condensation reaction; And four steps of condensing and coupling two or more materials obtained through the above three steps under basic conditions.

The silsesquioxane polymer represented by Formula 8 is prepared by mixing a basic catalyst and an organic solvent in a reactor, adding an organosilane compound, and preparing two types of the compound of Chemical Formula 10 whose condensation degree is controlled; A second step of adding an acidic catalyst to the reactor to adjust the acidity of the reaction mixture and then adding and stirring the organosilane compound to introduce the Bb structure and the Dd (OR ₁ ) ₂ structure into the formula 10 obtained in the first step; A third step of adding a basic catalyst to the reactor after each of the two-step reactions to convert the reaction solution to basicity to effect a condensation reaction; Four steps of condensing and connecting the two or more substances obtained in the above step 3 under basic conditions; Adding the acid catalyst to the reactor for introducing Dd (OR ₁ ) ₂ after the step 4, adjusting the reaction solution to acidity, adding and stirring the organosilane compound; And a sixth step of adding a basic catalyst to the reactor after the above-mentioned 5-step reaction to convert the reaction solution to basicity to carry out a condensation reaction.

The silsesquioxane polymer represented by Formula 9 is prepared by mixing a basic catalyst and an organic solvent in a reactor and then adding an organosilane compound to prepare two types of condensation-controlled compounds of Formula 4: A second step of adding an acidic catalyst to the reactor to adjust the acidity of the reaction solution, and then adding and stirring the organosilane compound in order to introduce the Bb structure and the Dd (OR ₁ ) ₂ structure into the formula 4 obtained in the above step ₁ ; A third step of adding a basic catalyst to the reactor after each of the two-step reactions to convert the reaction solution to basicity to effect a condensation reaction; Four stages of condensation and coupling of two or more compounds obtained through the above three steps under basic conditions; A fifth step of adding an acid catalyst to the reactor for introducing Dd (OR ₁ ) ₂ after the fourth step, adjusting the reaction solution to acidity, adding and stirring the organosilane compound; A sixth step of adding a basic catalyst to the reactor after the fifth step reaction to convert the reaction solution to basicity to perform a condensation reaction; And a seventh step of introducing an EeX ₂ structure into the end of the composite polymer after the sixth step, by adding an acidic catalyst to the reactor to convert the reaction solution into an acidic atmosphere and mixing and stirring the organosilane compound have.

Adding an acidic catalyst to the reactor to further introduce the Bb structure and the Dd (OR ₁ ) ₂ structure into each of the complex polymers, if necessary, to adjust the reaction liquid to acidity, and then adding and stirring the organosilane compound; And further adding a basic catalyst to the reactor after the above step to convert the reaction solution to basicity to carry out a condensation reaction, thereby further including a Bb repeating unit in the complex polymer.

Also, if necessary, an acidic catalyst is added to the reactor to introduce the EeX ₂ structure at the end of each complex polymer, thereby converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Lt; / RTI > repeating units.

In the present invention, the coating composition comprising the silsesquioxane polymer represented by any one of Chemical Formulas 1 to 9 may be used in combination with two or more kinds of complex polymers. Specifically, the coating composition may be represented by Chemical Formula 3, 4, 5 or 6 It is preferable to use a silsesquioxane polymer. In this case, by including the repeating unit Bb or Ee, the physical properties of the coating material including the adhesiveness can be further improved.

When the silsesquioxane polymer is in a liquid phase, the coating composition may be solely coated in a non-solvent type, and in the case of a solid phase, an organic solvent may be included. The coating composition may further comprise an initiator or a curing agent.

Specifically, the coating composition contains the silsesquioxane polymer represented by any one of Chemical Formulas 1 to 9, an organic solvent, an initiator, and a curing agent which are commonly used in the art and are compatible with the complex polymer, Additives such as plasticizers, ultraviolet screening agents and other functional additives can be further added to improve the curability, heat resistance, ultraviolet shielding, plasticizing effect and the like.

The coating composition may further comprise a pigment. The silsesquioxane polymer represented by any one of Chemical Formulas 1 to 9 of the present invention improves the dispersibility of the pigment and is excellent in compatibility with the pigment, so that when the coating composition contains the pigment, excellent coloring coating is provided on the plastic surface can do. It is needless to say that a known pigment can be used as the pigment, and the content of the pigment can be selected by a person skilled in the art within a suitable range.

In the coating composition of the present invention, the silsesquioxane polymer is preferably contained in an amount of at least 5 parts by weight based on 100 parts by weight of the coating composition, specifically 5 to 90 parts by weight, more specifically 10 to 50 parts by weight Is included in the negative amount. Within the above range, the mechanical properties of the cured product of the coating composition can be further improved.

Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve, ketones such as lactate, acetone and methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, But are not limited to, polar solvents such as tetrahydrofuran and tetrahydrofuran; polar solvents such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, But are not limited to, various solvents such as dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide and benzyl alcohol. The amount of the organic solvent is included in the balance excluding the complex polymer, the initiator, the curing agent, and optionally the additive.

In the coating composition of the present invention, the initiator and the curing agent may be appropriately selected depending on the organic functional group contained in the silsesquioxane polymer.

As a specific example, when an organic system capable of post-curing such as an unsaturated hydrocarbon, a silane system, an epoxy system, an amine system, or an isocyanate system is introduced into the organic functional group (R), various curing using heat or light is possible. At this time, a change due to heat or light can be achieved in the polymer itself. Specifically, the curing process can be carried out by diluting the organic solvent as described above.

In the present invention, various initiators may be used for the curing and post-reaction of the composite polymer, and the initiator is preferably contained in an amount of 0.1-10 parts by weight based on the total weight of the composition. When the content is within the above range, And coating stability at the same time.

When an unsaturated hydrocarbon or the like is introduced into the organic functional group (R), a radical initiator may be used. Examples of the radical initiator include trichloroacetophenone, diethoxyacetophenone, 1-phenyl- 2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methyl 2-methylthiophenyl) -2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide trimethyl benzoyl diphenylphosphine oxide, camphor quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methylbutylate) -Dimethyl-4-methoxy-benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenylethane- , t-butylpoxomaleic acid, t- Di (t-butylperoxy) -3,3,5-trimethylcyclohexane, N-butyl-4,4'-di (t-butylperoxy) Butyl peroxy) valerate, and various mixtures thereof can be used.

When epoxy or the like is contained in the organic functional group (R), a sulfonium-based or diphenyliodonium such as triphenylsulfonium or diphenyl-4- (phenylthio) phenylsulfonium as a photopolymerization initiator (cation) Iodonium such as bis (dodecylphenyl) iodonium, diazonium such as phenyldiazonium, ammonium such as 1-benzyl-2-cyanopyridinium or 1- (naphthylmethyl) -2- cyanopyridinium, (4-t-butylphenyl) hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, di (4-methylphenyl) Phenyltrifluoromethanesulfonate iodonium, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfoniumtrifluoromethanesulfonate, and (2 , 4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe and BF ₄ ^- , PF ₆ ^-, SbF ₆ ^-, such as [BQ _4] ^- can be used onium salt combinations (wherein, Q is a phenyl group substituted with at least a group of two or more fluorine or a trifluoromethyl group.).

Examples of the cationic initiator that acts by heat include cationic or protonic acid catalysts such as triflic acid salt, boron trifluoride ether complex, boron trifluoride, etc., various onium salts such as ammonium salts, phosphonium salts and sulfonium salts, and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide and the like can be used without limitation. These initiators can also be added in various mixing forms, and can be mixed with various radical initiators described above. Do.

Depending on the type of the organic functional group (R), amine curing agents such as ethylenediamine, triethylenetetramine, tetraethylenepentamine, 1,3-diaminopropane, dipropylenetriamine, 3- (2- Aminopropylamine, N, N'-bis (3-aminopropyl) -ethylenediamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxal tridecane- Diamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis (4-anisomyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, Can be used. The curing agent may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the composition.

As the curing accelerator for accelerating the curing action, triazine compounds such as acetoguanamine, benzoguanamine and 2,4-diamino-6-vinyl-s-triazine, imidazole compounds such as 2-methylimidazole Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole, Diazabicyclo [4.3.0] nonane-5,1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, diphenyl (p- ) Phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphosphonium phosphate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphoniumhydrogen difluoride, tetrabutylphosphonium dihydrogentry, Fluorine and the like may also be used.

Examples of the anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadonic anhydride, Acid anhydride curing agents such as phthalic anhydride, dodecenylsuccinic anhydride and 2,4-diethylglutaric anhydride can be widely used.

In the present invention, additives such as an ultraviolet absorber, an antioxidant, a defoaming agent, a leveling agent, a water repellent agent, a flame retardant, and an adhesion improver are added for the purpose of improving hardness, strength, durability and moldability of a coating material through a curing process or a post- As shown in FIG. Such an additive is not particularly limited in its use, but may be suitably added within a range that does not impair the physical properties of the coating material. It is preferable that each of the additives is included in an amount of 0.01-10 parts by weight per 100 parts by weight of the composition.

Examples of additives usable in the present invention include polyether-modified polydimethylsiloxane (e.g., BYK-300, BYK-301, BYK-302, BYK-331, BYK-335, BYK- , BYK-341, BYK-344, BYK-307, BYK-333 and BYK-310), polyether modified hydroxyfunctional poly-dimethyl-siloxane -373 and the like), polymethylalkylpolysiloxane (e.g., BYK-077 and BYK-085), polyether modified methylalkylpolysiloxane (e.g., BYK-320, BYK-325 Etc.), polyester modified poly-methyl-alkyl-siloxane (e.g., BYK-315 etc.), aralkyl modified methylalkyl polysiloxane (e.g., BYK- 322, BYK-323, etc.), polyester hydroxy modified siloxane (Polyester modified hydroxy functional (e.g. BYK-371, BYK-UV 3570, etc.), polyether-polyester hydroxypolydimethylsiloxane (e.g., polydimethylsiloxane such as BYK-370), polyester acrylic modified polydimethylsiloxane For example, polyether modified dimethylpolysiloxane (e.g., BYK-345, BYK-348, BYK-346, BYK-375, etc.) Ionic acrylic copolymer (e.g., BYK-380), an ionic acrylic copolymer (e.g., BYK-381, etc.) ), Polyacrylate (e.g., BYK-353, BYK-356, BYK-354, BYK-355, BYK-359, BYK- Etc.), polymethacrylates (e.g., BYK-390, etc.), polyetheracryl polydimethylsilanes Polyether modified siloxane (e.g., BYK-347), alcohol alkoxylates (BYK-UV 3530, etc.), polyether modified siloxane (E.g., BYK-DYNWET 800, etc.), acrylate (e.g., BYK-392), silicone-modified polyacrylate (OH-functional) Silclean 3700, etc.).

In addition, the method of coating the coating composition according to the present invention may be selected by a person skilled in the art from among known methods such as spin coating, bar coating, slit coating, spraying and dipping, Or thermosetting can be appropriately selected and applied according to the functional group of the complex polymer. Specifically, in the case of thermal curing, the curing temperature is from 50 to 200.

In the present invention, the coating thickness of the coating composition is optionally adjustable, specifically 0.01 to 500 μm, more specifically 0.1 to 300 μm, still more preferably 1 to 100 μm. Within the above range, excellent adhesion and surface hardness of 7H or more of the coating material can be stably secured.

The thickness of the coating material constituting the coating product of the present invention can be arbitrarily adjusted by those skilled in the art.

Accordingly, the coating product of the present invention can be used for a variety of daily necessities for injection molding, interior and exterior materials (elevator, intermediate door, etc.), industrial protective films, smart phones, tablet PCs, notebook PCs, All- ) It can be applied to cases of electronic products such as PCs, LCD monitors, internal / external advertisement displays, widescreen cover boards and protective films, protective plates, automobile windows, automobile interior instrument panels and display window covers.

The embodiments of the present invention described above are not implemented only by the apparatus and / or method, but may be implemented through a program for realizing functions corresponding to the configuration of the embodiment of the present invention, a recording medium on which the program is recorded And such an embodiment can be easily implemented by those skilled in the art from the description of the embodiments described above.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, It belongs to the scope of right.

100: hard coating film, hard coating layer
110: Coating material
120: substrate film
130: Hot melt material
140: substrate
150: roll
152, 154: stamp device
160: roll
200: Injection mold

Claims (13)

Forming a coating layer by coating a coating material inside an injection mold having a predetermined shape; And
Injecting an injection material into the injection mold to integrate the injection material and the material forming the coating layer and injection molding the mixture to form the coating layer on one side or both sides of the product. Coating a coating material on one side or both sides of a substrate to form a coating layer on the substrate; And
And molding the substrate on which the coating layer is formed through a rolling process. Coating a coating material on one side or both sides of a substrate to form a coating layer on the substrate; And
Inserting a substrate having the coating layer formed thereon into a stamp device having a shape formed on one surface thereof, and pressing the substrate to form a shape. Coating a coating material on an inner surface of a stamp device having a predetermined shape to form a coating layer; And
And pressing the substrate on the stamp device to form a shape on the substrate while coating the coating material. 3. The method of claim 2,
After the molding step,
Inserting a substrate having the coating layer formed thereon into a stamp device having a shape formed on one surface thereof, and pressing the substrate to form a shape. Coating a coating material on one side or both sides of a substrate to form a coating layer on the substrate; And
And passing the substrate having the coating layer formed therebetween through a roll having a predetermined shape to form a shape on the substrate on which the coating layer is formed. 7. The method according to any one of claims 1 to 6,
Wherein the substrate or the specific material is one of a hot-melt polymeric material, a hot-melt composite material, a solid metal, a solid plastic, and a solid composite material. The method according to any one of claims 1, 2, 3, 4, and 6,
Wherein the coating layer is cured and then molded or processed to form a shape. 7. The method according to any one of claims 1 to 6,
Wherein the coating material comprises a silsesquioxane polymer represented by any one of the following formulas (1) to (9).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 1 to 9,
A is

And B is

And D is

And E is

Lt;
Y are each independently O, NR ²¹ or _{[(SiO 3/2 R)} 4 + 2 n O] , and at least one of _{[(SiO 3/2 R) 4 +} 2n O],
X is each independently R ²² or _{[(SiO 3/2 R)} 4 + 2 n R] , and at least one of _{[(SiO 3/2 R) 4 +} 2n R],
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently hydrogen; heavy hydrogen; halogen; An amine group; An epoxy group; Cyclohexyl epoxy group; (Meth) acrylic group; A diazo group; Isocyanate group; A nitrile group; A nitro group; A phenyl group; A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a halogen atom, an amino group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group; A C ₂ to C ₄₀ alkenyl group; A C ₁ to C ₄₀ alkoxy group; A C ₃ to C ₄₀ cycloalkyl group; A C ₃ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₃ to C ₄₀ heteroaryl group; A C ₃ to C ₄₀ aralkyl group; A C ₃ to C ₄₀ aryloxy group; Or an aryl radical of C ₃ to C ₄₀ ,
a, b and d are each independently an integer of 1 to 100,000, b is 1 to 500, d is 1 to 500, e is 1 or 2, and n is 1 to 20 A coating product coated with a coating composition comprising a silsesquioxane polymer on one side or both sides of the product. 11. The method of claim 10,
Wherein the coating composition comprises a silsesquioxane polymer represented by any one of the following formulas (1) to (9).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 1 to 9,
A is

And B is

And D is

And E is

Lt;
Y are each independently O, NR ²¹ or _{[(SiO 3/2 R)} 4 + 2 n O] , and at least one of _{[(SiO 3/2 R) 4 +} 2n O],
X is each independently R ²² or _{[(SiO 3/2 R)} 4 + 2 n R] , and at least one of _{[(SiO 3/2 R) 4 +} 2n R],
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently hydrogen; heavy hydrogen; halogen; An amine group; An epoxy group; Cyclohexyl epoxy group; (Meth) acrylic group; A diazo group; Isocyanate group; A nitrile group; A nitro group; A phenyl group; A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with a halogen atom, an amino group, an epoxy group, a (meth) acrylic group, a silyl group, an isocyanate group, a nitrile group, a nitro group or a phenyl group; A C ₂ to C ₄₀ alkenyl group; A C ₁ to C ₄₀ alkoxy group; A C ₃ to C ₄₀ cycloalkyl group; A C ₃ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₃ to C ₄₀ heteroaryl group; A C ₃ to C ₄₀ aralkyl group; A C ₃ to C ₄₀ aryloxy group; Or an aryl radical of C ₃ to C ₄₀ ,
a, b and d are each independently an integer of 1 to 100,000, b is 1 to 500, d is 1 to 500, e is 1 or 2, and n is 1 to 20. 11. The method of claim 10,
The coating composition may comprise,
The silsesquioxane polymer;
Initiator;
Curing agent; And
Organic solvent
≪ / RTI > 11. The method of claim 10,
Wherein the silsesquioxane polymer is 5 to 90 parts by weight based on 100 parts by weight of the coating composition.

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