WO2018124826A1 - Coating compositions capable of realizing low curl and film manufactured therefrom - Google Patents

Abstract

The present invention relates to a coating composition capable of realizing a low curl and a film manufactured therefrom and, specifically, to a coating composition capable of reducing the curl of a coating layer by, especially, comprising a resin composition and a multi-functional organic compound containing an alcohol group, a thiol group, or a carboxyl group, and to a film manufactured therefrom.

Description

Coating compositions capable of low curl implementation and films made therefrom

The present invention relates to a coating composition capable of low curl implementation and a film prepared therefrom, and more particularly, to a coating composition capable of performing low curl including a polyfunctional organic compound and a film prepared therefrom. will be.

The contents described below merely provide background information related to the present invention and do not constitute a prior art.

With the recent development of the information industry and multimedia, various display fields have been widely spread, and as the display technology requiring new characteristics such as flexible, bendable, and foldable and smart devices using the same have emerged as future technologies, glass substrates of conventional displays It is expected that this cannot be implemented. In addition to the disadvantages of not being flexible, there is a fundamental problem that glass substrates are heavy and fragile and have a high defect rate when processing products.

In order to solve the above problems, polymer plastic substrates such as polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA) and polyimide (PI) are being applied. Due to the lack of chemical resistance, there is a problem that the scratches, abrasion, hardness and the like compared to the glass is weak.

In order to compensate for these disadvantages, attempts have been actively made to improve the properties by applying a hard coating composition on a polymer plastic substrate.

A general hard coating composition is composed of a resin containing a photocurable functional group such as (meth) acrylate or epoxy, a curing agent and an additive, and after coating on a polymer plastic substrate and undergoing a curing process, a coating layer having properties such as hardness and abrasion resistance may be formed. It can be formed, which can be applied as a protective substrate of the display.

Such photo-curable hard coating compositions based on (meth) acrylates or epoxy groups provide improved hardness, but it is difficult to realize high hardness at the glass level. Has difficulty in its practical application. By applying a thick coating layer can realize high hardness properties, but the thicker the coating layer becomes more difficult since the curl occurs due to shrinkage during curing becomes more difficult.

In order to solve this problem, various studies have been conducted to satisfy the high hardness and curl characteristics of the coating layer on the polymer plastic substrate at the same time.

For example, Korean Patent Application No. 10-2008-0114104 discloses a photocurable (meth) acrylate oligomer, a multi-pipe manufactured by the reaction of a polyester polyol containing 2 to 40 hydroxyl groups and a polyfunctional (meth) acrylate monomer. Although a hard coating composition consisting of a functional (meth) acrylate monomer, a photopolymerization initiator and a residual amount of solvent was prepared to form a coating layer to improve curl, it is difficult to control curl due to shrinkage during curing due to the properties of (meth) acrylate. There is this.

In addition, according to the Republic of Korea Patent Application No. 10-2015-0031865, using a silsesquioxane organic-inorganic composite has been formed a coating layer of high hardness, even in the case of the high hardness coating layer, the curl by the curing is a display and smart Applicability to the device was impaired.

Therefore, if a high-hardness coating layer of low curl is realized by controlling the curl of the coating layer formed using the silsesquioxane resin capable of high surface hardness, the coating film using the same may be an optical film, a protective film, or a plastic for electronic products. It can be usefully applied to various other products.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a coating composition and a film prepared therefrom that can be implemented low-cal including a polyfunctional organic compound.

The present invention to achieve the above object is a resin composition; And a polyfunctional organic compound including an alcohol group, a thiol group, or a carboxyl group, wherein the polyfunctional organic compound provides 1 to 100 parts by weight based on 100 parts by weight of the resin composition.

The multifunctional organic compound may include a compound of Formula 1 below:

[Formula 1]

[R] ━ {[X] ━ [R ']} _k

Where

k is an integer from 1 to 4,

R and R 'are each independently an alkyl group having 1 to 20 carbon atoms, an alcohol group connected to an alkyl group having 1 to 20 carbon atoms, a thiol group connected to an alkyl group having 1 to 20 carbon atoms, a carboxyl group connected to an alkyl group having 1 to 20 carbon atoms, and an alcohol group , A thiol group, or a carboxyl group,

X is a linking group derived from Formula 2, Formula 3, Formula 4 or Formula 5:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

Where

m, n, o, x and y are each independently an integer from 1 to 10,000.

The polyfunctional organic compound including the alcohol group, thiol group or carboxyl group may have a molecular weight of 100 to 1,000,000.

The resin composition may include an epoxy or acrylic resin, or may include a silsesquioxane resin.

In this case, the silsesquioxane resin may be a cage silsesquioxane, a ladder silsesquioxane, a random silsesquioxane, or a mixture thereof.

The coating composition may further comprise one or more of a cationic initiator, a radical initiator or a solvent initiated by light or heat.

The present invention also provides a film wherein the coating composition is coated on a substrate and cured.

The film may have an average value of 5 mm or less with four corners spaced apart from the bottom on an A4 size basis.

The present invention can prepare a coating composition capable of low curl implementation including a polyfunctional organic compound including an alcohol group, a thiol group or a carboxyl group.

The present invention can be used to produce a film with less occurrence of curl using the coating composition, it can be usefully applied to various products other than optical films, protective films, electronic products such as display panels and plastics.

In addition, the composition of the present invention can be applied to a plastic substrate having a flexible and high hardness properties that can replace the protective glass substrate of a display substrate such as LCD, OLED.

1 is a view showing that the film produced according to the present invention forms a low curl compared to the conventional film.

2 is a view showing that when the composition of the present invention is cured, an organic compound having an alcohol group, a thiol group, or a carboxyl group forms a crosslink to perform a three-dimensional buffer function.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

When any part of the specification is to "include" any component, this means that it may further include other components, except to exclude other components unless otherwise stated.

The coating composition of the present invention includes a resin composition; and a polyfunctional organic compound including an alcohol group, a thiol group, or a carboxyl group, and the polyfunctional organic compound includes 1 part by weight to 100 parts by weight based on 100 parts by weight of the resin composition.

When the content of the polyfunctional organic compound containing the alcohol group, the thiol group or the carboxyl group is less than 1 part by weight, it is difficult to expect the effect of curl control, the content of the polyfunctional organic compound including the alcohol group, thiol group or carboxyl group If it exceeds 100 parts by weight, the degree of curing may be inferior and the curing properties of the coating layer may be incomplete.

In the present invention, the multifunctional organic compound may include a compound of Formula 1 below:

[Formula 1]

[R] ━ {[X] ━ [R ']} _k

Where

k is an integer from 1 to 4,

R and R 'are each independently an alkyl group having 1 to 20 carbon atoms, an alcohol group connected to an alkyl group having 1 to 20 carbon atoms, a thiol group connected to an alkyl group having 1 to 20 carbon atoms, a carboxyl group connected to an alkyl group having 1 to 20 carbon atoms, and an alcohol group , A thiol group, or a carboxyl group,

X is a linking group derived from Formula 2, Formula 3, Formula 4 or Formula 5:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

Where

m, n, o, x and y are each independently an integer from 1 to 10,000.

In the present invention, the polyfunctional organic compound including the alcohol group, thiol group or carboxyl group may have a molecular weight of 100 to 1,000,000.

When the polyfunctional organic compound contains an alcohol group, the polyfunctional organic compound may be polyester polyol, polycarbonate polyol, polyethylene glycol, polypropylene glycol, polycaprotaxone polyol, polytetramethylene glycol, tetramethyltrimethylol, glycerin , Pentaerythritol tetraalcohol, dipentaerythritol hexaalcohol, polyacrylate polyol, polyvinyl alcohol, and one selected from the group consisting of polyols derived therefrom.

In addition, when the polyfunctional organic compound contains a thiol group, the polyfunctional organic compound may be 1,2-ethanedithiol, butanedithiol, 1,3-propanedithiol, or 1,2-ethanedithiol. Ol, butanedithiol, 1,3-propanedithiol, 1,5-pentanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 3,6-dioxa-1 , 8-octanedithiols, 1,8-octanedithiols, hexanedithiols, dithiodiglycols, pentanedithiols, decandithiols, 2-methyl 1,4-butanedithiols , 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 2,4,6-trimethyl, 1,3-benzenedimethane thiol, polypropylene ether It may be one or more selected from the group consisting of glycol bis, 1,2-dimercaptoethane and 1,6-dimercaptohexane.

In addition, when the polyfunctional organic compound contains a carboxyl group, the polyfunctional organic compound is naphthalene 1,8-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 2,2'-bipyridine- 4,4'-dicarboxylic acid, pyrrolidine-2,4-dicarboxylic acid, 4,5-imidazoledicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride It may be at least one selected from the group consisting of pyridine-2,5-dicarboxylate and diphenyl-4,4'-dicarboxylate.

In the present invention, the resin composition may include an epoxy or acrylic organic resin, or may include a silsesquioxane resin, and specifically, may include a silsesquioxane resin.

Epoxy-based organic resin of the resin composition may be used as long as it has two or more epoxy groups in one molecule, for example, alicyclic epoxy, bisphenol A and F type epoxy, phenol novolak type epoxy, naphthalene type epoxy, Biphenyl type epoxy, cyclopentadiene type epoxy, etc. are illustrated. Among these, an alicyclic epoxy and a phenol novolak-type epoxy are preferable for compatibility with a multifunctional organic compound and curing properties.

In the resin composition, the acryl-based organic resin may be any of 2 to 12 functional acrylic organic resins having two or more acrylic groups in one molecule, and 3 to 6 functional acrylic resins for controlling the degree of curing and curling of the cured product. Organic resins are preferred.

The acrylic organic resin means not only acrylate but also methacrylate or a derivative in which a substituent is introduced into acrylate or methacrylate, and examples thereof include trimethylolpropane triacrylate, trimethylolpropaneethoxy triacrylate, Glycerin propoxylated triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. are mentioned.

The silsesquioxane resin may be, for example, cage type silsesquioxane, ladder type silsesquioxane, random type silsesquioxane or a mixture thereof, and specifically, the structure of Formula 6 It may be a ladder type silsesquioxane having:

[Formula 6]

Where

Each R ′ ₁ is independently an alkyl group of C ₁ to C ₅ ,

Each R ₁₁ is independently hydrogen; heavy hydrogen; halogen; Amine group; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Thiol group; Isocyanate group; Nitrile group; Nitro group; Or a phenyl group; C ₁ to C ₄₀ alkyl group or C ₂ to C _{40 which} is unsubstituted or substituted with hydrogen, deuterium, halogen, amine group, epoxy group, (meth) acryl group, thiol group, isocyanate group, nitrile group, nitro group or phenyl group Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or C ₃ to C ₄₀ aralkyl group or C ₃ to C ₄₀ aryloxy group or C ₃ to C ₄₀ arylsilol group,

Z is an integer from 1 to 100,000.

More specifically, the silsesquioxane resin of the formula (6) usable in the present invention may be a ladder-type silsesquioxane resin, and the prior art, for example, Korean Patent Application No. 10-2015-0031865 or Korea Silsesquioxane resins, which may be prepared by patent application 10-2013-0163607, are also available.

The silsesquioxane composite polymer of the present invention may be adjusted to 1 to 99.9% condensation in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of alkoxy groups bonded to Si at the terminal and center can be controlled from 50% to 0.01% with respect to the bonding groups of the entire polymer.

In addition, the weight average molecular weight of the silsesquioxane composite polymer according to the present invention may be 1,000 to 1,000,000, specifically 5,000 to 100,000, and more specifically 7,000 to 50,000. In this case, the processability and physical properties of the silsesquioxane can be improved simultaneously.

In the coating composition of the present invention, the resin composition may further include one or more of a cationic initiator, a radical initiator or a solvent initiated by light or heat commonly used in the art, and optionally, a curing agent, a plasticizer, a sunscreen, Additives such as other functional additives may be further included to improve curability, heat resistance, UV blocking, plasticizing effect, and the like.

In the present invention, a photoinitiator may be used specifically, and may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of a resin, for example, a total weight of silsesquioxane resin.

As the photoinitiator usable in the present invention, photoinitiators conventionally used in the art may be used, and iron-arene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, pyridinium salts, and aluminum complexes / silyl At least one cationic polymerization initiator selected from the group consisting of ethers or at least one radical polymerization initiator selected from the group consisting of acetophenones, benzoin, acylfocipine oxides, titanocenes, benzophenones and thioxanthones initiators have.

In addition, the solvent usable in the present invention can be used without limitation so long as it is an organic solvent commonly used in the art, for example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, 2-methoxyethanol, Alkoxy alcohol solvents such as 2-ethoxyethanol, 1-methoxy-2-propanol, 2-isopropoxyethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, ketone solvents such as cyclohexanone , Propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol, monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol mono Ethers such as propyl ether, diethyl glycol monobutyl ether, diethylene glycol-2-ethylhexyl ether May be used reugye solvent, benzene, toluene, aromatic solvents such as xylene, it may be used by mixing one or more.

In the present invention, specifically the solvent may be included so that the solids content of the coating composition is 30% to 70% by weight.

The present invention also provides a film wherein the coating composition is coated on a substrate and cured.

The film may be prepared by coating the coating composition on a substrate and then curing by light irradiation.

In the multifunctional organic compound-resin formed by crosslinking of a photocurable resin with an organic compound having an alcohol, a thiol, and a carboxylic acid group, the polyfunctional organic compound is intermolecular by covalent bonds in a cured material. By restricting to have an appropriate intermolecular distance by performing a three-dimensional buffering effect to suppress the narrowing or stretching of the distance, it is possible to control the shrinkage / expansion generated during photocuring to reduce the curl of the coating layer.

The film obtained by applying the coating composition to the substrate by the method proposed in the present invention can be coated by easily adjusting the bending strength of the coating layer according to the degree of warpage of the substrate, and the curling of the substrate is remarkably small with only one side coating. The coating layer can be formed.

For example, although there may be a difference in numerical values depending on the thickness and the substrate of the applied coating composition, the average value of curls with four corners spaced from the bottom on the basis of A4 size may be 5 mm or less. At this time, the curl was placed in a flat place A4 size coating film, the average value of the height of the four corner ends spaced from the plane as the curl value.

In the present invention, the effect of lowering curl by the coating composition of the present invention can be expected without limiting the substrate.

As a substrate applicable to the present invention, a plastic film known as a substrate of a conventional optical coating film may be applied. Specifically, the plastic film may be appropriately selected from transparent or translucent according to a use, and may be, for example, polyethylene terephthalate or polybutyl. Polyester films such as lenterephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, poly Vinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethyl methacrylate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film , Polyimi Film, fluorine resin film, polyamide film, acrylic resin film, norbornene-based resin film, cycloolefin resin film and the like can be used.

In the case of the general coating composition, the thicker the coating thickness, the more the curl is increased as well, the process is impossible or there is a problem that the unevenness and cracks of the coating film surface occurs. However, the thickness of the coating composition of the present invention can be arbitrarily adjusted according to the substrate, for example, can be formed to a thickness of 1 ㎛ to 100 ㎛ or less, less curl occurs even in a thick thickness of 50 ㎛ or more process application and product application This is easy. From the viewpoint of effectively suppressing the curl phenomenon, the thickness may be 100 μm or less, and more specifically, 20 to 80 μm.

For example, when the coating composition is applied at 5 to 100 μm, the curl of the final coating film may be adjusted to 5 mm or less.

Specifically, when the coating composition of the present invention is applied to a polycarbonate (PC) substrate having a thickness of 0.3 mm at a thickness of 30 μm, the curl of the coating film may have an average value of four corners of 3 mm or less based on A4, and a thickness of 0.188 mm. When the coating composition of the present invention is applied to a polyethylene terephthalate (PET) substrate of 30 μm in thickness, the curl of the coating film may have an average value of four corners of 2 mm or less on the basis of A4, and a polymethyl meta of 0.3 mm in thickness. When the coating composition of the present invention is applied to a methacrylate (PMMA) substrate with a thickness of 30 μm, the curl of the coating film may have an average value of four corners of 2 mm or less based on A4, and a triacetyl cellulose (TAC) having a thickness of 0.1 mm. When the coating composition of the present invention is applied to the substrate to a thickness of 30 μm, the curl of the coating film may have an average value of four corners of 4 mm or less based on A4.

The coating composition may be applied on the plastic substrate film by a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, a spin coating method and the like.

In the curing of the present invention, mercury, metal halides, LEDs, and the like may be used as the light source of the ultraviolet lamp, and light having a wavelength of 250 to 400 nm may be used for curing the coating composition.

The coating composition according to the present invention comprises a polyfunctional organic compound comprising an alcohol group, a thiol group or a carboxyl group, a silsesquioxane resin, a photoinitiator and a solvent, so that the coating composition may Due to the buffering action, curing shrinkage can be alleviated to significantly reduce the occurrence of curl, and the hardness of the film can be improved.

Hereinafter, specific examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Preparation Example 1

Preparation Example 1-a Preparation of Catalyst

In order to control the acidity, a 25 wt% aqueous solution of tetramethylammonium hydroxide (TMAH), an amine basic catalyst, or a 10 wt% aqueous solution of potassium hydroxide (KOH), a metal basic catalyst, was prepared as a catalyst 1a.

Production Example 1-b Preparation of Silsesquioxane Resin

35% by weight of 3-acryloxypropyl trimethoxysilane and 60% by weight of tetrahydrofuran (THF) were mixed and stirred for 10 minutes. The reaction was carried out by dropping 5 wt% of the catalyst prepared in Preparation Example 1-a into the mixed solution. After stirring at room temperature for 5 days, the catalyst and impurities were removed by three washing processes. Tetrahydrofuran (THF) was separated and removed in vacuo from the obtained mixed solution to prepare a silsesquioxane resin.

Si-OH functional group was confirmed through IR analysis (3,200 cm-1), and the molecular weight was measured, it was confirmed that the produced silsesquioxane resin had a molecular weight in terms of styrene styrene.

EXAMPLE

According to the components and contents shown in Table 1, Examples and Comparative Examples were carried out as follows. All compositions were matched with coating thickness by using the same amount of solvent as the solids content of the resin composition and organic compound to facilitate comparison between samples after coating. In Table 1, the unit is parts by weight.

	Resin composition	Organic compounds	Photoinitiator	additive	menstruum
Example 1	100	One	2.0	0.20	101
Example 2	100	50	3.0	0.30	150
Example 3	100	100	4.0	0.40	200
Example 4	100	One	2.0	0.20	101
Example 5	100	50	3.0	0.30	150
Example 6	100	100	4.0	0.40	200
Example 7	100	100	4.0	0.40	200
Example 8	100	100	4.0	0.40	200
Example 9	100	100	4.0	0.40	200
Comparative Example 1	100	0.5	2.0	0.20	100
Comparative Example 2	100	110	4.2	0.42	210

Example 1

100 parts by weight of the silsesquioxane resin obtained in Preparation Example 1, 2.2 parts by weight of a photoinitiator (trade name: Synasia, PI-6976), 0.22 parts by weight of a silicone-based leveling additive (trade name: BYK, BYK-378), a polyhydric alcohol 1 part by weight of the organic compound (trade name: Daicel, PCL-305) and 101 parts by weight of 2-isopropyl alcohol were mixed to prepare a coating composition.

The coating composition was applied onto a polycarbonate substrate having a thickness of 0.3 mm and dried and cured so that the final coating had a thickness of 30 μm.

Example 2

A coating composition and a coating film were prepared in the same manner as in Example 1, except that 50 parts by weight of the alcohol organic composite (trade name: Daicel, PCL-305) was used instead of 1 part by weight.

Example 3

A coating composition and a coating film were prepared in the same manner as in Example 1, except that 100 parts by weight of the alcohol organic composite (trade name: Daicel, PCL-305) was used instead of 1 part by weight.

Example 4

A coating composition and a coating film were prepared in the same manner and composition as in Example 1, except that the thiol organic compound (Showa Denko, KarenzMT PE1) was used instead of the alcohol organic compound.

Example 5

A coating composition and a coating film were prepared in the same manner and composition as in Example 2, except that thiol organic composite (Showa Denko, KarenzMT PE1) was used instead of the alcohol organic composite.

Example 6

A coating composition and a coating film were prepared in the same manner and in the same manner as in Example 3 except that a thiol organic compound (Showa Denko, KarenzMT PE1) was used instead of the alcohol organic compound.

Example 7

3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate was used in place of the silsesquioxane resin obtained in Preparation Example 1 in the same manner as in Example 3 Coating film was prepared.

Example 8

Except for using the commercially available bisphenol A epoxy resin (KE-8128, Kolon Industries) instead of the silsesquioxane resin obtained in Preparation Example 1 in the same manner as in Example 3 and the coating composition and coating film Prepared.

Example 9

The coating composition was prepared in the same manner as in Example 3 except that trimethylolpropane triacrylate was used instead of the silsesquioxane resin obtained in Preparation Example 1, and IRGACURE-184 was used instead of PI-6976 as a photoinitiator. Coating film was prepared.

Comparative Example 1

A coating composition and a coating film were prepared in the same manner as in Example 1, except that 0.5 parts by weight of the alcohol organic composite (trade name: Daicel, PCL-305) was used instead of 1 part by weight.

Comparative Example 2

A coating composition and a coating film were prepared in the same manner as in Example 1, except that 110 parts by weight of the alcohol organic compound (trade name: Daicel, PCL-305) was used instead of 1 part by weight.

Test Example

The physical properties of the coating films prepared in Examples 1 to 9 and Comparative Examples 1 and 4 are shown in Table 2 below.

At this time, physical properties were measured as follows.

-Pencil hardness

 Using a pencil hardness tester and a pencil manufactured by Mitsubishi, the hardness of the coated film was measured by applying a load of 1 kg at a 45 degree angle. The hardness whose scratches generate | occur | produced once or less after measuring 5 times for each pencil hardness was made into the pencil hardness of the said coating film.

-Curl

 When the coating film of A4 size coated with the coating composition at a thickness of 30 μm was placed on a flat bottom, the average value of the distances at which each corner was spaced from the plane was calculated.

-Adhesion

 After eleven lines were drawn horizontally and vertically at intervals of 1 mm on the coating film to make 100 squares, three peel tests were performed using a tape (3M, 3M-810). The number of squares not peeled off even after the peel test was counted to determine the adhesion of the coating composition to the substrate. That is, if it is 0/100, all the coating composition was peeled off, and if it was 100/100, it was represented as maintaining adhesiveness.

	Pencil hardness	curl	Adhesion
Example 1	7H	4.0 mm	100/100
Example 2	7H	3.0 mm	100/100
Example 3	6H	1.0 mm	100/100
Example 4	8H	4.0 mm	100/100
Example 5	8H	2.0 mm	100/100
Example 6	7H	0.5 mm	100/100
Example 7	5H	1.2 mm	100/100
Example 8	4H	1.0 mm	100/100
Example 9	4H	1.5 mm	100/100
Comparative Example 1	8H	70.0 mm	100/100
Comparative Example 2	F	0.5 mm	100/100

As shown in Table 2, the coating film according to the present invention not only has excellent pencil hardness and adhesion as the content of the polyfunctional organic compound increases, and is significantly lower than that of the comparative example that does not include the polyfunctional organic compound. It can be seen that the curl. In addition, in the case of Comparative Example 2 in which the content of the polyfunctional organic compound exceeds the range of the present invention, it can be seen that the curl is very low but the hardness is not suitable for use as a coating composition.

Claims (13)

1. Resin composition; And

   It includes a polyfunctional organic compound containing an alcohol group, a thiol group or a carboxyl group,

   The polyfunctional organic compound is a coating composition comprising 1 part by weight to 100 parts by weight relative to 100 parts by weight of the resin composition.
2. The method of claim 1,

   The polyfunctional organic compound is a coating composition comprising a compound of formula (1).

   [Formula 1]

   [R] ━ {[X] ━ [R ']} _k

   Where

   k is an integer from 1 to 4,

   R and R 'are each independently an alkyl group having 1 to 20 carbon atoms, an alcohol group connected to an alkyl group having 1 to 20 carbon atoms, a thiol group connected to an alkyl group having 1 to 20 carbon atoms, a carboxyl group connected to an alkyl group having 1 to 20 carbon atoms, and an alcohol group , A thiol group, or a carboxyl group,

   X is a divalent linking group derived from Formula 2, Formula 3, Formula 4 or Formula 5:

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   [Formula 5]

   

   Where

   m, n, o, x and y are each independently an integer from 1 to 10,000.

   Resin composition; And

   It includes a polyfunctional organic compound containing an alcohol group, a thiol group or a carboxyl group,

   The polyfunctional organic compound is a coating composition comprising 1 part by weight to 100 parts by weight relative to 100 parts by weight of the resin composition.
3. The method of claim 1,

   The polyfunctional organic compound has a molecular weight of 100 to 1,000,000 coating composition.
4. The method of claim 1,

   The polyfunctional organic compound containing the alcohol group may be polyester polyol, polycarbonate polyol, polyethylene glycol, polypropylene glycol, polycaprotaxone polyol, polytetramethylene glycol, tetramethyltrimethylol, glycerin, pentaerythritol tetraalcohol, di Pentaerythritol hexaalcohol, polyacrylate polyol, polyvinyl alcohol and a coating composition which is one selected from the group consisting of polyols derived therefrom.
5. The method of claim 1,

   The polyfunctional organic compound containing the thiol group may be 1,2-ethanedithiol, butanedithiol, 1,3-propanedithiol, 1,2-ethanedithiol, butanedithiol, 1, 3-propanedithiol, 1,5-pentanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 3,6-dioxa-1,8-octanedithiol, 1 , 8-octanedithiol, hexanedithiol, dithiodiglycol, pentanedithiol, decandithiol, 2-methyl 1,4-butanedithiol, 1,2-benzenedithiol , 1,3-benzenedithiol, 1,4-benzenedithiol, 2,4,6-trimethyl, 1,3-benzenedimethanethiol, polypropylene ether glycol bis, 1,2- Coating composition of at least one selected from the group consisting of dimercaptoethane and 1,6-dimercaptohexane.
6. The method of claim 1,

   The polyfunctional organic compound containing the carboxyl group is naphthalene 1,8-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid , Pyrrolidine-2,4-dicarboxylic acid, 4,5-imidazoledicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxydione hydride, pyridine-2,5-dicarboxylic acid At least one coating composition selected from the group consisting of acid chlorides and diphenyl-4,4'-dicarboxylates.
7. The method of claim 1,

   The resin composition is a coating composition comprising an epoxy or acrylic organic resin.
8. The method of claim 1,

   The resin composition is a coating composition comprising a silsesquioxane resin.
9. The method of claim 8,

   The silsesquioxane resin is a cage type silsesquioxane, ladder type silsesquioxane, random type silsesquioxane or a mixture thereof.
10. The method of claim 1,

    The polyfunctional organic compound and the resin has a weight ratio of 1: 99 to 50: 50 coating composition.
11. The method of claim 1,

    The coating composition further comprises one or more of a cationic initiator, a radical initiator or a solvent initiated by light or heat.
12. A film, wherein the coating composition of any one of claims 1 to 11 is coated onto a substrate and cured.
13. The method of claim 12,

    A film with an average value of 5 mm or less, with four corners spaced from the bottom on an A4 size basis.

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