JP7100038B2 - Coating compositions capable of achieving low curl and films to be produced from this - Google Patents

Description

The present invention relates to a coating composition capable of achieving low curl and a film produced from the present invention. More specifically, the present invention comprises a polyfunctional organic compound and is capable of achieving low curl. Regarding the film.

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

Recently, while various display fields have become widespread due to the development of the information industry and multimedia, displays that require new characteristics such as flexible, bendable, and foldable and smart devices that utilize them will emerge as future technologies. Therefore, it is expected that this cannot be realized as a glass substrate of a conventional display. In addition to its inflexibility, glass substrates have the fundamental problem of being heavy and fragile, with a high defect rate during product processing.

To solve the above problems, polymer plastic substrates such as polyethylene terephthalate (PET), polycarbonate (PC), polymethylmethacrylate (PMMA), and polyimide (PI) have been applied, but these are wear resistant. There is a problem that heat resistance, chemical resistance, etc. are insufficient, and scratches, wear, hardness, etc. are fragile as compared with glass.

In order to compensate for such disadvantages, attempts to improve the properties by applying a hard coating composition on a polymer plastic substrate are being actively promoted.

A typical 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 is applied onto a polymer plastic substrate and then cured. A coating layer having properties such as hardness and abrasion resistance can be formed through the coating layer, which can be applied as a protective substrate for a display.

Such a photocurable hard coating composition containing a (meth) acrylate or epoxy group as a main component provides improved hardness, but it is difficult to achieve high hardness at the glass level, and the curl phenomenon due to shrinkage during curing occurs. It occurs largely and there is difficulty in actually applying a coating film using this. High hardness characteristics can be realized by applying a thick coating layer, but the thicker the coating layer, the more severe the curl due to shrinkage during curing, which makes the actual application even more difficult.

In order to solve such problems, various studies are underway to simultaneously satisfy the high hardness characteristics and curl characteristics of the coating layer on the polymer plastic substrate.

As an example, in Republic of Korea Patent Application No. 10-2008-0114104, a photocurable (meth) acrylate oligomer produced by a reaction of a polyester polyol containing 2 to 40 hydroxy groups and a polyfunctional (meth) acrylate monomer. A hard coating composition consisting of a polyfunctional (meth) acrylate monomer, a photopolymerization initiator, and a residual solvent has been produced to form a coating layer with improved curl, but the characteristics of (meth) acrylate. In addition, it is difficult to control curl due to shrinkage during curing.

Further, according to the Republic of Korea Patent Application No. 10-2015-0031865, a high-hardness coating layer is formed by using a silsesquioxane organic-inorganic complex, but even in the case of a high-hardness coating layer by this. Curling due to curing has hampered its applicability to displays and smart devices.

Therefore, when the curl of the coating layer formed by using the silsesquioxane resin capable of achieving high surface hardness is controlled to realize a high hardness coating layer having low curl, the coating film using this is an optical film. It can be usefully applied to various products other than protective films and plastics for electronic products.

In order to solve the above-mentioned problems of the prior art, it is an object of the present invention to provide a coating composition containing a polyfunctional organic compound and capable of achieving low curl, and a film produced from the same. ..

In order to achieve the above object, the present invention comprises a resin composition; and a polyfunctional organic compound containing an alcohol group, a thiol group or a carboxyl group, wherein the polyfunctional organic compound is 1 weight by weight based on 100 parts by weight of the resin composition. A coating composition containing 100 parts by weight is provided.

上記の式において、
ｋは１～４の整数であり、
Ｒ、およびＲ’は、それぞれ独立して、炭素数１～２０のアルキル基、炭素数１～２０のアルキル基に連結されたアルコール基、炭素数１～２０のアルキル基に連結されたチオール基、炭素数１～２０のアルキル基に連結されたカルボキシル基、アルコール基、チオール基、またはカルボキシル基であり、
Ｘは、下記の化学式２、化学式３、化学式４、または化学式５から誘導される連結基である：

上記の式において、
ｍ、ｎ、ｏ、ｘ、およびｙは、それぞれ独立して１～１０，０００の整数である。
前記アルコール基、チオール基またはカルボキシル基を含む多官能有機化合物は、１００～１，０００，０００の分子量を有することができる。 The polyfunctional organic compound can include a compound of the following Chemical Formula 1.

In the above formula
k is an integer from 1 to 4,
R and R'are independently an alkyl group having 1 to 20 carbon atoms, an alcohol group linked to an alkyl group having 1 to 20 carbon atoms, and a thiol group linked to an alkyl group having 1 to 20 carbon atoms. , A carboxyl group, an alcohol group, a thiol group, or a carboxyl group linked to an alkyl group having 1 to 20 carbon atoms.
X is a linking group derived from formula 2, formula 3, formula 4, or formula 5 below:

In the above formula
m, n, o, x, and y are each independently an integer of 1 to 10,000.
The polyfunctional organic compound containing an alcohol group, a thiol group or a carboxyl group can have a molecular weight of 100 to 1,000,000.

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

At this time, the silsesquioxane resin may be a cage-type silsesquioxane, a ladder-type silsesquioxane, a random-type silsesquioxane, or a mixture thereof.

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

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

The film may have an average curl of 5 mm or less with four corners separated from the bottom with respect to the A4 size.

INDUSTRIAL APPLICABILITY The present invention can produce a coating composition containing a polyfunctional organic compound containing an alcohol group, a thiol group or a carboxyl group and capable of achieving low curl.

INDUSTRIAL APPLICABILITY The present invention can produce a film having less curl by using the coating composition, and is usefully applicable to various products other than those for optical films such as display panels and plastics, protective films, and electronic products. ..

The composition of the present invention can also be applied to a plastic substrate having a flexible and high hardness property that can replace a protective glass substrate of a display substrate such as an LCD or an OLED.

It is a figure which shows that the film produced by this invention forms low curl as compared with the existing film. It is a figure which shows that when the composition of this invention is cured, an organic compound which has an alcohol group, a thiol group or a carboxyl group forms a cross-linking bond and acts as a three-dimensionally buffering action.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so as to be easily carried out by a person having ordinary knowledge in the technical field to which the present invention belongs. However, the present invention can be realized in a variety of different forms and is not limited to the embodiments described herein.

When we say that a part "contains" a component throughout the specification, it may include more components rather than excluding other components, unless otherwise stated to be the opposite. means.

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

When the content of the polyfunctional organic compound containing an alcohol group, a thiol group or a carboxyl group is less than 1 part by weight, it is difficult to expect the effect of curl adjustment, and the polyfunctional organic compound containing the alcohol group, a thiol group or a carboxyl group If the content of is more than 100 parts by weight, the degree of curing may be lowered and the curing characteristics of the coating layer may not be perfect.

上記の式において、
ｋは１～４の整数であり、
Ｒ、およびＲ’は、それぞれ独立して、炭素数１～２０のアルキル基、炭素数１～２０のアルキル基に連結されたアルコール基、炭素数１～２０のアルキル基に連結されたチオール基、炭素数１～２０のアルキル基に連結されたカルボキシル基、アルコール基、チオール基、またはカルボキシル基であり、
Ｘは、下記の化学式２、化学式３、化学式４、または化学式５から誘導される連結基である：

上記の式において、
ｍ、ｎ、ｏ、ｘ、およびｙは、それぞれ独立して１～１０，０００の整数である。 In the present invention, the polyfunctional organic compound can include a compound of the following Chemical Formula 1.

In the above formula
k is an integer from 1 to 4,
R and R'are independently an alkyl group having 1 to 20 carbon atoms, an alcohol group linked to an alkyl group having 1 to 20 carbon atoms, and a thiol group linked to an alkyl group having 1 to 20 carbon atoms. , A carboxyl group, an alcohol group, a thiol group, or a carboxyl group linked to an alkyl group having 1 to 20 carbon atoms.
X is a linking group derived from formula 2, formula 3, formula 4, or formula 5 below:

In the above formula
m, n, o, x, and y are each independently an integer of 1 to 10,000.

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

When the polyfunctional organic compound contains an alcohol group, the polyfunctional organic compound is a polyester polyol, a polycarbonate polyol, a polyethylene glycol, a polypropylene glycol, a polycaprolactone polyol, a polytetramethylene glycol, a tetramethyltrimethylol, a glycerin, a pentaerythritol tetra. It can be one selected from the group consisting of alcohols, dipentaerythritol hexaalcohols, polyacrylate polyols, polyvinyl alcohols, and polyols derived from them.

When the polyfunctional organic compound contains a thiol group, the polyfunctional organic compound is 1,2-ethanedithiole, 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-methyl1,4-butanedithiol , 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 2,4,6-trimethyl, 1,3-benzenedimethanethiol, polypropylene ether glycol bis, 1,2-di It can be one or more selected from the group consisting of mercaptoethane and 1,6-dimercaptohexane.

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-imidazole dicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxydianhydride, pyridine-2,5-dicarboxylate, and diphenyl- It can be one or more selected from the group consisting of 4,4'-dicarboxylic acid salts.

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

The epoxy-based organic resin in the resin composition is not particularly limited as long as it has two or more epoxy groups in one molecule, and as an example, an alicyclic epoxy, a bisphenol A type, and an F type epoxy. , Phenol novolak type epoxy, naphthalene type epoxy, biphenyl type epoxy, cyclopentadiene type epoxy and the like. Among these, alicyclic epoxies and phenol novolac epoxies are desirable for compatibility with polyfunctional organic compounds and cured physical properties.

The acrylic organic resin in the resin composition is not particularly limited as long as it is a 2 to 12 functional acrylic organic resin having two or more acrylic groups in one molecule, and the degree of curing and curling of the cured product are not particularly limited. A 3 to 6 functional acrylic organic resin is desirable for adjustment.

The acrylic organic resin means not only acrylate but also methacrylate or all derivatives in which a substituent is introduced into acrylate or methacrylate, and examples thereof include trimethylolpropane triacrylate, trimethylolpropane ethoxytriacrylate, and glycerin propoxytri. Examples thereof include acrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate and the like.

上記の式において、
Ｒ’_１は、それぞれ独立して、Ｃ_１～Ｃ_５のアルキル基であり、
Ｒ_１１は、それぞれ独立して、水素；重水素；ハロゲン；アミン基；エポキシ基；シクロヘキシルエポキシ基；（メタ）アクリル基；チオール基；イソシアネート基；ニトリル基；ニトロ基；またはフェニル基；水素、重水素、ハロゲン、アミン基、エポキシ基、（メタ）アクリル基、チオール基、イソシアネート基、ニトリル基、ニトロ基、またはフェニル基で置換または非置換のＣ_１～Ｃ_４０のアルキル基、またはＣ_２～Ｃ_４０のアルケニル基、またはＣ_１～Ｃ_４０のアルコキシ基、またはＣ_３～Ｃ_４０のシクロアルキル基、またはＣ_３～Ｃ_４０のヘテロシクロアルキル基、またはＣ_６～Ｃ_４０のアリール基、またはＣ_３～Ｃ_４０のヘテロアリール基、またはＣ_３～Ｃ_４０のアラルキル基、またはＣ_３～Ｃ_４０のアリールオキシ基、またはＣ_３～Ｃ_４０のアリールチオール基であり、
Ｚは、１～１００，０００の整数である。 The silsesquioxane resin may be, for example, a cage-type silsesquioxane, a ladder-type silsesquioxane, a random-type silsesquioxane, or a mixture thereof, and specifically, the structure of the following chemical formula 6 Can be a ladder-type silsesquioxane with:

In the above formula
_{R'1 is an independently alkyl group of C 1 to C 5 , respectively} .
R ₁₁ is independently hydrogen; heavy hydrogen; halogen; amine group; epoxy group; cyclohexyl epoxy group; (meth) acrylic group; thiol group; isocyanate group; nitrile group; nitro group; or phenyl group; hydrogen, C ₁ to C ₄₀ alkyl groups substituted or unsubstituted with a heavy hydrogen, halogen, amine group, epoxy group, (meth) acrylic group, thiol group, isocyanate group, nitrile group, nitro group, or phenyl group, or C ₂ Alkenyl groups of ~ C ₄₀ , or alkoxy groups of C ₁ to C ₄₀ , or cycloalkyl groups of C ₃ to C ₄₀ , or heterocycloalkyl groups of C ₃ to C ₄₀ , or aryl groups of C ₆ to C ₄₀ , Or a heteroaryl group of C ₃ to C ₄₀ , an aralkyl group of C ₃ to C ₄₀ , an aryloxy group of C ₃ to C ₄₀ , or an arylthiol group of C ₃ to C ₄₀ .
Z is an integer from 1 to 100,000.

More specifically, the silsesquioxane resin of the chemical formula 6 that can be used in the present invention may be a ladder type silsesquioxane resin, and conventional techniques, for example, Korean Patent Application No. 10-2015-0031865. , Or can be manufactured by Republic of Korea Patent Application No. 10-2013-0163607, and commercially available silsesquioxane resins can also be used.

The degree of condensation of the silsesquioxane composite polymer of the present invention can be adjusted to 1 to 99.9% in order to secure excellent storage stability and obtain a wide range of applications. That is, the content of the alkoxy group bonded to the terminal and central Si can be adjusted from 50% to 0.01% with respect to the binding group of the whole polymer.

Further, in the present invention, the weight average molecular weight of the silsesquioxane composite polymer is 1,000 to 1,000,000, specifically 5,000 to 100,000, more specifically 7,000. It can be up to 50,000. In this case, the processability and physical properties of silsesquioxane can be improved at the same time.

In the coating compositions of the invention, the resin composition may further comprise one or more of the light or heat-initiated cation initiators, radical initiators, or solvents commonly used in the art. , It is possible to selectively further include additives such as a curing agent, a plasticizer, an ultraviolet blocking agent, and other functional additives to improve the curing property, heat resistance characteristics, ultraviolet blocking, and plasticizing effect.

Specifically, in the present invention, a photoinitiator can be used and may be contained in 0.1 to 20 parts by weight based on 100 parts by weight of the total weight of the resin, for example, silsesquioxane resin.

As the photoinitiator that can be used in the present invention, a photoinitiator commonly used in the art can be used, and an iron-allene complex compound, an aromatic diazonium salt, an aromatic iodonium salt, an aromatic sulfonium salt, and a pyridinium can be used. Consists of one or more cationic polymerization initiators or acetophenones, benzoins, acylphosphine oxides, titanosen, benzophenones, and thioxanthone initiators selected from the group consisting of salts and aluminum complex / silyl ethers. It can be one or more radical polymerization initiators selected from the group.

Further, the solvent that can be used in the present invention can be used without limitation as long as it is an organic solvent usually used in the art, and for example, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, butanol, 2- Alkoxy alcoholic solvents such as methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-isopropoxyethanol, ketone solvents such as acetone, methylethylketone, methylisobutylketone, methylpropylketone, 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 monopropyl ether, diethyl glycol monobutyl ether, diethylene glycol An ether solvent such as -2-ethylhexyl ether, an aromatic solvent such as benzene, toluene, and xylene can be used, and one or more of them can be mixed and used.

In the present invention, specifically, the solvent can be contained so that the solid content of the coating composition is 30% by weight to 70% by weight.

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

The film can be produced by coating a substrate with the coating composition and then irradiating with light to cure the film.

According to the present invention, in a polyfunctional organic compound-resin formed by cross-linking a photocurable resin and an organic compound having an alcohol, thiol, or carboxylic acid group, the polyfunctional organic compound is covalently bonded between molecules in the cured substance. Coating by controlling the shrinkage / expansion that occurs during photocuring by limiting the presence of appropriate intermolecular distances by sterically buffering to prevent the distance from shrinking or increasing. Layer curl can be reduced.

The film obtained by applying the coating composition to the substrate by the method presented in the present invention can be coated by easily adjusting the bending strength of the coating layer depending on the degree of bending of the substrate, and the curl of the substrate can be obtained by only one-sided coating. Remarkably less coating layer can be formed.

For example, although there may be differences in numerical values depending on the thickness of the coated coating composition and the substrate, the average value of curls in which the four corners are separated from the bottom based on the A4 size can be 5 mm or less. At this time, for the curl, after the A4 size coating film was placed on a flat surface, the average value of the heights of the four ends separated from the flat surface was taken as the curl value.

In the present invention, the curl reducing effect of the coating composition of the present invention can be expected without limitation on the base material.

As the base material applicable to the present invention, a plastic film known as a base material of a conventional optical coating film can be applied, and specifically, transparent or translucent is appropriately selected and used depending on the application. It can be, for example, polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, poly. Vinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylmethacrylate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyetherimide A film, a polyimide film, a fluororesin film, a polyamide film, an acrylic resin film, a norbornene-based resin film, a cycloolefin resin film and the like can be used.

In the case of a normal coating composition, there is a problem that the curl increases as the coating thickness increases, making it impossible to proceed with the process, or the surface of the coating film becomes non-uniform and cracks occur. However, the thickness of the coating composition of the present invention can be arbitrarily adjusted depending on the substrate, for example, it can be formed to a thickness of 1 μm to 100 μm or less, and even if the thickness is 50 μm or more, there is little curl. Easy to apply to processes and products. From the viewpoint of effectively exerting the curl phenomenon suppressing action, the thickness may be 100 μm or less, and more specifically, it may be in the range of 20 to 80 μm.

As an example, when the coating composition is applied to 5 to 100 μm, the curl of the final coating film can 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 to a thickness of 30 μm, the curl of the coating film is the average value of the four corners based on the A4 standard. When the coating composition of the present invention is applied to a polyethylene terephthalate (PET) substrate having a thickness of 0.188 mm and a thickness of 30 μm, the curl of the coating film has four corners based on A4. When the coating composition of the present invention is applied to a polymethylmethacrylate (PMMA) substrate having a thickness of 0.3 mm to a thickness of 30 μm, the curl of the coating film is based on A4 standard. When the coating composition of the present invention is applied to a triacetyl cellulose (TAC) substrate having a thickness of 0.1 mm and the average value of the four corners is 2 mm or less, the curl of the coating film is 30 μm. , The average value of the four corners may be 4 mm or less based on the A4 standard.

The coating composition can be applied onto the plastic base 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, or the like.

At the time of curing of the present invention, mercury, a metal halide compound, an LED or the like can be used as the light source of the ultraviolet lamp, and light having a wavelength of 250 to 400 nm can be used for curing the coating composition.

The coating composition according to the present invention comprises a polyfunctional organic compound containing an alcohol group, a thiol group, or a carboxyl group, a silsesquioxane resin, a photoinitiator, and a solvent so that the coating composition is formed on a base film. During coating, the buffering action of the polyfunctional organic compound can alleviate curing shrinkage and significantly reduce curl, which can improve the hardness of the film.

Hereinafter, specific examples will be presented to help the understanding of the present invention, but the following examples are merely examples of the present invention, and the scope of the present invention is not limited by the following examples. do not have.

Production Example 1
[Production Example 1-a] Production of catalyst For adjusting the acidity, a 25 wt% aqueous solution of tetramethylammonium hydroxide (TMAH), which is an amine-based basic catalyst, or potassium hydroxide (KOH), which is a metal-based basic catalyst. A 10 wt% aqueous solution was prepared as a catalyst 1a.

[Production Example 1-b] Production of silsesquioxane resin 35% by weight of 3-acrylicoxypropyltrimethoxysilane and 60% by weight of tetrahydrofuran (THF) were mixed and stirred for 10 minutes. The catalyst produced in Production Example 1-a was added dropwise to the mixed solution in an amount of about 5% by weight to carry out the reaction. After that, stirring was continued at room temperature for 5 days, and the catalyst and impurities were removed through three washing processes. Tetrahydrofuran (THF) was separated and removed from the obtained mixed solution under vacuum to produce silsesquioxane resin.

The Si-OH functional group can be confirmed through IR analysis (3,200 cm ^-1 ), and as a result of measuring the molecular weight, it can be confirmed that the produced silsesquioxane resin has a molecular weight equivalent to 4,000 styrene. rice field.

[Example]
Examples and comparative examples were carried out as follows according to the components and contents listed in Table 1 below. All compositions were matched to the thickness of the coating by using the same amount of solvent as the solid content of the resin composition and the organic compound for easy comparison between samples after coating. In Table 1 below, the unit is a part by weight.

Example 1
100 parts by weight of the silsesquioxane resin obtained in Production Example 1, a photoinitiator (trade name: manufactured by Synasia, PI-6769), 2.2 parts by weight, a silicone-based leveling additive (trade name: manufactured by BYK). , BYK-378) 0.22 parts by weight, 1 part by weight of polyhydric alcohol organic composite (trade name: Daicel, PCL-305), and 101 parts by weight of 2-isopropyl alcohol (isopoly alcohol) are mixed and coated. The composition was produced.

The coating composition was applied onto a polycarbonate substrate having a thickness of 0.3 mm, and the thickness of the final coating film was adjusted to 30 μm through drying and curing processes.

Example 2
The coating composition was prepared in the same manner as in Example 1 above, except that the content of the alcohol organic composite (trade name: Daicel, manufactured by PCL-305) was 50 parts by weight instead of 1 part by weight. And manufactured a coating film.

Example 3
The coating composition was prepared in the same manner as in Example 1 above, except that the content of the alcohol organic composite (trade name: Daicel, manufactured by PCL-305) was 100 parts by weight instead of 1 part by weight. And manufactured a coating film.

Example 4
Coating composition and coating film with the same method and composition content as in Example 1 above, except that a thiol organic composite (Showa Denko, KarenzMT PE1) was used instead of the alcohol organic composite. Manufactured.

Example 5
Coating composition and coating film with the same method and composition content as in Example 2 above, except that a thiol organic composite (Showa Denko, KarenzMT PE1) was used instead of the alcohol organic composite. Manufactured.

Example 6
Coating composition and coating film with the same method and composition content as in Example 3 above, except that a thiol organic composite (Showa Denko, KarenzMT PE1) was used instead of the alcohol organic composite. Manufactured.

Example 7
The same method and composition as in Example 3 except that 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate was used instead of the silsesquioxane resin obtained in Production Example 1. A coating composition and a coating film were produced according to the content of the substance.

Example 8
Except that a commercially available bisphenol A type epoxy resin (KE-8128, manufactured by Coron Industry Co., Ltd.) was used instead of the silsesquioxane resin obtained in Production Example 1, the same as in Example 3. Coating compositions and coating films were produced with similar methods and composition content.

Example 9
Example 3 except that trimethylolpropane triacrylate was used in place of the silsesquioxane resin obtained in Production Example 1 and IRGACURE-184 was used in place of PI-6976 as the photoinitiator. The coating composition and the coating film were produced by the same method and the content of the composition as in the above.

Comparative Example 1
Coated by the same method as in Example 1 above, except that the content of the alcohol organic composite (trade name: Daicel, manufactured by PCL-305) was 0.5 parts by weight instead of 1 part by weight. Compositions and coating films were produced.

Comparative Example 2
The coating composition was prepared in the same manner as in Example 1 above, except that the content of the alcohol organic composite (trade name: Daicel, manufactured by PCL-305) was 110 parts by weight instead of 1 part by weight. And manufactured a coating film.

Test Example The physical characteristics of the coating films produced in Examples 1 to 9 and Comparative Examples 1 and 4 are confirmed and shown in Table 2 below.

At this time, the physical properties were measured as follows.
-Pencil hardness Using a pencil hardness tester and a Mitsubishi pencil, the hardness of the coating film was measured by applying a load of 1 kg at an angle of 45 degrees. After measuring 5 times for each pencil hardness, the hardness at which scratches were generated once or less was defined as the pencil hardness of the coating film.
-When an A4 size coating film coated with the curl coating composition to a thickness of 30 μm was placed on a flat bottom, the average value of the distances at which each corner was separated from the flat surface was calculated.
-Adhesive After drawing 11 lines horizontally and vertically on the coating film at 1 mm intervals to make 100 squares, perform three peeling tests using tape (3M-810 manufactured by 3M). gone. Even after the peeling test, the number of quadrangles that were not peeled off was counted to determine the adhesiveness of the coating composition to the substrate. That is, if it is 0/100, it means that the coating composition is completely peeled off, and if it is 100/100, it means that all the adhesiveness is maintained.

As shown in Table 2 above, the coating film according to the present invention not only has excellent pencil hardness and adhesiveness as the content of the polyfunctional organic compound increases, but also does not contain the polyfunctional organic compound. It can be seen that it shows a significantly lower low curl than the example. Further, 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 low and it is not suitable for use as a coating composition.

Claims (9)

A film formed by coating a coating composition on a substrate and curing the coating composition.
The coating composition is
Contains silsesquioxane resins and polyfunctional organic compounds containing alcohol, thiol or carboxyl groups.
The polyfunctional organic compound contains 1 part by weight to 100 parts by weight with respect to 100 parts by weight of the silsesquioxane resin.
The average value of curl in a film having four corners separated from the bottom based on the A4 size is 5 mm or less.
The film. The film according to claim 1, wherein the polyfunctional organic compound contains the compound of the following chemical formula 1.

In the above formula
R and R'are independently an alkyl group having 1 to 20 carbon atoms, an alcohol group linked to an alkyl group having 1 to 20 carbon atoms, and a thiol group linked to an alkyl group having 1 to 20 carbon atoms. , A carboxyl group, an alcohol group, a thiol group, or a carboxyl group linked to an alkyl group having 1 to 20 carbon atoms.
X is a linking group derived from formula 2, formula 3, formula 4, or formula 5 below:

In the above formula
m, n, o, x, and y are each independently an integer of 1 to 10,000. The film according to claim 1, wherein the polyfunctional organic compound has a molecular weight of 100 to 1,000,000. The polyfunctional organic compound containing an alcohol group includes polyester polyol, polycarbonate polyol, polyethylene glycol, polypropylene glycol, polycaprolactone polyol, polytetramethylene glycol, tetramethyltrimethylol, glycerin, pentaerythritol tetraalcohol, dipentaerythritol hexaalcohol, and the like. The film according to claim 1, which is one selected from the group consisting of polyacrylate polyols, polyvinyl alcohols, and polyols derived from these. The polyfunctional organic compounds containing a thiol group include 1,2-ethanedithiole, 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, decandithiole, 2-methyl1,4-butanedithiol, 1,2-benzenedithiol, 1, 3-benzenedithiothane, 1,4-benzenedithiol, 2,4,6-trimethyl, 1,3-benzenedimethanethiol, polypropylene ether glycolbis, 1,2-dimercaptoethane, and 1,6-dimercapto The film according to claim 1, which is one or more selected from the group consisting of hexane. The polyfunctional organic compound containing a carboxyl group includes naphthalene 1,8-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid, and pyrrolidine-2,4-. From dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxydianhydride, pyridine-2,5-dicarboxylate, and diphenyl-4,4'-dicarboxylate. The film according to claim 1, wherein the film is one or more selected from the group. The film according to claim 1 , wherein the silsesquioxane resin is a cage-type silsesquioxane, a ladder-type silsesquioxane, a random-type silsesquioxane, or a mixture thereof. The film according to claim 1, wherein the polyfunctional organic compound and the silsesquioxane resin have a weight ratio of 1:99 to 50:50. The film of claim 1, wherein the coating composition further comprises one or more of a light or heat-initiated cation initiator, radical initiator, or solvent.

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