KR20140138807A - Resin composition for coating paint - Google Patents

Abstract

Provided is a non-aqueous resin composition which is low in bubble-forming property and excellent in defoaming property even when bubbles are generated, and therefore hardly causes defects in a coating film to be formed. Also provided is a resin composition which gives a cured film which gives excellent hardness, scratch resistance, transparency, stain resistance and durability. A resin composition comprising a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1000 or more, a hydrocarbon monomer containing at least one selected from a (meth) acryloyl group and a vinyl group, 0.01 to 25% by weight, and a solvent having an SP value of 10.0 or less.

Description

RESIN COMPOSITION FOR COATING PAINT [0001]

The present invention relates to a resin composition for a coating paint useful as a stainproofing agent having excellent hardness and scratch resistance and excellent in leveling property after a cured film is hardly bubbled in a state of a composition, And an article such as an optical recording medium. In particular, the present invention relates to a composition which gives a cured film having a sufficient performance even if it is a thin film.

The present invention relates to an optical article, particularly an optical recording medium such as a read-only optical disk, an optical recording disk, a magneto-optical recording disk or the like, or a transparent article for an optical display such as a touch panel or a liquid crystal television.

Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene copolymer (ABS), methyl methacrylate-styrene copolymer (MS resin), acryl Styrene resins such as styrene-butadiene styrene copolymer, styrene-butadiene styrene copolymer, styrene-butadiene styrene copolymer, styrene-butadiene styrene copolymer, styrene-butadiene styrene copolymer, Such as an instrument panel, an outer panel, a window, a roofing material, a packaging material, various housing materials, an optical disk substrate, a plastic lens, a substrate for a display device such as a liquid crystal display, a plasma display and a projection TV.

However, these plastic products are susceptible to damage because of their low surface hardness, and in the case of transparent resins such as polycarbonate and polyethylene terephthalate, the inherent transparency or appearance of the resin is remarkably impaired, and wear resistance is required It is difficult to use the plastic product in the field. For this reason, there is a demand for a surface hardened film (covering material) for imparting abrasion resistance by increasing the surface hardness of these plastic products.

Such a surface-hardened film is usually obtained by dissolving or suspending the resin composition in a solvent, applying it to the surface of the product in the form of a paint, and then curing it. When a coating film is obtained by coating and further a cured film is obtained, leveling property is required for the resin composition. If the leveling property is inferior, a so-called cratering or a spot defect on the surface called "cratering" may occur in the coating film or the cured film, which may be a serious obstacle in the production of the cured film. Examples of causes of the cratering include those in which bubbles are generated in the coating liquid or the coating film, and those in which bubbles are hard to disappear.

In general, bubbles are likely to be generated with respect to water-based paints, and measures are taken to solve the above-mentioned problem of cratering. For example, in a water-based paint containing a surfactant, it is known to contain saturated hydrocarbons in order to eliminate bubbles caused by the surfactant (Patent Document 1). On the other hand, it has been considered that conventional non-aqueous paints are difficult to generate bubbles in general because it is general that non-polar solvents are used.

However, surface hardening films used for large-screen flat panel TV displays such as optical discs, touch panel displays, liquid crystal televisions, and plasma TVs are required to impart not only surface hardness and durability but also stain resistance at a high level. In optical products such as next-generation optical information media and touch panels, there has recently been a serious problem that contaminants such as fingerprint contamination affect not only appearance but also performance.

In such a situation, development of a resin composition for a non-aqueous coating paint containing a fluorine-based compound having an active energy ray-curable group has been made, and a cured film obtained by curing the resin composition has attracted attention because it exhibits excellent stain resistance For example, Patent Document 2). The present inventors have also found that a specific copolymer containing a specific perfluoroalkyl group and an epoxy group or a (meth) acrylic acid reaction product thereof is effective as a pollution imparting agent having excellent polishability and durability (Patent Documents 3 to 4).

Japanese Patent Application Laid-Open No. 2001-261908 Japanese Laid-Open Patent Publication No. 2005-112900 International publication 2006/059702 Brochure Japanese Laid-Open Patent Publication No. 2009-102513

However, while developing a resin composition containing a polymer having a fluoroalkyl group and a hydroxyl group, the inventors of the present invention have found that since they are generally non-aqueous paints that are thought to be difficult to generate bubbles, The leveling property is deteriorated. Therefore, there has been a new problem of improving the leveling property of the obtained coating film or cured film.

Sufficient bubble resistance can not be obtained only by adding saturated hydrocarbons as in Patent Document 1 for water-based paints. In addition, the above polymer has low solubility in saturated hydrocarbons, and when the amount of saturated hydrocarbons to be added is increased, the transparency of the cured film obtained by clouding is impaired, so that it is difficult to apply the polymer to a coating material for optical articles.

In order to suppress the formation of bubbles in the composition, various additives are generally added as a defoaming agent. However, such an additive is usually a solid component in many cases, and may affect the properties of a coating film or a cured film obtained from the resin composition. In addition, many additives are expensive and there is a problem in that the cost is increased in industrial production. In addition, when there is an imbalance between the constitutional components of the resin composition and poor compatibility between the resin composition and the additive, there is a possibility that the properties of the resin composition itself may be deteriorated. The additives must be individually selected for each resin composition, There is a demand for a fouling method which can be applied to the entire non-aqueous coating material, which is a resin composition containing a polymer having an alkyl group and a hydroxyl group, without hindering its properties.

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide a non-aqueous resin composition which is small in bubble-forming property and excellent in defoaming property even when bubbles are generated and consequently hardly causes defects in the formed coating film The purpose. It is another object of the present invention to provide a resin composition which gives a cured film which gives excellent hardness, scratch resistance, transparency, stain resistance and durability.

The present invention also provides a cured product of such a composition and an article having the cured product on the surface thereof, particularly an article for optical use such as an optical recording medium and a touch panel display, which has high hardness and abrasion resistance on the surface, , An article having excellent stain resistance and durability against stain resistance.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, they have found that a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1,000 or more and one or two kinds selected from a (meth) acryloyl group and a vinyl group Of a hydrocarbon monomer, a specific amount of a saturated hydrocarbon, and a solvent having a SP (Solubility Parameter) value of 10.0 or less, so that the bubble generation property of the resin composition can be reduced.

Also, a hydrocarbon monomer having a hydroxyl group and a fluoroalkyl group, a polymer having a weight average molecular weight of 1000 or more, a hydrocarbon monomer containing at least one selected from a (meth) acryloyl group and a vinyl group, m < 2 > / m < 2 > or more, and a solvent having an SP value of 10.0 or less, the bubble generating property of the resin composition can be reduced.

When the polymer has a polysiloxane structure and the silicon at the terminal of the polysiloxane structure or a saturated hydrocarbon group bonded to the silicon is bonded to the main chain of the polymer via an oxygen atom or a sulfur atom, The present invention has been accomplished on the basis of these findings.

That is, the present invention is as follows.

[1] A polymer composition comprising a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1000 or more, a hydrocarbon monomer containing at least one member selected from a (meth) acryloyl group and a vinyl group, a saturated hydrocarbon having a saturated hydrocarbon of 0.01 To 25% by weight, and an SP value of 10.0 or less.

[2] The resin composition according to [1], wherein the saturated hydrocarbon has 5 to 18 carbon atoms.

(3) a hydrocarbon monomer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1000 or more, a hydrocarbon monomer containing one or more selected from a (meth) acryloyl group and a vinyl group, A resin having a fluorine group-containing oligomer of 2 mN / m or more and a solvent having an SP value of 10.0 or less.

[4] The resin composition according to any one of [1] to [3], wherein the polymer has a hydroxyl group content of 0.2 to 5.0% by weight.

[5] The resin composition according to any one of [1] to [4], wherein the content of fluorine atoms in the polymer is 1.0 to 34.0% by weight.

[6] The resin composition according to any one of [1] to [5], wherein the polymer has an unsaturated double bond group in a side chain.

[7] The resin composition according to any one of [1] to [6], wherein the polymer has a polysiloxane structure.

[8] The resin composition according to [7], wherein the silicon at the terminal of the polysiloxane structure or the saturated hydrocarbon group bonded to the silicon is bonded to the main chain of the polymer through an oxygen atom or a sulfur atom.

[9] The resin composition according to any one of [1] to [8], wherein the hydrocarbon-based monomer is a polyfunctional (meth) acrylate having at least three (meth) acryloyl groups in one molecule.

[10] The resin composition according to any one of [3] to [9], wherein the fluorine group-containing oligomer has a weight average molecular weight of 5000 or more.

[11] The resin composition according to any one of [3] to [10], wherein the fluorine group-containing oligomer is nonionic.

[12] The resin composition according to any one of [3] to [11], wherein the content of the fluorine group-containing oligomer in the resin composition is 0.005 to 10% by weight based on the whole resin composition.

[13] The organic electroluminescent device described in any one of [1] to [12], wherein the solvent is at least one solvent selected from the group consisting of a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent and an aromatic hydrocarbon solvent ≪ / RTI >

[14] The resin composition according to any one of [3] to [13], which contains saturated hydrocarbons having 5 to 18 carbon atoms.

[15] The resin composition according to any one of [1] to [14], which contains a radical polymerizable photoinitiator.

[16] A cured product obtained by curing the composition according to any one of [1] to [15].

[17] The cured product according to [16], which is obtained by irradiating the composition with an active energy ray.

[18] A molded article having the cured product according to [16] or [17].

[19] A molded article according to [18], which is used for optical purposes.

[20] A laminated chain for an optical recording medium or an optical display, as described in [19].

According to the present invention, there is provided a resin composition which is low in bubble generation property and bubbles to be generated, and which is excellent in defoaming property and therefore hardly causes defects in the formed coating film. Further, when it is coated thinly on the surface of an article or the like and cured, the article or the like provides a cured film which gives excellent hardness, scratch resistance, transparency, stain resistance and durability.

Therefore, the resin composition of the present invention is suitable for a wide range of applications such as protection of the surface of an optical recording medium, optical display such as a touch panel and a flat display, protection of a transparent part of a mobile phone casing, automotive transparent part protection, .

Hereinafter, the embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of the embodiment of the present invention, and the present invention is not limited to these embodiments, It is possible to carry out various modifications within the scope of the present invention. Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, " " is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

The term " polymerization " in the present invention is broad-spectrum polymerization including so-called " copolymerization " Therefore, in the present invention, the term " polymer " also includes " copolymer ".

The term " room temperature " in the present invention refers to a temperature at a place where the experiment is conducted, for example, at a temperature of 15 to 30 캜, more preferably 20 to 25 캜.

The " normal oxygen concentration " means 18 to 22%, more preferably 19 to 21%.

The term "(meth) acrylate" means "acrylate and / or methacrylate", and the same applies to "(meth) acryloyl" and "(meth) acrylate".

<1. Resin composition>

The resin composition (hereinafter abbreviated as &quot; the resin composition (A) related to the present invention &quot; in some cases) may be a polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1000 or more, ) Acryloyl group and a vinyl group, a solvent containing 0.01 to 25% by weight of a saturated hydrocarbon and an SP value of 10.0 or less as essential components.

The resin composition (hereinafter abbreviated as &quot; the resin composition (B) related to the present invention &quot; in some cases) may be a polymer having a hydroxyl group and a fluoroalkyl group, (Meth) acryloyl group and vinyl group, a fluorine group-containing oligomer having a surface tension lowering ability of 2 mN / m or more, and a solvent having an SP value of 10.0 or less are required .

<1-1. Polymers>

The polymer which is an essential component of the resin composition of the present invention has a hydroxyl group and a fluoroalkyl group and has a weight average molecular weight of 1000 or more. The weight average molecular weight is not particularly limited as long as it is 1,000 or more, but is preferably 1,000 to 30,000, more preferably 1,000 to 20,000. Here, the weight average molecular weight is measured using GPC (HLC-8120 GPC manufactured by TOSOH Corporation), tetrahydrofuran as a solvent, and polystyrene as a standard sample.

It is preferable that the polymer has an unsaturated double bond group in the side chain from the viewpoint of curing of the resin composition.

In addition, the above-mentioned polymer preferably has a polysiloxane structure from the viewpoint of imparting leveling property, slipperiness and releasability to the cured film. In this case, it is more preferable that the silicon at the terminal of the polysiloxane structure or a saturated hydrocarbon group bonded to the silicon is bonded to the main chain of the polymer through an oxygen atom or a sulfur atom.

The polymer in the resin composition of the present invention can be produced by polymerizing a polymerizable monomer described below. A preferred method for producing the polymer is described below.

Hereinafter, the amount (parts by weight) of each component in 100 parts by weight of the monomer mixture as the raw material for producing the polymer of the present invention may be referred to as the &quot; usage amount &quot;.

As a polymerizable monomer for producing a polymer, firstly, a (meth) acrylate having a hydroxyl group is described. Examples of some representative examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, pentaerythritol triacrylate, and the like, but are not limited to them at all, Or a monomer having a functional group to be produced. When the amount of the (meth) acrylate having a hydroxyl group is too small, the hardness of the cured film obtained from the resin composition is decreased, which is not preferable.

With respect to the monomer having a functional group that generates a hydroxyl group by the reaction, examples of such a reaction include a reaction between an epoxy group and a carbonyl group, a ring-opening reaction or addition reaction of an oxysilane skeleton, and the like.

Examples of (meth) acrylates having an epoxy group include (meth) acrylate having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate, 3,4-epoxycyclohexyl acryl (Meth) acrylate in which an epoxy group is directly bonded to an alicyclic structure such as 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate, Rate, but is not limited to them at all.

Of these, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate and the like are preferable in terms of easiness to obtain and ease of modification with (meth) -Epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate and the like are particularly preferable.

These (meth) acrylates having an epoxy group may be used singly or in combination of two or more kinds.

When the amount of the (meth) acrylate having an epoxy group is small, it is possible to exhibit an effect of improving the hardenability, the hardening effect and the surface hardenability by the photo radical polymerization by the modification of the carboxylic acid having the (meth) acryloyl group When the amount is too large, there is a case where the viscosity of the polymer solution and the liquid stability are lowered. In addition, neither the hardening property nor the hardening of the upper layer can be seen.

Examples of some representative examples of (meth) acrylates having a carbonyl group include acrylic acid, methacrylic acid, succinic acid-modified pentaerythritol triacrylate, and the like, but are not limited thereto at all.

In the resin composition (A) or the resin composition (B) according to the present invention, the lower limit is preferably 0.2% by weight or more, more preferably 0.4% by weight or less, More preferably 0.5% by weight or more, particularly preferably 0.7% by weight or more, and most preferably 1.0% by weight or more. The upper limit is preferably 5.0% by weight or less, more preferably 4.0% by weight, further preferably 3.5% by weight or less, and most preferably 3.0% by weight.

In the production of the polymer, the amount of the monomer having a hydroxyl group is adjusted so as to be within this range.

Further, in the monomer mixture for producing the polymer, the amount of the monomer having a hydroxyl group with respect to the whole monomer is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.

Monomers having fluoroalkyl groups are described as monomers for use in the production of polymers. As such a monomer, a (meth) acrylate containing a fluoroalkyl group is preferably exemplified. The (meth) acrylate containing a fluoroalkyl group is not particularly limited, but a (meth) acrylate containing a fluoroalkyl group other than (meth) acrylate having a linear chain perfluoroalkyl group having at least 8 carbon atoms is preferable Do. When a large amount of (meth) acrylate having a linear chain of perfluoroalkyl groups is used, the bubble-forming property of the polymer solution of the present invention or the composition solution using the polymer is remarkably increased, . In addition, (meth) acrylates having a linear chain perfluoroalkyl group having at least 8 carbon atoms are not necessarily used.

Examples of the (meth) acrylate having a preferable fluoroalkyl group include (meth) acrylates having a linear chain fluoroalkyl group having 4 to 7 carbon atoms, and examples thereof include perfluorohexylethyl (meth) acrylate , A (meth) acrylic acid adduct of perfluorohexyl glycidyl ether, and a (meth) acrylic acid adduct of perfluoroheptyl glycidyl ether. Examples of the (meth) acrylate having 6 or more carbon atoms and a fluoroalkyl group having a difluoromethyl group at the end include, for example, 1H, 1H, 7H-dodecafluoroheptyl (meth) 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate and the like are preferable.

Of these, (meth) acrylates having a linear or saturated fluoroalkyl group having 6 carbon atoms such as perfluorohexylethyl (meth) acrylate, (meth) acrylic acid esters of perfluorohexylglycidyl ether Water is particularly preferred.

These (meth) acrylates having a fluoroalkyl group may be used singly or in combination of two or more kinds.

Examples of the (meth) acrylate having a linear chain perfluoroalkyl group having at least 8 carbon atoms include perfluorooctylethyl (meth) acrylate, perfluorodecylethyl (meth) acrylate, 2- (Meth) acrylic acid adduct of perfluorooctylglycidyl ether, and (meth) acrylic acid adduct of perfluorooctylglycidyl ether, and the like. .

In the resin composition (A) or the resin composition (B) related to the present invention, the lower limit of the content is preferably 1.0% by weight or more, more preferably 4.0% by weight More preferably at least 4.5% by weight, particularly preferably at least 5.0% by weight, most preferably at least 10.0% by weight. The upper limit value is preferably 34.0 wt% or less, more preferably 30.0 wt% or less, and further preferably 25.0 wt%. If the content of fluorine atoms is less than this lower limit, the effect of improving the oil resistance and stain resistance derived from the oil repellency of the fluoroalkyl group is not sufficiently manifested. If the content exceeds the upper limit, the compatibility of the polymer with other components may deteriorate, There is a possibility that the hardness of the film is lowered and the scratch resistance and pencil hardness of the surface are lowered. In the production of the polymer, the amount of the monomer having a fluoroalkyl group is adjusted so as to fall within this range.

The amount of the (meth) acrylate having a perfluoroalkyl group to the whole monomer in the monomer mixture for producing the polymer is preferably 80.0% by weight or less, and more preferably 60.0% by weight or less.

It is preferable that the polymer of the present invention has a polysiloxane structure as described above. Here, the polysiloxane structure preferably has a repeating structural unit represented by the following general formula (1).

- (SiR ¹ R ² -O) - (1)

Wherein R &lt; ¹ &gt; and R &lt; ^{2 &} Each independently represents an alkyl group which may have a substituent or a phenyl group which may have a substituent, preferably an alkyl group which may be substituted with a hydroxyl group or an alkoxy group (more preferably, the alkoxy group and the alkyl group have 1 to 3 carbon atoms More preferably an alkyl group having 1 to 3 carbon atoms, which has no substituent, and is most preferably a methyl group.

In the present invention, the polymer having a polysiloxane structure is preferably a polymer having, in addition to the hydroxyl group or the epoxy group and the fluoroalkyl group, at least a part of the epoxy group of the radical polymer of the monomer mixture containing (meth) acrylate or dimercaptan having a polysiloxane structure , A carboxylic acid having a (meth) acryloyl group, or a polymer having a structure corresponding to a structure obtained by reacting a carboxyl group having a polysiloxane structure with at least a part of an epoxy group of a radical polymer of a monomer mixture having a hydroxyl group and a fluoroalkyl group Is a polymer having a structure corresponding to a structure formed by reacting a carboxylic acid, a carboxylic acid, a malonic acid, a carboxylic acid,

The monomer used in the production of the polymer having such a polysiloxane structure is preferably (meth) acrylate or dimercaptan having a polysiloxane structure in which two or more repeating structural units represented by the above formula (1) are connected. Examples of such monomers include polydimethylsiloxane having a methacryloyl group at one end ("Saifrafene FM-0725" manufactured by JNC (formerly JNC), polydimethylsiloxane having methacryloyl groups at both terminals (X-22-164A, manufactured by Shin-Etsu Chemical Co., Ltd.), polydimethylsiloxane having epoxy groups at both terminals, polydimethylsiloxane having epoxy groups at both terminals and side chains, polydimethylsiloxane derivative having an acryloyl group in the side chain (For example, &quot; DMS-U22 &quot; manufactured by Gelest) having an acryloyl group at both ends, polydimethylsiloxane having a mercapto group at both terminals (For example, &quot; X-22-167B &quot; manufactured by Shin-Etsu Chemical Co., Ltd.), copolymers having polydimethylsiloxane in the main chain or side chain and having an acryloyl group and / or an epoxy group at the side chain and / .

It is preferable that the polysiloxane structure of the polymer of the present invention has a terminal silicon or a saturated hydrocarbon group bonded to the silicon bonded to the main chain of the polymer via an oxygen atom or a sulfur atom as described above. Examples of the monomer having a polysiloxane structure for producing such a polymer include methacrylates such as dimethylpolysiloxyl methacrylate,? -Butyl-? - (3-methacryloxypropyl) polydimethyl Siloxane, and are not limited thereto. Examples of dimercaptans include α, ω-dimercapto-polydimethylsiloxane, α, ω-dimercaptopro- diethylsiloxane, α, ω-dimercapto-polymethylethylsiloxane, α, ω-dimercaptopolididic hydroxymethylsiloxane, α, ω-dimercaptopolidimethoxymethylsiloxane, and the like. Among these,?,? - dimercapto-polydimethylsiloxane is preferred, and the mercapto group may be directly bonded to the polysiloxane group or may be connected to the polysiloxane group via an alkylene group. More preferably, it is a polysiloxane (?,? - dimercapto-polydimethylsiloxane) having a mercapto group linked to a polysiloxane group via a propylene group. However, the present invention is not limited thereto.

(Meth) acrylate or dimercaptan having a polysiloxane structure preferably has a number average molecular weight of about 1000 to 10000 in order to balance contamination and hardness. Here, the number average molecular weight is measured using GPC (HLC-8120GPC manufactured by Toso Co., Ltd.), tetrahydrofuran as a solvent, and polystyrene as a standard sample.

(Meth) acrylate or dimercaptan having a polysiloxane structure may be used singly or in combination of two or more kinds.

The amount of the (meth) acrylate or dimercaptan having a polysiloxane structure is preferably 0.01 to 30% by weight, more preferably 0.1 to 25% by weight, more preferably 0.1 to 25% by weight based on the total amount of monomers in the monomer mixture for producing the polymer 1 to 20% by weight. When the amount of the (meth) acrylate or dimercaptane having a polysiloxane structure is less than 0.01% by weight, the impartation of stain resistance is insufficient. When the amount exceeds 30% by weight, compatibility of the obtained polymer with other components Uniform compatibility and compatibility with other components of the polymer when the composition is formed into a composition) is lowered or the hardness of the cured film is lowered.

Preferably, the amount of (meth) acrylate or dimercaptan having a polysiloxane structure is 0.1% by weight or more, more preferably 1% by weight or more.

The amount of (meth) acrylate or dimercaptan having a polysiloxane structure is preferably 25% by weight or less, more preferably 20% by weight or less.

The monomer mixture prepared at the time of producing the polymer of the present invention may contain other (meth) acrylate. The other (meth) acrylate is not particularly limited, but it preferably has a low reactivity with an epoxy group, does not lower the stability of the resulting polymer, or has a rigid skeleton and does not lower its hardness, And so on.

Some examples of such other (meth) acrylates are styrene, its lower alkyl (having 1 to 4 carbon atoms), alkenyl group substituted derivatives, alkyl (meth) acrylates having 1 to 20 carbon atoms, alkyl (Meth) acrylamides, cycloalkyl (meth) acrylates having (poly) cycloalkyl side chains of 5 to 20 carbon atoms, and (meth) acrylamides.

The other (meth) acrylates may be used singly or in combination of two or more.

The other (meth) acrylate is used in an amount of 50% by weight or less. If the amount of other (meth) acrylate used exceeds 50% by weight, the hardness of the polymer is lowered, and the surface damage and pencil hardness are lowered.

Preferably, the other (meth) acrylate is used in an amount of 45% by weight or less, more preferably 40% by weight or less.

In the production of the polymer of the present invention, the above-mentioned mixture of monomers is subjected to radical polymerization, but in order to improve the uniformity of the reaction, a solvent may be added to the monomer mixture.

Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA) and isobutanol, ethylene glycol dimethyl ether , Propylene glycol monomethyl ether and the like; esters such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene; and water as preferred examples .

These solvents may be used singly or in combination of two or more kinds.

In the radical polymerization of the monomer mixture containing the above-described components, it is preferable to use a radical polymerization initiator.

As the radical polymerization initiator, known initiators generally used for radical polymerization can be used, and organic peroxides such as benzoyl peroxide and di-t-butyl peroxide, 2,2'-azobisbutyronitrile, 2,2'- Azo compounds such as azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).

These radical polymerization initiators may be used singly or in combination of two or more kinds.

The method of mixing and dissolving the monomer component and the solvent when the radical polymerization is carried out using a solvent and a radical polymerization initiator in addition to the monomer mixture containing the above-mentioned components is not particularly limited, , It is preferable to initiate polymerization by adding a radical polymerization initiator within a certain period of time, preferably within 3 hours, after mixing the monomer component and the solvent.

The total concentration of the monomer components in the reaction liquid to be added to the radical polymerization is preferably 10% by weight or more and 60% by weight or less, and the radical polymerization initiator is preferably 0.1% by weight or more , More preferably not less than 0.2 wt%, preferably not more than 10 wt%, and more preferably not more than 2 wt%.

The preferred polymerization conditions are different depending on the radical polymerization initiator to be used, but the polymerization temperature is 20 to 150 占 폚, the polymerization time is 1 to 72 hours, more preferably the polymerization temperature is 50 to 100 占 폚, 3 to 36 hours.

The polymer in the present invention is a polymer obtained by adding at least a part of the epoxy group of the radical polymer obtained as described above to a carboxylic acid having a (meth) acryloyl group, preferably 1 to 5 (meth) acryl It is preferable to add a carboxylic acid having a diazo group. This is because the (meth) acryloyl group becomes a crosslinking point and the polymer takes a crosslinked structure, thereby improving the wiping property of the contaminant and the durability thereof.

Examples of the carboxylic acid having a (meth) acryloyl group used herein include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid , Adducts of acid anhydrides such as pentaerythritol tri (meth) acrylate and succinic anhydride, phthalic anhydride and hexahydrophthalic anhydride, dipentaerythritol penta (meth) acrylate and succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride , And the like. These may be used alone or in combination of two or more.

In this addition reaction, an epoxy group contained in the radical polymer reacts with a carboxyl group of a carboxylic acid having a (meth) acryloyl group.

Examples of the carboxylic acid having a (meth) acryloyl group and a radical polymer include a ratio of an epoxy group of a radical polymer to a carboxyl group of a carboxylic acid having a (meth) acryloyl group (hereinafter sometimes simply referred to as "epoxy group / carboxyl group" ) Is 1 or more. The epoxy group / carboxyl group is preferably 10 or less, more preferably 5 or less, still more preferably 2 or less.

If the epoxy group / carboxyl group is lower than the lower limit, it is possible to prevent the stability from being lowered by the carboxylic acid having a (meth) acryloyl group remaining unreacted. If the upper limit is exceeded, the stability of the epoxy group remaining It is preferable.

It is also preferable that 50 to 99% of the epoxy groups of the radical polymer react with the carboxyl group of the carboxylic acid having a (meth) acryloyl group, more preferably 70 to 98%.

The addition reaction is preferably carried out at 50 to 110 ° C for 3 to 50 hours, more preferably at 80 to 110 ° C for 3 to 30 hours.

In the present reaction, in order to accelerate the reaction, a known catalyst such as triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride and triphenylphosphine One or more of them may be used. The amount thereof is preferably 0.01% by weight or more, more preferably 0.05% by weight or more based on the total amount of the reaction mixture (that is, the total of the radical polymer and the carboxylic acid having a (meth) acryloyl group). The content is preferably 2% by weight or less, more preferably 1% by weight or less.

In this reaction, in order to prevent radical polymerization of the (meth) acryloyl group-containing carboxylic acid with the (meth) acryloyl group, for example, hydroquinone, hydroquinone monomethyl ether, catechol, pt -Butyl catechol, phenothiazine, and the like are preferably used. The amount of the polymerization inhibitor to be used is preferably 0.01% by weight or more, more preferably 0.05% by weight or more based on the reaction mixture. The content is preferably 1% by weight or less, more preferably 5% by weight or less.

The method for producing a polymer according to the present invention has been described above with specific examples. However, the polymer in the present invention may have the structure described above, and is not limited to those obtained by the above production method.

The resin composition of the present invention may contain only one kind of the above-mentioned polymers, or two or more kinds of them.

The content of the polymer in the composition of the present invention is preferably 0.5% by weight or more, more preferably 1% by weight or more, and still more preferably 1% by weight or more, though it varies depending on the use of the composition, the type of polymer used, By weight is 20% by weight or less, more preferably 15% by weight or less. When the content of the polymer is 0.5% by weight or more, the stain resistance is better. When the content is 20% by weight or less, the hardness is increased and the coating property is excellent.

<1-2. Hydrocarbon-based monomers>

The hydrocarbon-based monomer which is an essential component of the resin composition of the present invention contains one or more kinds selected from a (meth) acryloyl group and a vinyl group, and preferably contains a (meth) acryloyl group.

This component imparts good hardness to the cured film obtained from the resin composition. The term "hydrocarbon-based monomer" in the present specification may contain a bond containing atoms other than carbon and hydrogen.

Examples of the hydrocarbon-based monomer containing a vinyl group include styrene, p-chlorostyrene, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, ethylene glycol di Vinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified bisphenol A divinyl ether, pentaerythritol trivinyl Ether, dipentaerythritol hexa vinyl ether, and ditrimethylol propane polyvinyl ether.

Examples of the hydrocarbon-based monomer containing a (meth) acryloyl group include those having one or more (meth) acryloyl groups per molecule.

(Meth) acrylic acid, alkyl (meth) acrylates (C ₁ -C ₁₈ ), phenoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate having one (meth) acryloyl group in one molecule (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl Hydroxyethyl (meth) acryloylphosphate, tetrahydrofurfuryl ( (Meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentadienethoxy (meth) acrylate, p-benzylphenoxyethyl (Meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (Meth) acrylate, 2-hydroxy-3-octyloxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol 400 mono ) Ethyl (meth) acrylate, and CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ .

(Meth) acryloyl group in the molecule, it is generally known in the art as polyfunctional (meth) acrylate or special (meth) acrylate, prepolymer, base resin, oligomer , Or an acrylic oligomer, and specifically includes the following (i) to (v).

(i) a polyfunctional (meth) acrylate having two or more (meth) acrylic acid bound to a polyhydric alcohol.

(ii) a polyester acrylate in which two or more (meth) acrylic acids are bonded to a polyester polyol obtained by the reaction of a polyhydric alcohol with a polybasic acid.

Examples of the polyhydric alcohol in (i) and (ii) include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, Pentaerythritol, dipentaerythritol, and the like. Examples of the polybasic acid include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alkenylsuccinic acid and the like.

(iii) an epoxy acrylate obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid to obtain a (meth) acryloyl group as a functional group.

Examples of the epoxy resin in (iii) include bisphenol A-epichlorohydrin type, phenol novolac-epichlorohydrin type, and alicyclic resin.

(iv) A polyurethane acrylate obtained by reacting a polyfunctional isocyanate compound with a hydroxyl group-containing (meth) acrylate.

Examples of the polyvalent isocyanate compound in (iv) include those having a structure such as polyester, polyether, and polyurethane at the central part of the molecule and containing isocyanate groups at both ends.

(v) Other examples include polyether (meth) acrylate, melamine (meth) acrylate, alkyd (meth) acrylate, isocyanurate (meth) acrylate and silicone (meth) acrylate.

Examples of these more specific compounds are 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di Acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) (3 '' - acryloxyethoxy-2'-hydroxypropyl) 5,5-dimethylhydantoin, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra Mat (Acryloxyethyl) isocyanurate, FA-731A, manufactured by Hitachi Chemical Co., Ltd.), dipentaerythritol monohydroxypenta (meth) acrylate, tris (acryloxyethyl) isocyanurate, bis (2) to (7) (wherein R &lt; ₆ &gt; Is H or -CH ₃ , And n and x each represent an integer of 1 to 10). However, the present invention is not limited thereto.

[Chemical Formula 1]

In the present invention, among those having at least two (meth) acryloyl groups in one molecule, polyfunctional (meth) acrylates having at least three (meth) acryloyl groups are more preferable. This is because the hardness of the cured film obtained from the resin composition can be further improved by using such a hydrocarbon-based monomer.

Specific examples include pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (Meth) acrylate, polyepoxy (meth) acrylate, isocyanurate ring (meth) acrylate, polyoxyethylene (meth) acrylate, ditrimethylolpropane tetra (For example, Toon Synthesis, Aronix M315, M313, and the like) having a hydroxyl group and a hydroxyl group, but are not limited thereto. Of these, polyfunctional acrylates are preferred from the viewpoint of satisfactory performance such as hardness and tris (acryloxyethyl) isocyanurate, bis (acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

The various hydrocarbon-based monomers exemplified above may be used singly or in combination of two or more kinds.

The content of the total amount of these components in the composition is not specifically defined as far as it does not deviate from the object of the present invention. However, when the composition is used as a composition requiring particularly high hardness, the weight ratio of the hydrocarbon monomer / More polymer than 99.9 / 0.1, more preferably more polymer than 99/1, less polymer than 50/50, less polymer than 80/20, in particular less polymer than 85/15 . By setting the polymer to not more than the upper limit, a higher hardness can be maintained with respect to the resulting cured product, and when it is not lower than the lower limit, it is possible to exhibit better stain resistance to the obtained cured product.

<1-3. Saturated hydrocarbons>

The saturated hydrocarbon which is an essential component of the resin composition (A) according to the present invention can be widely known, and preferably has 5 to 18 carbon atoms. Those having a carbon number of less than 5 are gases at room temperature and those having a carbon number of 18 or more are solid at room temperature and are difficult to handle. Preferred examples thereof include hexane, heptane, octane, cyclohexane, cycloheptane and the like.

The resin composition (B) according to the present invention also preferably contains saturated hydrocarbons. As in the case of the resin composition (A) related to the present invention, saturated hydrocarbons can be widely known, and the number of carbon atoms is preferably 5 to 18.

The content of the saturated hydrocarbon in the resin composition (A) according to the present invention is 0.01 to 25% by weight, preferably 0.5% by weight or more, and more preferably 1% by weight or more.

The content of the saturated hydrocarbon in the resin composition (B) according to the present invention varies depending on the use of the composition, the type of polymer used, and the composition of other components, but is preferably 0.01% by weight or more, more preferably 0.5% More preferably not less than 1% by weight, further preferably not more than 25% by weight, more preferably not more than 23% by weight, particularly preferably not more than 20% by weight. When the content of the polymer is less than this lower limit, defoaming property is not imparted. If the content of the polymer is higher than this upper limit, there is a possibility that the polymer is precipitated.

In the resin composition of the present invention, it is preferable that the polymer and the saturated hydrocarbon, which are essential components, are in a weight ratio of 5: 1 to 1:20. When the ratio is in this range, the bubble generation property of the resin composition is easily suppressed by the interaction of the two components, and the bubble resistance tends to be improved.

<1-4. Fluorine group-containing oligomer having a surface tension lowering ability of 2 mN / m or more>

The known fluorine group-containing oligomer having a surface tension lowering ability of 2 mN / m or more, which is an essential component of the resin composition (B) according to the present invention, can be widely used. Here, the surface tension lowering ability refers to a decrease in the surface tension of PGMAc (1-methoxypropyl-2-propanol) when the fluorine group-containing oligomer is dissolved in 1 mass% Tension &quot; - &quot; surface tension of 1% PGMAc solution &quot;).

The upper limit of the upper limit is preferably 15 mN / m or less, more preferably 12 mN / m or less, particularly preferably 10 mN / m or less, although the surface tension lowering ability of the fluorine group-containing oligomer is not particularly limited as long as it is 2 mN / m or less. The lower limit value is preferably 2 mN / m or more, more preferably 3.5 mN / m or more, particularly preferably 5 mN / m or more. If the upper limit is lower than the upper limit, it is preferable because the compatibility is good, and if it is lower than the lower limit, it is preferable because the foaming property is good. In addition, the surface tension lowering ability is a value calculated by using a surface tension meter ("Drop Master series" manufactured by Kyowa Interface Science Co., Ltd.). The surface tension lowering ability is a numerical value determined by the molecular structure of the additive. When the fluorine atom or Si atom is present, the surface tension lowering ability tends to increase, and when the polar group is included in large amount, the surface tension lowering ability tends to decrease .

The lower limit of the weight average molecular weight is preferably 5000 or more, more preferably 6000 or more, particularly preferably 7000 or more, even though the fluorine group-containing oligomer is not particularly limited as far as the surface tension lowering ability is 2 mN / Or more. The upper limit value is preferably not more than 40,000, more preferably not more than 20,000, and particularly preferably not more than 15,000. If the upper limit is not exceeded, compatibility with other components is preferable. If it is at least the lower limit, it is preferable because the bubble resistance is good. Here, the weight average molecular weight refers to a value measured by using GPC (HLC-8120GPC manufactured by Toso Co., Ltd.), tetrahydrofuran as a solvent, and polystyrene as a standard sample.

It is preferable that the fluorine group-containing oligomer does not contain an acryloyl group because the oligomer has good defoaming property.

Further, the fluorine group-containing oligomer is preferably nonionic in that it is excellent in defoaming property. Specifically, there may be mentioned, for example, Futagonto 710FM of Neos, Megapak F-555 of DIC, and NS-9013 of Daikensha. A plurality of oligomers may be used in combination.

The content of the fluorine group-containing oligomer in the resin composition (B) according to the present invention is not particularly limited as long as it does not deviate from the object of the present invention, but it is preferably 0.005 to 10% by weight of the total of the resin composition (B) And more preferably 0.01 to 5% by weight. When the content is less than 0.005% by weight, the formation of bubbles in the resin composition may not be suppressed. When the content is more than 10% by weight, defects such as stripes and cratering may occur at the time of applying the resin composition.

The resin composition (A) related to the present invention also preferably contains a fluorine group-containing oligomer and preferably contains a non-ionic fluorine group-containing oligomer. This is to further improve prevention of bubble formation of the resin composition.

The oligomer having a nonionic fluorine group preferably has a polymerization average molecular weight of 5,000 to 20,000, more preferably 5,000 to 10,000. For example, FutaZento 710FM manufactured by NEOS Corporation, Megafac F-554, Megafac F-555, Megafac F-556, Megaface RS-75 manufactured by DIC Corporation, NS-9013 and DSN- But are preferably Futazento 710FM, Megafac F-555, and NS-9013. Here, the polymerization average molecular weight is measured using GPC (HLC-8120GPC manufactured by Toso Co., Ltd.), tetrahydrofuran as a solvent, and polystyrene as a standard sample.

The content of the nonionic fluorine group-containing oligomer in the resin composition (A) according to the present invention is not particularly limited, but is preferably 0.005 to 10% by weight, more preferably 0.01 to 5% by weight, , And particularly preferably 0.1 to 2% by weight. When the content is less than 0.005% by weight, the formation of bubbles in the resin composition may not be suppressed. When the content is more than 10% by weight, defects such as stripes and cratering may occur at the time of applying the resin composition.

<1-5. Solvent>

The solvent which is an essential component of the resin composition of the present invention has an SP value of 10.0 or less, preferably 9.5 or less, more preferably 9.3 or less, particularly preferably 9.0 or less. If the upper limit is not more than the upper limit, it is preferable because the foaming property is good. The lower limit is preferably at least 7.5, more preferably at least 7.8, even more preferably at least 8.0, particularly preferably at least 8.2, most preferably at least 8.5. If it is more than the lower limit, it is preferable because compatibility is good.

The SP value represents the solubility parameter, which is calculated by the method proposed by Fedors. Specifically, &quot; POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 147 to 154). The SP value is a property value determined by the content of the hydrophobic group or the hydrophilic group in the molecule. When a mixed solvent is used, it is also possible to prepare a mixture by mixing a solvent having a low SP value and a large solvent.

In general, when a solvent having a high SP value is used in a resin organism which dissolves a polymer, since a hydrophilic group is increased, colloid is easily formed and bubbles tend to be generated. When a solvent having a low SP value is used, bubble formation can be prevented . However, in order to increase the solubility of the polymer, which is an essential component of the resin composition of the present invention, it is preferable to use a solvent having a high SP value to some extent to obtain a homogeneous solution. Therefore, a solvent having an SP value in the above range is used as the solvent in the present invention.

As the solvent in the present invention, any of known solvents can be widely used as long as the SP value is within the above range, but ketone solvents such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) , Isopropyl alcohol (IPA) and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ethers such as ethyl acetate, butyl acetate, propyleneglycol monomethyl ether acetate, 2-ethoxyethyl An ester solvent such as acetate; an aromatic hydrocarbon solvent such as toluene; and the like. Among them, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) of ketone solvents are more preferable from the viewpoint of low bubble generation and high compatibility with the polymer of the present invention.

These solvents may be used singly or in combination of two or more kinds.

When the resin composition of the present invention is used for a coating application as described later, the solid content concentration of the resin composition is 10 wt% or more, particularly 20 wt% or more, 90 wt% or less, Particularly preferably 70% by weight or less.

<1-6. Radical Polymerizable Photoinitiator>

It is preferable that the resin composition of the present invention further contains a radical polymerization initiator in addition to the above essential components. This is for efficiently carrying out curing of the resin composition. Normally, the curing of the resin composition is carried out by irradiating the active energy ray, but it can be omitted if irradiation energy is very strong like the electron beam (EB), and addition of the radical polymerization initiator is not required.

As the radical-polymerizable photoinitiator, it is possible to widely adopt known ones, but it is preferable to use an alkylphenone type compound (? -Hydroxyacetophenone type,? -Aminoacetophenone type, benzylketal type, etc.), acylphosphine oxide Oxime ester compounds, oxyphenylacetic acid esters, benzoin ethers, phenyl formic acid esters, ketone / amine compounds, and the like. Specific examples thereof include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclo Methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, methylbenzoylformate, Michler's ketone, N, N-dimethylaminobenzoic acid isoamyl, 2-chlorothioxanthone, 2 , 4-diethyl thioxanthone and the like are preferable.

These radically polymerizable photoinitiators may be used singly or in combination of two or more.

The content of the radically polymerizable photoinitiator in the resin composition of the present invention can be appropriately determined depending on the kind of the radically polymerizable photoinitiator to be used. However, the content of the polymer in the composition, An organic-inorganic hybrid substance having a (meth) acryloyl group bonded via an O-Si-R- bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms), a radical polymerizable organic ) Is preferably 10% by weight or less, more preferably 10% by weight or less, and more preferably 10% by weight or less, based on the total amount of the polymerizable components in the composition such as the acrylate compound and / or the radically polymerizable organic (meth) acrylamide compound and the polymer having radically polymerizable groups other than the polymer By weight or less, more preferably 0.5% by weight or more. When the content of the radical-polymerizable photoinitiator is smaller than this range, the curing becomes insufficient, whereas when the content is larger than that range, the hardness is lowered and the stain resistance is lowered.

Further, as the radically polymerizable photoinitiator, there may be mentioned 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2- Naphthyl) -butan-1-one, oxime ester initiators such as Irgacure OXE-01 manufactured by Ciba Specialty Chemicals, 1-hydroxycyclohexyl phenyl ketone and Michler's ketone Is used in an amount of not less than 20% by weight based on the total amount of the radical polymerizable photoinitiator component, the polymerization inhibition by oxygen is further reduced, The surface hardening property and the film hardening property can be further improved, which is particularly preferable.

<1-7. Other optional components>

In the resin composition of the present invention, in order to control the properties of the coating film such as the hardness and the like when the composition is used as a coating film and to control the liquid properties such as the viscosity of the composition, (Meth) acryloyloxy group bonded through a -O-Si-R- bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms) to inorganic oxide fine particles mainly comprising a polymer and colloidal silica An organic-inorganic hybrid having a weather, and an inorganic fine particle.

The content thereof is not particularly limited as long as it does not deviate from the object of the present invention, but it is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight based on the whole resin composition. If such a content is smaller than 0.1% by weight, it is difficult to obtain a praying effect (for example, improvement of the hardness of the coated film, curl suppression or the like) by the addition of these additional components, and if it is larger than 50% by weight, May be lowered.

Here, as the polymer other than the polymer of the present invention, a (meth) acrylate polymer other than the polymer of the present invention having a side chain with a radically polymerizable group such as an acryloyl group or a methacryloyl group, And copolymers of other radically polymerizable monomers such as styrene. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3 , A polymer having a (meth) acryloyl group in the side chain obtained by adding (meth) acrylic acid to a polymer obtained by polymerizing 4-epoxycyclohexylmethyl methacrylate as a main component is preferable. Of course, they do not exclude other things. These may be used singly or in combination of two or more kinds.

In addition to the components described above, other components may be blended into the resin composition of the present invention for the purpose of imparting various functions.

For example, when an ultraviolet absorber and a hindered amine light stabilizer are incorporated, the weatherability is remarkably improved, which is preferable. Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based, cyanoacrylate-based, and triazine-based ultraviolet absorbers. In addition, for the purpose of improving the physical properties of the coating film, it is also possible to use this kind of antifouling agent (such as a hindered phenol-based, sulfur-based, phosphorus-based antioxidant), antiblocking agent, slipping agent, May be blended with various additives. The blending amount of these additives is preferably 0.01% by weight or more and 2% by weight or less, respectively, with respect to the other solid components.

In order to further improve the hardness and blocking resistance, the resin composition of the present invention may be blended with inorganic oxide fine particles used in the organic-inorganic hybrid substance (C2) as described above.

In addition, a commercially available antifoaming agent such as a silicone compound or the like may be supplementarily contained.

<1-8. Defoaming>

The resin composition of the present invention has excellent defoaming property. Therefore, when used as a coating paint, the coating film is not cratered, and the leveling property of the cured film obtained from the coating film is excellent.

Here, the excellent antifoaming property means that the solid content (polymer and hydrocarbon monomer as essential components of the resin composition) is adjusted so that the solid concentration is 50% by weight and the proportion of the polymer in the solid content is 5% 15 ml of a phosphoric acid-saturated hydrocarbon (10% by weight of the total solution) and 15 ml of a solution dissolved in a solvent, which is an indispensable ingredient, were placed in a 30 ml cylindrical container having an inner diameter of 1.5 cm, And the time until the bubbles on the surface of the produced liquid disappeared was visually measured. The bubbles on the surface of the liquid preferably disappear in less than 15 minutes, more preferably in less than 2 minutes.

<1-9. Reasons why the present invention is effective>

The reason why the present invention exerts the effect is presumed as follows. Generally, in a solvent having a high SP value, a polymer having a hydroxyl group and a fluoroalkyl group as in the present invention, that is, a polymer having a hydrophilic and hydrophobic group, arranges hydrophobic groups externally to form bubbles in the solution. Thus, in the first aspect of the present invention, it is considered that the solvent having a SP value of not more than a specific value is used and saturated hydrocarbon is added to increase the hydrophobicity of the solvent and to prevent the polymer from forming bubbles, It is presumed that the hydrocarbon becomes a starting point of the vesicle by destroying the arrangement of molecules in the solution of the polymer having hydrophilic and hydrophobic groups forming bubbles and exerts the effect of the present invention. Likewise, in the second aspect of the present invention, by using a solvent having a SP value of not more than a specific value and adding an additive having a surface tension lowering ability and a certain level or more, the hydrophobicity of the solvent is increased and the polymer is inhibited from forming bubbles The defoaming property becomes good and the fluorine group-containing oligomer breaks the arrangement of molecules in a solution of a polymer having hydrophilic and hydrophobic groups forming bubbles, thereby becoming a starting point of the bubbles and exhibiting the effect of the present invention It is presumed.

<2. Cured goods>

By curing the resin composition of the present invention, it is possible to obtain a cured film exhibiting excellent physical properties to be described later.

The cured film can be obtained by polymerizing the polymerizable component in the composition by applying a resin composition of the present invention, forming a coating film by solvent drying, and then irradiating an active energy ray. Examples of the application method include spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, air knife coating and the like. The thickness of the film obtained by coating, drying, polymerization and curing is not particularly limited, and may be, for example, 5 탆 or more and 2 탆 or less. That is, the resin composition of the present invention is very meaningful in that both of thinning and thickening are possible. The thickness of the cured film is particularly preferably not less than 0.01 탆 and not more than 50 탆, particularly preferably not less than 2 탆 and not more than 20 탆 when the hardness is emphasized, particularly preferably not more than 0.04 탆 Or more and 2 m or less.

Examples of the active energy ray irradiation include ultraviolet rays generated from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a carbon arc lamp or a tungsten lamp, or an electron beam ,? -ray,? -ray,? -ray and the like can be used. These active energy rays are irradiated to the coating film and cured to form a cured film.

Such a cured film formed by irradiation with an active energy ray is particularly preferable because it has excellent balance of productivity and physical properties.

The resin composition of the present invention described above of the cured product of the present invention is irradiated with an active energy ray to polymerize the polymerizable component in the composition, and it is particularly preferable to satisfy the following appropriate physical properties. The curing of the coating film containing the resin composition of the present invention is not limited to ultraviolet rays, and active energy rays such as electron beams, alpha rays, beta rays and gamma rays can be used. In the present invention, Photo-radical polymerization or photo-cation polymerization can be mentioned as a preferable example. In the following description, ultraviolet irradiation is usually conducted in an oxygen concentration atmosphere.

<2-1. Properties of Cured Products>

The cured product obtained by curing the resin composition of the present invention has the following properties.

<2-1-1. Longitude>

The cured product of the present invention exhibits high hardness. Here, the hardness is high, and pencil hardness means hardness of not less than HB under the condition of the standard of JIS K-5400. The pencil hardness is determined by the order of 6B, 5B, ..., B, HB, F, H, 2H, 3H, ..., 9H.

The resin composition of the present invention was coated on a PET substrate having an adhesive property of 188 탆 in thickness, and a high-pressure mercury lamp with an output density of 120 W / cm was used to apply ultraviolet rays having a wavelength of 254 nm to a cumulative light quantity of 500 mJ / The pencil hardness of the cured film having a thickness of 5 占 퐉 is preferably B or more, particularly preferably HB or more.

Particularly, when the resin composition of the present invention contains dipentaerythritol hexaacrylate, it is coated on a PET base material having a thickness of 188 탆, and a high-pressure mercury lamp with an output density of 120 W / cm , A pencil hardness of a cured film having a thickness of 5 占 퐉 formed by irradiating ultraviolet rays having a wavelength of 254 nm to an integrated light quantity of 500 mJ / cm2 is preferably 3H or more.

However, the composition used for evaluating the pencil hardness was such that only 1-hydroxycyclohexyl phenyl ketone was used as the radical polymerizable photoinitiator, and in addition to 100 parts by weight of solids other than 1-hydroxycyclohexyl phenyl ketone, And 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone.

<2-1-2. Water and oil repellency>

The cured product of the present invention shows excellent water repellency and oil repellency.

The excellent water and oil repellency is obtained by applying the resin composition of the present invention onto a PET substrate having an adhesive property of 188 탆 and using a high pressure mercury lamp with a power density of 120 W / cm to obtain a coating film having a wavelength of 254 nm The contact angle of the surface of the cured film having a thickness of 5 占 퐉 formed by irradiating ultraviolet rays to an integrated light quantity of 500 mJ / cm2 with respect to water is not less than 100 degrees and not more than 120 degrees, particularly not less than 102 degrees and not more than 115 degrees, Can be evaluated by a contact angle of not less than 50 degrees, not more than 90 degrees, particularly not less than 52 degrees, and not more than 75 degrees. The method of measuring the contact angle will be described in detail in the following embodiments.

<2-1-3. Stain resistance and durability>

The cured product of the present invention is excellent in stain resistance and has excellent durability. In particular, it exhibits excellent antifouling property against persistent pollution.

When the black magic is attached to the surface of the cured product or the cured film of the resin composition of the present invention and wiped with a tissue paper at a load of 200 g, the wiping operation within 3 round trips, more preferably 2 The fingerprint can be completely removed by the operation within the round trip, and the fingerprint can be evaluated by being very high to high.

In addition, excellent durability against stain resistance can be evaluated by the fact that the fingerprint removing property is not deteriorated even by repeating the wiping operation five times by attaching black magic and wiping three times with tissue paper at a load of 200 g, It is a further feature of the cured product of the present invention.

Even if a stain resistance imparting agent for wiping with a small number of times of wiping is used, since the conventional stiffness is insufficient or is not fixed to the surface of the membrane, repeating the affixing and wiping operations may result in fine The fingerprint (or the artificial fingerprint liquid) entered the gap, or the stain resistance imparting agent disappeared from the surface, and the durability of the fingerprint removing property was deteriorated. On the other hand, since the resin composition of the present invention has a high hardness after curing and is fixed on the surface of the film, the wiping property of black magic does not deteriorate even if the operation is repeated 5 times or more, preferably 10 times or more. And has high wiping performance durability.

<3. Molded products having a cured film>

As described above, the cured product obtained by polymerizing the polymerizable component in the composition by irradiating the active energy ray to the resin composition of the present invention is excellent in properties such as stain resistance and hardness.

Therefore, an article having a cured film obtained by irradiating the resin composition of the present invention with an active energy ray has excellent properties such as stain resistance and hardness.

The cured film may be formed by applying the resin composition of the present invention onto the surface of the article body and then polymerizing the film by irradiation with an active energy ray. Alternatively, the cured film may be formed by irradiating an active energy ray, .

Hereinafter, a cured product of the present invention, particularly an article comprising a cured film, will be described.

The cured film of the present invention can be applied to various articles. For example, it is necessary to use an optical recording medium, an optical display, a transparent film of a vinyl house for agriculture ), Solar cell surface protection film (to prevent deterioration of battery efficiency, internal pollution function is required), retroreflective surface protective film (headlamp light or relatively dark light of external light, An optical lens, an optical prism, a prism sheet, a window pane of automobile, a window pane of a dried product, a spectacle lens, and the like. Particularly, it is preferable to apply it to an optical article requiring high transparency.

The resin composition of the present invention is preferably used for forming a hard coat layer by applying, drying and curing various substrates. In this case, the kind of the substrate is not particularly limited, but a substrate made of a resin is preferable because of high adhesiveness. The resin base material may be a plate, a sheet, or a film, or may be a molded product of any desired shape. The substrate may be a part of the laminate, or another layer may be interposed between the substrate and the cured film.

The resin substrate may be a thermoplastic resin or a cured resin cured by heat or an active energy ray.

Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polymethyl methacrylate (PMMA), and copolymers containing methyl methacrylate (MMA) (methyl methacrylate-styrene copolymer Butadiene-styrene copolymer (ABS resin), modified polyolefin resin, fluororesin (e.g., vinylidene fluoride resin (PVDF), polyvinylidene fluoride resin Polyvinyl fluoride resin (PVF)), hydrogenated polystyrene resin, cycloolefin resin (for example, Aton manufactured by JSR, Zeonex manufactured by Nippon Zeon, Zeonoa, and Arpel manufactured by Mitsui Chemicals).

Examples of the cured resin include epoxy resins, urethane resins, cured products of thermosetting and photo-curable acrylic resins, and cured products of thermosetting and photo-curable organic-inorganic hybrid resins.

These substrates may be, for example, self-coating films or molded products obtained by various molding methods.

The cured film of the present invention is excellent in transparency, excellent in stain resistance and hardness, and thus is very useful when applied to optical articles requiring high transparency. In this case, when it is necessary that the base material is also transparent, it is preferable that the base material is formed by a coating method, a melt extrusion molding method, or a solvent casting method. When the substrate contains an active energy ray or a heat-curable functional group, it may be more preferable to cure it by irradiation with active energy rays or heating. In order to increase the hardness of the substrate or reduce the hardening shrinkage, it is preferable to contain inorganic oxide fine particles and / or urethane acrylate. In addition, transparency means that the transmittance of light of a target wavelength is generally 80% or more.

The cured film of the present invention can also be suitably used as an anti-staining hard coat layer of an optical recording medium.

The resin composition of the present invention can be preferably used for optical display applications. Particularly, it is preferable as an agent for imparting stain resistance to a display panel surface of a flat panel display (a liquid crystal display, a plasma display, a rear projection display, a screen for a front projector, an inorganic EL display, an organic EL display, etc.) It can be suitably used as a hard coat layer on the surface of a flat panel TV (especially a liquid crystal television) widely used in the home, a display having a touch panel input function in a telephone, a mobile information terminal (PDA etc.), a PC monitor and the like.

When the resin composition of the present invention is applied to a laminate used for such an optical recording medium or a display, a transparent resin base material is used, and at least one surface of the laminate is coated with an active energy ray To form a cured film formed by polymerization.

The cured product obtained by polymerizing the resin composition of the present invention by irradiation with an active energy ray is excellent in properties such as stain resistance and hardness.

An article having a film formed by polymerizing the resin composition of the present invention by irradiation with active energy rays has excellent properties such as stain resistance and hardness. The composition may be coated on the surface of the article, and then irradiated with an active energy ray to polymerize it. Alternatively, a film polymerized by irradiation with an active energy ray may be laminated on the article.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless they depart from the gist of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

In the examples, "part" and "%" mean "part by weight" and "% by weight", respectively.

&Lt; Synthesis Example 1: Synthesis of Polymer (A-01) &gt;

55 g of perfluorohexylethyl methacrylate, 11 g of lauryl methacrylate, 34 g of glycidyl methacrylate, 0.9 g of dodecyl mercaptan (M (a1) / M (a3) = 1.78), 1- 200 g of methoxy-2-propanol was added, and the internal temperature was raised to about 60 DEG C under nitrogen flow. Thereafter, a total of 1.2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (V65) was divided into two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 DEG C to completely inactivate V65, and the temperature was returned to room temperature. The solid concentration was about 34%.

Next, the mixture was heated to 90 DEG C under a 7% oxygen atmosphere, then 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 127.2 g of pentaerythritol tri (meth) acrylate was dissolved in 54.5 g of 1-methoxypropyl-2-acetate and added dropwise over 30 minutes. During this time, the liquid temperature was maintained at 90 to 105 ° C. Thereafter, the solution temperature was raised to 110 DEG C, held at this temperature for 12 hours, and returned to room temperature. The solids content was 35% (A-01).

The fluorine atom content and the hydroxyl group content calculated from the injection weight were 12.3 wt% and 1.6 wt%, respectively.

Synthesis Example 2: Synthesis of polymer (A-02)

50 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of?,? - dimercapto-polydimethylsiloxane (number average molecular weight 1600), 30 g of glycidyl methacrylate, 0.9 g of mercaptan and 200 g of 1-methoxy-2-propanol were added, and the internal temperature was raised to about 60 캜 under a nitrogen stream. Thereafter, a total of 1.2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (V65) was divided into two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 DEG C to completely inactivate V65, and the temperature was returned to room temperature. The solid concentration was about 34%.

Next, the mixture was heated to 90 DEG C under a 7% oxygen atmosphere, then 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 15.5 g of acrylic acid was dissolved in 54.5 g of 1-methoxypropyl-2-acetate and added dropwise over 30 minutes. During this time, the liquid temperature was maintained at 90 to 105 ° C. Thereafter, the solution temperature was raised to 110 DEG C, held at this temperature for 12 hours, and returned to room temperature. The solids content was 30% (A-02).

&Lt; Synthesis Example 3: Synthesis of Polymer (A-03) &gt;

50 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of?,? - dimercapto-polydimethylsiloxane (number average molecular weight 1600), 30 g of glycidyl methacrylate, 0.9 g of mercaptan and 200 g of 1-methoxy-2-propanol were added, and the internal temperature was raised to about 60 캜 under a nitrogen stream. Thereafter, a total of 1.2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (V65) was divided into two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 DEG C, V65 was completely deactivated, and the temperature was returned to room temperature. The solid concentration was about 34%.

Next, the mixture was heated to 90 DEG C under a 7% oxygen atmosphere, then 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 127.2 g of pentaerythritol tri (meth) acrylate was dissolved in 54.5 g of 1-methoxypropyl-2-acetate and added dropwise over 30 minutes. During this time, the liquid temperature was maintained at 90 to 105 ° C. Thereafter, the solution temperature was raised to 110 DEG C, held at this temperature for 12 hours, and returned to room temperature. The solids content was 35% (A-03).

The content of fluorine atoms calculated from the weight of the solution was 12.1% by weight, and the content of hydroxyl groups was 1.5% by weight.

Synthesis Example 4: Synthesis of Polymer (A-04)

10 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of polydimethylsiloxane-containing methacrylate (number average molecular weight 1000, manufactured by Chisso Corporation, FM0711), 30 g of glycidyl methacrylate, 0.9 g of silmercaptan and 200 g of 1-methoxy-2-propanol were added, and the internal temperature was raised to about 60 캜 under a nitrogen stream. Thereafter, a total of 1.2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (V65) was divided into two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 DEG C, V65 was completely deactivated, and the temperature was returned to room temperature. The solid concentration was about 34%.

Next, the mixture was heated to 90 DEG C under a 7% oxygen atmosphere, then 0.5 g of p-methoxyphenol and 4.6 g of triphenylphosphine were added. After 5 minutes, 127.2 g of pentaerythritol tri (meth) acrylate was dissolved in 54.5 g of 1-methoxypropyl-2-acetate and added dropwise over 30 minutes. During this time, the liquid temperature was maintained at 90 to 105 ° C. Thereafter, the solution temperature was raised to 110 DEG C, held at this temperature for 12 hours, and returned to room temperature. The solids content was 35% (A-04).

The content of fluorine atoms calculated from the weight of the solution was 12.1% by weight, and the content of hydroxyl groups was 1.5% by weight.

Reference Synthesis Example 1: Synthesis of Polymer (X-01)

2 g of methyl methacrylate, 98 g of glycidyl methacrylate, 3.3 g of mercaptopropyltrimethoxysilane and 200 g of 1-methoxy-2-propanol were added and the internal temperature was adjusted to about 60 캜 It has warmed up. Thereafter, 1.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (V65) was added in two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 DEG C, V65 was completely deactivated, and the temperature was returned to room temperature. The solid concentration was about 34%.

Next, the mixture was heated to 90 DEG C in an air atmosphere, and then 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 50.6 g of acrylic acid was dissolved in 19 g of 1-methoxy-2-propanol and added dropwise over 30 minutes. During this time, the liquid temperature was maintained at 90 to 105 ° C. Thereafter, the solution temperature was raised to 110 DEG C, held at this temperature for 12 hours, and returned to room temperature. The solids content was 35% (X-01).

Reference Synthesis Example 2: Synthesis of Polymer (X-02)

22 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 68 g of methyl methacrylate, 0.9 g of dodecyl mercaptan and 200 g of 1-methoxy-2-propanol were added, The temperature was raised to about 60 占 폚 under a nitrogen stream. Thereafter, a total of 1.2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (V65) was divided into two portions, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 DEG C, V65 was completely deactivated, and the temperature was returned to room temperature. The solid concentration was about 34% (X-02).

[Examples 1-1 to 1-11]

&Lt; Preparation and evaluation of resin composition &gt;

Resin compositions of Examples 1-1 to 1-11 and Comparative Examples 1 to 9 were prepared in the formulations shown in Table 1 (weight ratio).

* SP value was calculated using the Fedors estimation method (Reference: R. F. Fedors: Polym. Eng. Sci., 14 [2], 147-154 (1974))

※ Heptane (saturated hydrocarbon) was not included in the SP value of the solvent.

DPHA: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)

M-313: Isocyanuric acid EO-modified di- and triacrylate (Aronix M-313, manufactured by Toagosei Co., Ltd.)

irg184: hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF Corporation)

Megafac F-555: "Megafac F-555" manufactured by DIC Corporation

Futagento 710 FM: "Futagento 710 FM" manufactured by Neos Corporation

MIBK: methyl isobutyl ketone

MEK: methyl ethyl ketone

PGM: 1-methoxy-2-propanol

PGMAc: 1-Methoxypropyl-2-acetate

The resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1 to 9 prepared as described above were evaluated for defoaming property.

The evaluation method is as follows. 15 ml of each of the resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1 to 9 was placed in a cylindrical container having a capacity of 30 ml with an inner diameter of 1.5 cm and shaken 20 times for 5 seconds (⊚: less than 3 minutes, ∘: more than 3 minutes and less than 20 minutes, ×: less than 3 minutes), and the time required until the bubbles on the surface of the liquid disappeared was visually measured. : 20 minutes or more). In addition, transparency and uniformity of the liquid before shaking were observed and evaluated as "appearance" in two steps (o: transparent, ×: cloudy or precipitated). The results are shown in Table 2.

* The numbers in parentheses indicate the time until the bubble on the liquid surface disappears.

As shown in Table 2, the resin compositions of Examples 1-1 to 1-9 exhibited excellent defoaming properties. On the other hand, in the resin compositions of Comparative Examples 1 to 7, bubbles were easily generated, and bubbles were rarely lost. In particular, in Comparative Example 3, it was difficult to observe the liquid because the liquid was opaque, and evaluation of the defoaming property could not be made. Further, as shown in Comparative Example 8 using a polymer having a hydroxyl group and no fluoroalkyl group, and Comparative Example 9 using a polymer having no hydroxyl group and having a fluoroalkyl group, the bubbles of the resin composition are the hydroxyl groups and Lt; RTI ID = 0.0 &gt; fluoroalkyl &lt; / RTI &gt;

&Lt; Preparation and evaluation of cured film &

The resin compositions of Examples 1-4, 1-5, 1-7, 1-9, and 1-9 and Comparative Example 2 prepared as described above were each coated on a PET substrate (thickness 188 탆) so that a cured film having a thickness of 3-4 탆 was formed And then dried at 80 DEG C to remove the solvent to form a dried film. This coated film was irradiated with ultraviolet rays having a wavelength of 254 nm at a power density of 120 W / cm 2 under a normal oxygen concentration atmosphere so as to obtain an accumulated light quantity of 500 mJ / cm 2 and cured to obtain a cured film.

The following items (1) to (6) were evaluated for the cured film prepared as described above.

(1) Transparency: The haze value of the cured film was measured using a haze meter ("HAZE METER HM-65W" manufactured by Murakami Color Research Laboratory) according to JIS K-7105.

(2) Hardness: Measurement was carried out on the basis of the conditions of JIS K-5400 using a JIS-compliant pencil hardness tester (manufactured by Tairu Co., Ltd.) and expressed as the number of the hardest pencils without scratches.

(3) Water-repellent and oil repellency: The cured film was stopped for 24 hours in a constant-temperature chamber at a temperature of 23 占 폚 and a humidity of 60% RH to adjust the state. Thereafter, the cured film was cured with a contact angle meter (&quot; Drop Master DM500 &quot; 0.002 ml of pure water or hexadecane was added dropwise and 1 minute later, the contact angle to water and the contact angle to hexadecane were measured using a contact angle meter (Drop Master 500, Kyowa Interface Science Co., Ltd.) Unit).

(4) Adhesion: The test was conducted by the cross-cut method described in JIS K5400. The cured film was tested with a cellophane tape (manufactured by Nichibei Reflective Co., Ltd.) by inserting 100 checkerboard scales at intervals of 1 mm. The same operation was repeated five times (a cellophane tape was always replaced with a new one). The results were rated as?: No scratch or peeling occurred at all,?: No scratch or peeling occurred at 10% or less, I appreciated.

(5) Magic adhesion: A line is drawn on a cured film with a planar magic marker (Zebra Makishi-keika super fine (black)), and after 30 seconds, when the line is outward, ×, and evaluated in two steps.

(6) Magic wiping Durability: The surface of the woven fabric was wiped with a vaginal magic marker (three times of Zeroglyphic superfine (black) manufactured by Zebra), and after 10 seconds, the surface was wiped with tissue paper (Cressia) From the number of times until the operation was repeated until the wipes were not wiped, the evaluation was made in three steps from ∘ to 5, from 4 to 4, and from 1 to 1.

The evaluation results of the cured film are shown in Table 3.

The cured film obtained by curing the resin composition of the present invention was good in transparency, hardness, water and oil repellency, adhesion, stain resistance and durability against stain resistance.

According to the above examples, the resin composition of the present invention exhibited low bubble generating property and excellent leveling property. Further, by curing the resin composition of the present invention, it has been found to realize a cured product having high hardness, excellent stain resistance, excellent durability, water and oil repellency, and adhesion.

[Examples 2-1 to 2-25]

&Lt; Preparation and evaluation of resin composition &gt;

Resin compositions of Examples and Comparative Examples were prepared in the formulations shown in Table 4 (weight ratio). Concretely, the polymer and the polyfunctional acrylate synthesized in the above-mentioned synthesis examples were mixed in a total amount of 100 parts by weight in the ratio shown in Table 4, and 100 parts by weight of the mixture of the polymer and the polyfunctional acrylate was mixed with the initiator and the additive Were mixed in the proportions shown in Table 4, respectively. A solvent was added thereto in the weight ratios shown in Table 4, and saturated hydrocarbons were also added in Examples 2-4, 2-5, 2-10, 2-11, and 2-15 to 2-18 to prepare a resin composition .

* SP value was calculated using the Fedors estimation method (Reference: R. F. Fedors: Polym. Eng. Sci., 14 [2], 147-154 (1974))

※ Heptane (saturated hydrocarbon) was not included in the SP value of the solvent.

DPHA: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)

M-313: Isocyanuric acid EO-modified di- and triacrylate (Aronix M-313, manufactured by Toagosei Co., Ltd.)

irg184: hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF Corporation)

Megafac F-555: "Megafac F-555" manufactured by DIC Corporation

Mega Park F-477: "Mega Park F-477" manufactured by DIC Corporation

Megafac F-444: "Megafac F-444" manufactured by DIC Corporation

Futagento 710 FM: "Futagento 710 FM" manufactured by Neos Corporation

Futagento 208G: "Futagento 208G" manufactured by NEOS Corporation

Futagento 215M: "Futagento 215M" manufactured by NEOS Corporation

Futazento 245F: "Futazento 245F" manufactured by NEOS Corporation

MIBK: methyl isobutyl ketone

PGM: 1-methoxy-2-propanol

PGMAc: 1-Methoxypropyl-2-acetate

Methods for measuring the physical properties of the additives used in Examples and Comparative Examples are as follows. The SP value of the solvent was determined using the literature value (IUPAC Gold Book-solubility parameter).

The surface tension was determined by measuring the surface tension of a 1% PGMAc solution of a fluorine group-containing oligomer using a surface tension meter (&quot; Drop Master series &quot; manufactured by Kyowa Interface Science Co., Ltd.) - surface tension of 1% PGMAc solution &quot;.

The weight average molecular weight refers to a value measured using GPC (HLC-8120GPC manufactured by Toso Co., Ltd.), tetrahydrofuran as a solvent, and polystyrene as a standard sample. Table 5 shows the results of measuring the physical properties of the oligomer.

The resin compositions of the prepared examples and comparative examples were evaluated for bubble resistance.

The evaluation method is as follows. 15 ml of the resin compositions of the examples and comparative examples were placed in a cylindrical container of 30 ml in inner diameter of 1.5 cm in inner diameter and shaken 20 times (amplitude: 10 to 20 cm) for 5 seconds, The time required for the disappearance of the test piece was visually measured. The above 15 minutes is actually a comparative example because the productivity is bad. In addition, transparency and uniformity of the liquid before shaking were observed and evaluated as "appearance" in two steps (o: transparent, ×: cloudy or precipitated). The results are shown in Table 6.

As shown in Table 6, the resin compositions of the examples exhibited excellent defoaming properties. On the other hand, in the resin composition of the comparative example, bubbles were easily generated, and the bubbles hardly disappeared.

&Lt; Preparation and evaluation of cured film &

The resin compositions of Examples 2-2, 2-4, 2-8 and 2-10 and Comparative Example 10 prepared as described above were each coated on a PET substrate (188 占 퐉 thick) so that a cured film having a thickness of 3-4 占 퐉 was formed And then dried at 80 DEG C to remove the solvent to form a dried film. This coated film was irradiated with ultraviolet rays having a wavelength of 254 nm at a power density of 120 W / cm 2 under a normal oxygen concentration atmosphere so as to obtain an accumulated light quantity of 500 mJ / cm 2 and cured to obtain a cured film.

The following items (1) to (6) were evaluated for the cured film prepared as described above.

(1) Transparency: The haze value of the cured film was measured using a haze meter ("HAZE METER HM-65 W" manufactured by Murakami Color Research Laboratory) according to JIS K-7105.

(2) Hardness: The measurement was carried out on the basis of the conditions of JIS K-5400 using a JIS-compliant pencil hardness tester (manufactured by Tairu Co., Ltd.) and expressed as the number of the hardest pencils without scratches.

(3) Water-repellent and oil repellency: The cured film was stopped for 24 hours in a constant-temperature chamber at a temperature of 23 占 폚 and a humidity of 60% RH to adjust the state. Thereafter, the cured film was cured with a contact angle meter (&quot; Drop Master DM500 &quot; And the contact angle with respect to water and the contact angle with respect to hexadecane were measured by using a contact angle meter (Drop Master 500, manufactured by Kyowa Interface Science Co., Ltd.) after 1 second of dropwise addition of 0.002 ml of pure water or hexadecane Unit).

(4) Adhesion: The test was conducted by the cross-cut method described in JIS K5400. The cured film was tested with a cellophane tape (manufactured by Nichibei Reflective Co., Ltd.) by inserting 100 checkerboard scales at intervals of 1 mm. The same operation was repeated five times (a cellophane tape was always replaced with a new one). All the samples were evaluated as having no flaws or peelings. The results were rated as?, 10% or less flaws or peelings occurred, did.

(5) Magnetic adhesion: A line was drawn on the cured film with a planetary magic marker (three times of superficial black mark made by zebra manufacturing). After 30 seconds, if the line was outward, .

(6) Magic wiping Durability: The surface of the woven fabric was wiped with a vaginal magic marker (three times of Zeroglyphic superfine (black) manufactured by Zebra), and after 10 seconds, the surface was wiped with tissue paper (Cressia) From the number of times until the operation was repeated until the wipes were not wiped, the evaluation was made in three steps from ∘ to 5, from 4 to 4, and from 1 to 1.

Table 7 shows the evaluation results of the cured film.

The cured film obtained by curing the resin composition of the present invention was good in transparency, hardness, water and oil repellency, adhesion, stain resistance and durability against stain resistance.

According to the above examples, the resin composition of the present invention exhibited low bubble generating property and excellent leveling property. Further, by curing the resin composition of the present invention, it has been found to realize a cured product having high hardness, excellent stain resistance, excellent durability, water and oil repellency, and adhesion.

Industrial availability

According to the present invention, there is provided a resin composition which is low in bubble generation property and bubbles to be generated, and which is excellent in defoaming property and therefore hardly causes defects in the formed coating film. Further, when it is coated thinly on the surface of an article or the like and cured, a cured film which gives excellent hardness, scratch resistance, transparency, stain resistance and durability to the article is provided. Therefore, the resin composition of the present invention is suitable for a wide range of applications such as protection of the surface of an optical recording medium, optical display such as a touch panel or a flat display, protection of a transparent part of a mobile phone casing, automotive transparent part protection, So it is very useful in industry.

Claims (20)

A polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1000 or more,
(Meth) acryloyl group and a vinyl group, a hydrocarbon-based monomer containing at least one member selected from
0.01 to 25% by weight of saturated hydrocarbons,
A resin having an SP value of 10.0 or less. The method according to claim 1,
Wherein the saturated hydrocarbon has 5 to 18 carbon atoms. A polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of 1000 or more,
(Meth) acryloyl group and a vinyl group, a hydrocarbon-based monomer containing at least one member selected from
A fluorine group-containing oligomer having a surface tension lowering ability of 2 mN / m or more,
A resin having an SP value of 10.0 or less. 4. The method according to any one of claims 1 to 3,
Wherein the polymer has a hydroxyl group content of 0.2 to 5.0% by weight. 5. The method according to any one of claims 1 to 4,
Wherein the content of fluorine atoms in the polymer is 1.0 to 34.0% by weight. 6. The method according to any one of claims 1 to 5,
Wherein the polymer has an unsaturated double bond group in a side chain. 7. The method according to any one of claims 1 to 6,
Wherein the polymer has a polysiloxane structure. 8. The method of claim 7,
Wherein the silicon at the terminal of the polysiloxane structure or the saturated hydrocarbon group bonded to the silicon is bonded to the main chain of the polymer via an oxygen atom or a sulfur atom. 9. The method according to any one of claims 1 to 8,
Wherein the hydrocarbon-based monomer is a polyfunctional (meth) acrylate having at least three (meth) acryloyl groups in one molecule. 10. The method according to any one of claims 3 to 9,
Wherein the fluorine group-containing oligomer has a weight average molecular weight of 5,000 or more. 11. The method according to any one of claims 3 to 10,
Wherein the fluorine group-containing oligomer is nonionic. 12. The method according to any one of claims 3 to 11,
Wherein the content of the fluorine group-containing oligomer in the resin composition is 0.005 to 10% by weight based on the whole resin composition. 13. The method according to any one of claims 1 to 12,
Wherein the solvent is at least one solvent selected from the group consisting of a ketone-based solvent, an alcohol-based solvent, an ether-based solvent, an ester-based solvent and an aromatic hydrocarbon solvent. 14. The method according to any one of claims 3 to 13,
And a saturated hydrocarbon having 5 to 18 carbon atoms. 15. The method according to any one of claims 1 to 14,
A resin composition containing a radical polymerizable photoinitiator. A cured product obtained by curing the composition according to any one of claims 1 to 15. 17. The method of claim 16,
A cured product obtained by irradiating the composition with an active energy ray. A molded article having the cured product according to claim 16 or 17. 19. The method of claim 18,
A molded article used for optical purposes. 20. The method of claim 19,
A molded article which is laminated for an optical recording medium or an optical display.