KR102078998B1 - Resin composition for coating paint - Google Patents

Abstract

Even if foamability is small and foam may generate | occur | produce, it is excellent in defoaming property, Therefore, the non-aqueous resin composition which hardly produces a defect in the coating film formed is provided. Moreover, the resin composition which gives the cured film which gives the outstanding hardness, damage resistance, transparency, contamination resistance, and durability is provided. In the resin composition, a polymer having a hydroxyl group and a fluoroalkyl group, a weight average molecular weight of 1000 or more, a hydrocarbon monomer containing one or two or more selected from a (meth) acryloyl group and a vinyl group, and a saturated hydrocarbon 0.01-25 weight% and SP value contain a 10.0 or less solvent.

Description

Resin composition for coating paints {RESIN COMPOSITION FOR COATING PAINT}

In the present invention, since bubbles are unlikely to occur in the state of the composition, the resin composition for coating paints useful as a fouling resistance imparting agent having a high leveling property and excellent hardness and damage resistance after curing, and the composition thereof It relates to articles such as a cured product and an optical recording medium using the same. In particular, it is related with the composition etc. which provide the cured film which has these sufficient performance even in a thin film.

The present invention relates to an optical article, in particular an optical recording medium such as a reproduction-only optical disc, an optical recording disc, a magneto-optical recording disc, or a transparent article for an optical display such as a touch panel or 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), acrylic Resin materials, such as styrene resins, such as a ronitrile styrene copolymer (AS resin), vinyl chloride type resin, and cellulose acetates, such as a triacetyl cellulose, are especially excellent in light weight, processability, impact resistance, etc. It is used for various uses, such as an instrument panel, an outer plate, a window material, a roof material, a packaging material, various housing materials, an optical disk board, a plastic lens, a base material of display apparatuses, such as a liquid crystal display, a plasma display, and a projection TV.

However, these plastic products are easily damaged due to their low surface hardness, and in the case of transparent resins such as polycarbonate and polyethylene terephthalate, there is a drawback that the inherent transparency or appearance of the resin is remarkably impaired, which requires wear resistance. The use of plastic products in the field is difficult. For this reason, the surface cured film (coating material) for raising the surface hardness of these plastic products and providing abrasion resistance is calculated | required.

Such a surface cured film is obtained by melt | dissolving or suspending a resin composition in a solvent normally, and apply | coating to the surface of a product as a form of paint, and hardening it. When a coating film is obtained by application | coating and a cured film is further obtained, leveling property is calculated | required by the resin composition. If the leveling property is inferior, the surface roughness and coating failure point called so-called cratering may occur in the coating film or the cured film, which may cause serious obstacles in the production of the cured film. As a cause of cratering, the thing which bubbles generate | occur | produce in a coating liquid or a coating film and the bubble which is hard to disappear are mentioned.

Generally, bubbles are apt to occur in water-based paints, and measures for solving the above-mentioned cratering problems are taken. For example, it is known to contain a saturated hydrocarbon in order to remove the bubble which originates in surfactant in the aqueous coating containing surfactant (patent document 1). On the other hand, since it is common to use a nonpolar solvent with respect to non-aqueous paint, it has been considered that foam | bubble is hard to generate | occur | produce conventionally.

By the way, in the surface cured film used for big screen flat panel TV displays, such as an optical disk, a touch panel display, a liquid crystal television, or a plasma TV, not only surface hardness and durability but also imparting pollution resistance at high level are calculated | required. In addition, in next-generation optical information media and optical articles such as touch panels, in recent years, it has become a problem that pollutants such as fingerprint contamination affect not only appearance but also performance.

In such a situation, since the development of the resin composition for non-aqueous coating coatings containing a fluorine-based compound having an active energy ray-curable group is made, and the cured film obtained by curing it exhibits excellent stain resistance, it is attracting attention (Example For example, patent document 2). The present inventors have known that a specific copolymer containing a specific perfluoroalkyl group and an epoxy group, or the (meth) acrylic acid reactant is effective as a stain resistance imparting agent having excellent wiping resistance or durability thereof. (Patent documents 3-4).

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

However, while developing a resin composition containing a polymer having a fluoroalkyl group and a hydroxyl group, the present inventors have cured it into a coating film because they are highly bubble-prone even though they are generally non-aqueous paints which are considered to be difficult to generate bubbles. When it makes it, leveling property will fall. Therefore, the new subject which improves the leveling property of the obtained coating film and cured film was faced.

Sufficient defoaming property is not obtained only by adding a saturated hydrocarbon like patent document 1 concerning an aqueous coating material. In addition, the polymers described above have low solubility in saturated hydrocarbons, and since the transparency of the cured film obtained by turbidity is impaired when the amount of saturated hydrocarbons added is increased, it is difficult to apply the coating material for an optical article.

Moreover, in order to suppress foaming of a composition, it is common to add various additives as an antifoamer. However, such additives are usually a solid component and can affect the properties of the coating film and cured film obtained from the resin composition. Moreover, many additives are expensive, and there exists a problem that cost increases in industrial production. In addition, when there is a compatibility with the constituent components of the resin composition, and the resin composition and the additive have poor compatibility, there is a possibility that the properties of the resin composition itself may be lowered, and additives must be selected individually for each resin composition, and fluoro The antifoaming method which can be applied to the whole non-aqueous paint which is a resin composition containing the polymer which has an alkyl group and a hydroxyl group without impairing the characteristic is calculated | required.

In view of such a situation, the present invention provides a non-aqueous resin composition having a low bubble generation property and excellent in defoaming property even if bubbles may be generated, and as a result, defects are unlikely to occur in the coating film formed. The purpose. Moreover, it aims at providing the resin composition which gives the cured film which gives the outstanding hardness, damage resistance, transparency, contamination resistance, and durability.

Moreover, this invention is the hardened | cured material of such a composition, and the article which has the hardened | cured material on the surface, especially the article for optical uses, such as an optical recording medium and a touch panel display, and has high hardness and abrasion resistance on the surface, It is an object to provide an article having excellent stain resistance and stain resistance durability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors have a hydroxyl group and a fluoroalkyl group, the weight average molecular weight is 1000 or more, 1 type or 2 types chosen from a (meth) acryloyl group and a vinyl group. It was found that the bubble generation property of the resin composition can be reduced by containing a hydrocarbon-based monomer containing the above, a specific amount of saturated hydrocarbon, and a solvent having a SP (Solubility Parameter) value of 10.0 or less.

Moreover, the polymer which has a hydroxyl group and a fluoroalkyl group, the weight average molecular weight is 1000 or more, the hydrocarbon type monomer containing 1 type (s) or 2 or more types chosen from a (meth) acryloyl group and a vinyl group, and the surface tension fall ability is 2 When the fluorine group containing oligomer which is mN / m or more and a solvent with a SP value of 10.0 or less were contained, it was found that the bubble generation property of a resin composition can be made small.

Furthermore, when the polymer has a polysiloxane structure and the silicon at the terminal of the polysiloxane structure or the saturated hydrocarbon group bonded to the silicon is a polymer bonded to the main chain of the polymer via an oxygen atom or a sulfur atom, high water / oil repellency It discovered that it becomes the especially outstanding resin composition to express, and came to complete this invention.

That is, this invention is as follows.

[1] a hydrocarbon monomer having a hydroxyl group and a fluoroalkyl group, containing a polymer having a weight average molecular weight of 1000 or more, one or two or more selected from a (meth) acryloyl group and a vinyl group, and a saturated hydrocarbon; The resin composition containing-25 weight% and a solvent whose SP value is 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, containing a polymer having a weight average molecular weight of 1000 or more, one or two or more selected from a (meth) acryloyl group and a vinyl group, and a surface tension reducing ability The resin composition containing the fluorine-group containing oligomer which is 2 mN / m or more, and the solvent whose SP value is 10.0 or less.

[4] The resin composition according to any one of [1] to [3], wherein the content of the hydroxyl group in the polymer is 0.2 to 5.0 wt%.

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

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

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

[8] The resin composition according to [7], wherein 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.

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

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

[13] The solvent according to 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. The resin composition described.

[14] The resin composition according to any one of [3] to [13], containing a saturated hydrocarbon having 5 to 18 carbon atoms.

[15] The resin composition according to any one of [1] to [14], containing 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], obtained by irradiating an active energy ray to the composition.

[18] A molded article having the cured product described in [16] or [17].

[19] The molded article according to [18], which is used for optics.

[20] The molded article according to [19], which is a laminate for an optical recording medium or an optical display.

The present invention provides a resin composition having a small bubble generation property and excellent in defoaming property even if bubbles may be generated, and thus less likely to cause defects in the formed coating film. Moreover, when this is apply | coated thinly on the surface of articles etc., the article etc. provides the cured film which provides the outstanding hardness, damage resistance, transparency, stain resistance, and durability.

Therefore, the resin composition of this invention is suitable for a wide range of uses, such as protection of the surface of an optical recording medium, optical displays, such as a touchscreen and a flat panel display, mobile phone casing, automobile transparent parts protection, and the protection of transparent parts, such as an agricultural vinyl house. Can be applied.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described in detail, description of the element | module described below is a typical example of embodiment of this invention, This invention is not limited to these content, The scope of the summary Various modifications can be made within. EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail.

In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification.

In addition, unless otherwise indicated, "polymerization" as used in this invention is extensive polymerization including what is called "copolymerization." Therefore, in this invention, a "copolymer" is also contained in a "polymer."

In addition, "room temperature" as used in the present invention means the temperature at the place where the experiment or the like is carried out, and means, for example, a temperature of 15 to 30 ° C, more preferably 20 to 25 ° C.

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

In addition, "(meth) acrylate" means "acrylate and / or methacrylate", and is the same also about "(meth) acryloyl" and "(meth) acryl".

<1. Resin Composition

The resin composition (Hereinafter, it may abbreviate as "the resin composition (A) concerning this invention.") Which is one aspect of this invention has a hydroxyl group and a fluoroalkyl group, the weight average molecular weight is 1000 or more polymer, and (meth A hydrocarbon monomer containing one or two or more selected from a) acryloyl group and a vinyl group, 0.01 wt% to 25 wt% of saturated hydrocarbon, and a solvent having an SP value of 10.0 or less are included as essential components.

Moreover, the resin composition (Hereinafter, it may abbreviate as "the resin composition (B) concerning this invention.") Which is another aspect of this invention has a hydroxyl group and a fluoroalkyl group, the weight average molecular weight is 1000 or more, A hydrocarbon monomer containing one or two or more selected from the (meth) acryloyl group and the 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 essential It contains as a component.

<1-1. Polymer>

The polymer which is an essential component of the resin composition of this invention has a hydroxyl group and a fluoroalkyl group, and a weight average molecular weight is 1000 or more. Although a weight average molecular weight will not be specifically limited if it is 1000 or more, Preferably it is 1000-30000, More preferably, it is 1000-20000. Here, a weight average molecular weight says what was measured using GPC ("HLC-8120 GPC" by Toso Corporation) and using tetrahydrofuran as a solvent and polystyrene as a standard sample.

Moreover, it is preferable from the viewpoint of hardening of a resin composition that the said polymer has unsaturated double bond group in a side chain.

Moreover, it is preferable that the said polymer has a polysiloxane structure from a viewpoint of providing leveling property, slipperiness | lubricacy, and peelability to a cured film. In this case, it is more preferable that the silicon at the terminal of the polysiloxane structure or the saturated hydrocarbon group bonded to the silicon are bonded to the main chain of the polymer via an oxygen atom or a sulfur atom.

The polymer in the resin composition of this invention can be manufactured by superposing | polymerizing the polymerizable monomer demonstrated below. Below, the preferable manufacturing method of a polymer is described.

In addition, below, the quantity (weight part) of each component in 100 weight part of monomer mixtures as a manufacturing raw material of the polymer of this invention may be called "usage use."

As a polymerizable monomer which manufactures a polymer, the (meth) acrylate which has a hydroxyl group is demonstrated first. When several representative specific examples of the (meth) acrylate which has a hydroxyl group are shown, 2-hydroxyethyl acrylate, pentaerythritol triacrylate, etc. are mentioned, It is not limited to these at all, A hydroxyl group is reacted by reaction. The monomer which has a functional group to produce may be sufficient. When there is little usage-amount of the (meth) acrylate which has a hydroxyl group, the hardness of the cured film obtained from a resin composition will fall, and neither is preferable.

As a monomer which has a functional group which produces | generates a hydroxyl group by reaction, reaction of an epoxy group and a carbonyl group, ring-opening reaction of an oxysilane skeleton, or addition reaction is mentioned as an example.

When several typical specific examples of the (meth) acrylate which has an epoxy group are shown, (meth) acrylate which has glycidyl groups, such as glycidyl acrylate and glycidyl methacrylate; 3, 4- epoxycyclohexyl acryl (Meth) acrylic in which an epoxy group is directly bonded to an alicyclic structure, such as a rate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, or 3,4-epoxycyclohexylmethyl methacrylate Although a rate is mentioned, it is not limited to these at all.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4, from the availability and the ease of modification by (meth) acrylic acid. -Epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate and the like are particularly preferred.

The (meth) acrylate which has such an epoxy group may be used individually by 1 type, and may mix and use 2 or more types.

When the usage-amount of the (meth) acrylate which has an epoxy group is small, the high hardening property by photo radical polymerization by the carboxylic acid modification which has a (meth) acryloyl group, the high hardening effect, the improvement effect of surface hardenability, etc. can be expressed. If the amount is large, the thickening of the polymer solution and the lowering of the liquid stability may be observed, and further high hardening properties and high hardening properties are not observed.

When some typical specific examples of the (meth) acrylate having a carbonyl group are shown, acrylic acid, methacrylic acid, succinic acid-modified pentaerythritol triacrylate, etc. may be mentioned, but the present invention is not limited thereto.

Although content of the hydroxyl group in the polymer in the resin composition of this invention is not specifically limited, In the case of the resin composition (A) or resin composition (B) which concerns on this invention, it is preferable that it is 0.2 weight% or more as a lower limit, and it is 0.4 weight% It is more preferable that it is more than the above, It is further more preferable that it is 0.5 weight% or more, It is especially preferable that it is 0.7 weight% or more, It is most preferable that it is 1.0 weight% or more. As an upper limit, it is preferable that it is 5.0 weight% or less, It is more preferable that it is 4.0 weight%, It is further more preferable that it is 3.5 weight% or less, It is most preferable that it is 3.0 weight%.

In manufacture of a polymer, the usage-amount of the monomer which has a hydroxyl group is adjusted so that it may become this range.

Moreover, in the monomer mixture which manufactures a polymer, it is preferable that it is 5-50 weight%, and, as for the usage-amount of the monomer which has a hydroxyl group with respect to the whole monomer, it is more preferable that it is 10-30 weight%.

As a monomer used for manufacture of a polymer, the monomer which has a fluoroalkyl group is demonstrated. As such a monomer, (meth) acrylate containing a fluoroalkyl group is mentioned preferably. Although there is no restriction | limiting in particular as (meth) acrylate containing a fluoroalkyl group, The (meth) acrylate containing a fluoroalkyl group other than the (meth) acrylate which has a C8 or more linear perfluoroalkyl group is preferable. Do. When carbon number is 8 or more and a large amount of (meth) acrylate which has a linear perfluoroalkyl group is used, the bubble generation property of the polymer solution of this invention or the composition solution using this polymer will become remarkably high, and a problem will arise. Because it becomes. In addition, the (meth) acrylate which has a C8 or more linear perfluoroalkyl group is not necessarily used.

As a (meth) acrylate which has a preferable fluoroalkyl group, the (meth) acrylate which has a C4-C7 linear fluoroalkyl group is mentioned, For example, perfluorohexylethyl (meth) acrylate , (Meth) acrylic acid adduct of perfluorohexyl glycidyl ether, (meth) acrylic acid adduct of perfluoroheptyl glycidyl ether, and the like are preferable. Moreover, the (meth) acrylate which has a C6 or more, and the terminal has a fluoroalkyl group of a difluoromethyl group is also mentioned, For example, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, etc. are preferable.

Among these, (meth) acrylate which has a C6 linear saturation fluoroalkyl group, for example, (meth) acrylic acid addition of perfluorohexylethyl (meth) acrylate and perfluorohexyl glycidyl ether Water is particularly preferred.

The (meth) acrylate which has these fluoroalkyl groups may be used individually by 1 type, and may mix and use 2 or more types.

As a (meth) acrylate which has a C8 or more linear perfluoroalkyl group, For example, perfluoro octylethyl (meth) acrylate, perfluorodecylethyl (meth) acrylate, 2- (perfluoro 1 type (s) or 2 or more types, such as rho-7-methyl octyl) ethyl (meth) acrylate, heptadecafluorononenyl (meth) acrylate, and the (meth) acrylic acid addition product of perfluorooctyl glycidyl ether Can be mentioned.

Although content of the fluorine atom in the polymer in the resin composition of this invention is not specifically limited, In the case of the resin composition (A) or resin composition (B) which concerns on this invention, it is preferable that it is 1.0 weight% or more as a lower limit, and it is 4.0 weight. It is more preferable that it is% or more, It is further more preferable that it is 4.5 weight% or more, It is especially preferable that it is 5.0 weight% or more, It is most preferable that it is 10.0 weight% or more. As an upper limit, it is preferable that it is 34.0 weight% or less, It is more preferable that it is 30.0 weight% or less, It is further more preferable that it is 25.0 weight%. When content of a fluorine atom is less than this lower limit, the effect, such as the improvement of oil-resistant fouling resistance resulting from the oil and oil repellency of a fluoroalkyl group, will not fully be exhibited, and when this upper limit is exceeded, compatibility with a polymer and another component will fall or harden | cure. There is a possibility that the hardness of the film is lowered and the surface damage resistance and pencil hardness are lowered. In manufacture of a polymer, the usage-amount of the monomer which has a fluoroalkyl group is adjusted so that it may become this range.

Moreover, in the monomer mixture which manufactures a polymer, it is preferable that the usage-amount of the (meth) acrylate which has a perfluoroalkyl group with respect to the whole monomer is 80.0 weight% or less, and it is more preferable that it is 60.0 weight% or less.

Moreover, it is preferable that the polymer in this invention has a polysiloxane structure as mentioned above. Here, it is preferable that a polysiloxane structure has a repeating structural unit represented by following General formula (1).

-(SiR ¹ R ² -O)-(1)

In the formula, each of R ¹ and R ² 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 an alkoxy group and C1-C3 of an alkyl group), More preferably, it is a C1-C3 alkyl group which does not have a substituent, Most preferably, it is a methyl group.

In the present invention, the polymer having a polysiloxane structure is added to at least a part of the epoxy group of the radical polymer of the monomer mixture containing a (meth) acrylate or dimercaptan or the like having a polysiloxane structure in addition to a hydroxyl group or an epoxy group and a fluoroalkyl group. Or a polymer having a polysiloxane structure in at least part of an epoxy group of a polymer having a structure corresponding to a structure formed by reacting a carboxylic acid having a (meth) acryloyl group or a radical polymer of a monomer mixture having a hydroxyl group and a fluoroalkyl group. It is a polymer which has a structure corresponding to the structure formed by making an acid or a mercaptan, an amine, etc. react.

As for the monomer used for manufacture of the polymer which has such a polysiloxane structure, the (meth) acrylate or dimercaptan which has a polysiloxane structure in which 2 or more repeating structural units represented by said Formula (1) is connected is preferable. Examples of such monomers include polydimethylsiloxane having a methacryloyl group at one end (&quot; Cyrafrain FM-0725 &quot; manufactured by JNC (formerly Chisoso)), and polydimethylsiloxane having a methacryloyl group at both ends (eg For example, Shin-Etsu Chemical Co., Ltd. (X-22-164A)), polydimethylsiloxane having an epoxy group at both ends, polydimethylsiloxane having an epoxy group at both ends and the side chain, and a polydimethylsiloxane derivative having an acryloyl group at the side chain (Example For example, "Tego-Rad" manufactured by Evonik Degus Co., Ltd., polydimethylsiloxane having acryloyl group at both ends (for example, "DMS-U22" manufactured by Gelest), and polydimethylsiloxane having a mercapto group at both ends. (E.g., "X-22-167B" manufactured by Shin-Etsu Chemical Co., Ltd.), a copolymer having polydimethylsiloxane in the main chain or side chain, and having acryloyl group and / or epoxy group in the side chain and / or terminal Can be mentioned.

Moreover, it is preferable that the polysiloxane structure in the polymer of this invention is couple | bonded with the principal chain of the said polymer through the oxygen atom or the sulfur atom through the silicon of the terminal or the saturated hydrocarbon group couple | bonded with the silicon as mentioned above. As a monomer which has a polysiloxane structure for manufacturing such a polymer, when exemplified by methacrylate, for example, dimethyl polysiloxy propyl methacrylate, (alpha)-butyl- (omega)-(3-methacryloxypropyl) polydimethyl There are siloxanes, but they are not limited to them at all. Moreover, when exemplified by dimercaptan, for example, α, ω-dimercaptopolydimethylsiloxane, α, ω-dimercaptopolydiethylsiloxane, α, ω-dimercaptopolymethylethylsiloxane, α, ? -dimercaptopolydihydroxymethylsiloxane,?,?-dimercaptopolydimethoxymethylsiloxane and the like. Among them, α, ω-dimercaptopolydimethylsiloxane is preferable, and this mercapto group may be directly linked to a polysiloxane group or may be connected to a polysiloxane group via an alkylene group. More preferably, the mercapto group is a polysiloxane (?,?-Dimercaptopropylpolydimethylsiloxane) in which a mercapto group is linked to a polysiloxane group via a propylene group. However, it is not limited to these at all.

It is preferable that the (meth) acrylate or dimercaptan which has a polysiloxane structure is about 1000-10000 in number average molecular weight, in order to achieve the balance of pollution resistance and hardness. Here, a number average molecular weight says what was measured using GPC ("HLC-8120GPC" by the Tosoh Corporation), and using tetrahydrofuran as a solvent and polystyrene as a standard sample.

The (meth) acrylate or dimercaptan which has a polysiloxane structure may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, the usage-amount of the (meth) acrylate or dimercaptan which has a polysiloxane structure is 0.01-30 weight% with respect to the whole monomer in the monomer mixture which manufactures a polymer, Preferably it is 0.1-25 weight%, More preferably, 1-20 weight%. If the amount of the (meth) acrylate or dimercaptan having a polysiloxane structure is less than 0.01% by weight, imparting fouling resistance is insufficient, and if it exceeds 30% by weight, the resulting polymer is compatible with other components. The homogeneity and compatibility with the polymer and other components when the composition is made) or the hardness of the cured film are lowered, which is not preferable.

Preferably, the usage-amount of the (meth) acrylate or dimercaptan which has a polysiloxane structure is 0.1 weight% or more, More preferably, it is 1 weight% or more.

Moreover, Preferably the usage-amount of the (meth) acrylate or dimercaptan which has a polysiloxane structure is 25 weight% or less, More preferably, it is 20 weight% or less.

Other (meth) acrylate may be contained in the monomer mixture prepared when manufacturing the polymer in this invention. Although it does not specifically limit as another (meth) acrylate, Preferably, it is low in reactivity with an epoxy group, and does not reduce stability of the produced polymer, or a skeleton is rigid, does not lower hardness, and further pollution resistance What can be improved is required.

Some specific examples of such other (meth) acrylates include styrene or a lower (C1-4) alkyl group, an alkenyl group substituted derivative, a C1-20 alkyl (meth) acrylate, and alkyl ( Radical polymerizable monomers, such as a meth) acrylamide, the cycloalkyl (meth) acrylate which has a C5-20 (poly) cycloalkyl side chain, and (meth) acrylamide, etc. can be illustrated.

Other (meth) acrylates may be used individually by 1 type, and may mix and use 2 or more types.

The usage-amount of another (meth) acrylate is 50 weight% or less. When the usage-amount of another (meth) acrylate exceeds 50 weight%, since the hardness of a polymer falls and the damage resistance and pencil hardness of a surface fall, it is also not preferable.

Preferably, the usage-amount of other (meth) acrylate is 45 weight% or less, More preferably, it is 40 weight% or less.

In manufacture of the polymer of this invention, although the mixture of the monomer mentioned above is radically polymerized, in order to improve the uniformity of the reaction, you may add a solvent to a monomer mixture.

Examples of such a 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 Ether solvents such as propylene glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene, and water; .

These solvent may be used individually by 1 type, and may mix and use 2 or more types.

It is preferable to use a radical polymerization initiator for radical polymerization of the monomer mixture containing the component mentioned above.

As a radical polymerization initiator, the well-known initiator generally used for radical polymerization can be used, Organic peroxides, such as benzoyl peroxide and di-t- butyl peroxide, 2,2'- azobis butyronitrile, 2,2 Azo compounds, such as' -azobis (2,4-dimethylvaleronitrile) and 2,2'- azobis (4-methoxy-2,4-dimethylvaleronitrile), are mentioned as a preferable example.

These radical polymerization initiators may be used individually by 1 type, and may mix and use 2 or more types.

Although there is no restriction | limiting in particular in the mixing and dissolution method of a monomer component and a solvent at the time of carrying out radical polymerization using a solvent and a radical polymerization initiator further as needed to the monomer mixture containing the component mentioned above, For example After mixing of the monomer component and the solvent, it is preferable to add the radical polymerization initiator within a certain time period, preferably within 3 hours, to start the polymerization.

The total concentration of the monomer components in the reaction solution provided for 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 with respect to the total of the monomer components. More preferably, it is 0.2 weight% or more, Preferably it is 10 weight% or less, More preferably, it is 2 weight% or less.

Moreover, although preferable superposition | polymerization conditions change with radical polymerization initiators used, 20-150 degreeC of polymerization temperature, 1-72 hours of polymerization time, More preferably, polymerization temperature is 50-100 degreeC normally, and the polymerization time is 3 to 36 hours.

The polymer in this invention is a carboxylic acid which has a (meth) acryloyl group in at least one part of the epoxy group of the radical polymer obtained as mentioned above, Preferably 1-5 (meth) acryl in 1 molecule It is preferable to add the carboxylic acid which has a royl group. This is because the (meth) acryloyl group becomes a crosslinking point and a polymer takes a crosslinked structure, thereby improving the wiping property of the contaminant and its durability.

As a carboxylic acid which has a (meth) acryloyl group used here, it is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, for example. , Adducts of acid anhydrides such as pentaerythritol tri (meth) acrylate and succinic anhydride, phthalic anhydride, hexahydro phthalic anhydride, dipentaerythritol penta (meth) acrylate and succinic anhydride, phthalic anhydride, hexahydro phthalic anhydride Additives of acid anhydrides, such as these, etc. are mentioned. This may be used individually by 1 type, and may mix and use 2 or more types.

In this addition reaction, the epoxy group which a radical polymer has, and the carboxyl group of the carboxylic acid which has a (meth) acryloyl group react.

The carboxylic acid which has a radical polymer and a (meth) acryloyl group may be called ratio of the carboxyl group of the epoxy group of the radical polymer and the carboxyl group of the carboxylic acid which has a (meth) acryloyl group (hereinafter simply "epoxy group / carboxyl group"). ) Is preferably used at a ratio of 1 or more. Moreover, it is preferable that an epoxy group / carboxyl group is 10 or less, More preferably, it is 5 or less, More preferably, it is 2 or less.

If an epoxy group / carboxyl group is more than this lower limit, the fall of stability by the carboxylic acid which has an unreacted (meth) acryloyl group can be prevented, and if it is this upper limit, it will prevent the fall of stability by the remaining epoxy group. It is preferable because it can.

Moreover, it is preferable in 50-99% of the epoxy groups which a radical polymer has reacted with the carboxyl group of the carboxylic acid which has a (meth) acryloyl group, More preferably, it is 70-98%.

It is preferable to perform this addition reaction at 50-110 degreeC for 3 to 50 hours, More preferably, it is 3 to 30 hours at 80-110 degreeC.

Moreover, in this reaction, in order to accelerate | stimulate reaction, well-known catalysts, such as triethylamine, tributylamine, triethylenediamine, N, N- dimethylbenzylamine, benzyl trimethylammonium chloride, and triphenylphosphine, are mentioned, for example. 1 type, or 2 or more types can be used. It is preferable that it is 0.01 weight% or more with respect to the reaction mixture (that is, the sum total of a radical polymer and the carboxylic acid which has a (meth) acryloyl group), and it is preferable that it is 0.05 weight% or more. Moreover, it is preferable that it is 2 weight% or less, and it is more preferable that it is 1 weight% or less.

Moreover, in this reaction, in order to prevent radical polymerization by the (meth) acryloyl group of the carboxylic acid which has a (meth) acryloyl group, it is hydroquinone, hydroquinone monomethyl ether, catechol, pt, for example. -It is preferable to use 1 type (s) or 2 or more types of polymerization inhibitors, such as butyl catechol and phenothiazine. It is preferable that it is 0.01 weight% or more with respect to a reaction mixture, and, as for the usage-amount of a polymerization inhibitor, it is more preferable that it is 0.05 weight% or more. Moreover, it is preferable that it is 1 weight% or less, and it is more preferable that it is 5 weight% or less.

As mentioned above, although the manufacturing method of the polymer in this invention was given the specific example, the polymer should just have the structure demonstrated above in this invention, and is not limited to what was obtained by the said manufacturing method.

In the resin composition of this invention, only 1 type of the above-mentioned polymer may be contained and 2 or more types may be contained.

Although content of the polymer in the composition of this invention changes also with the use of a composition, the kind of polymer used, and the composition of another containing component, Preferably it is 0.5 weight% or more, More preferably, it is 1 weight% or more, and it is preferable. Preferably it is 20 weight% or less, More preferably, it is 15 weight% or less. If content of a polymer is 0.5 weight% or more, pollution resistance becomes more favorable, and if it is 20 weight% or less, hardness will become high and it is excellent in applicability | paintability.

<1-2. Hydrocarbon Monomer>

The hydrocarbon monomer which is an essential component of the resin composition of this invention contains 1 type (s) or 2 or more types chosen from a (meth) acryloyl group and a vinyl group, Preferably it contains a (meth) acryloyl group.

This component gives favorable hardness to the cured film obtained from a resin composition. In addition, the "hydrocarbon monomer" as used in this specification may contain the bond containing atoms other than carbon and hydrogen.

As a hydrocarbon-type monomer containing a vinyl group, for example, styrene, p-chlorstyrene, p-methoxy styrene, divinylbenzene, N-vinylpyrrolidone, N-vinyl caprolactam, acrylonitrile, ethylene glycol di Vinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropanedivinyl ether, ethylene oxide modified hydroquinonedivinyl ether, ethylene oxide modified bisphenol A divinyl ether, pentaerythritol trivinyl Ether, dipentaerythritol hexavinyl ether, ditrimethylol propane polyvinyl ether, etc. are mentioned.

As a hydrocarbon type monomer containing a (meth) acryloyl group, what has one or two or more (meth) acryloyl groups in 1 molecule is mentioned.

In the molecule as having a group of one (meth) acrylate, the (meth) acrylic acid, (meth) acrylic acid alkyl (C ₁ ~ C _18), phenoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate Rate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (Meth) acrylate, allyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2- Ethoxyethoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2- Hydroxyethyl (meth) acryloyl phosphate, tetrahydrofurfuryl ( Meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentadieneethoxy (meth) acrylate, p-benzylphenoxyethyl (meth) acrylate, 1,6-hexanediol mono (meth) Acrylate, neopentyl glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, 2-hydroxy-3-phenyloxy Propyl (meth) acrylate, 2-hydroxy-3-octyloxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol 400 mono (meth) acrylate, 2- (perfluorooctyl ) and the (meth) acrylate, such as _{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3.

As what has two or more (meth) acryloyl groups in 1 molecule, what is generally called polyfunctional (meth) acrylate or a special (meth) acrylate in the said technical field, A prepolymer, a base resin, and an oligomer Or what is called an acryl oligomer is contained, and the following (i)-(v) is mentioned specifically ,.

(i) A polyhydric (meth) acrylate in which two or more (meth) acrylic acids are bonded to a polyhydric alcohol.

(ii) Polyester acrylate in which 2 or more of (meth) acrylic acid couple | bonded with the polyester polyol obtained by reaction of a polyhydric alcohol and 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 and alkenylsuccinic acid.

(iii) The epoxy acrylate which esterified the epoxy group of an epoxy resin with (meth) acrylic acid, and made it into a (meth) acryloyl group as a functional group.

As an epoxy resin in said (iii), a bisphenol A- epichlorohydrin type, a phenol novolak- epichlorohydrin type, alicyclic resin, etc. are mentioned.

(iv) Polyurethane acrylate obtained by making a hydroxyl group containing (meth) acrylate react with a polyhydric isocyanate compound.

As a polyvalent isocyanate compound in said (iv), the molecular center part has structures, such as polyester, a polyether, and polyurethane, and the thing containing an isocyanate group in the both ends, etc. are mentioned.

(v) Others include polyether (meth) acrylate, melamine (meth) acrylate, alkyd (meth) acrylate, isocyanurate (meth) acrylate, silicone (meth) acrylate, and the like.

Examples of these more specific compounds include 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, diethylene glycoldi ( Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, hydroxy pivalic acid ester neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-bis (3 ''-acryloxyethoxy-2'-hydroxypropyl) 5,5-dimethyl hydantoin, hydroxy pivalic acid ester neopentyl glycol di (meth) acrylate, trimethylolpropane tree ( Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropanedi (meth) acrylate, bisphenol A di ( MET ) Acrylic acid, dipentaerythritol monohydroxypenta (meth) acrylate, tris (acryloxyethyl) isocyanurate, bis (acryloxyethyl) isocyanurate, Hitachi Chemical Co., Ltd. FA-731A, to be mentioned formula (2) to (7) (where, R ₆ is H or -CH _3, n and x is an integer from 1 to 10, respectively), but not limited to these.

[Formula 1]

In this invention, the polyfunctional (meth) acrylate which has three or more (meth) acryloyl groups among the thing which has two or more (meth) acryloyl groups in the said 1 molecule is more preferable. It is because the hardness of the cured film obtained from a resin composition can be improved more by using such a hydrocarbon type monomer.

Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tree (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, polyester (meth) acrylate, polyfunctional urethane (meth) acrylate, polyepoxy (meth) acrylate, isocyanurate ring Although triethoxy (meth) acrylate (for example, Toa synthetic make, Aronix M315, M313 etc.) which has the following can be illustrated, it is not limited to these. Among these, polyfunctional acrylate is good in terms of good performance such as hardness, tris (acryloxyethyl) isocyanurate, bis (acryloxyethyl) isocyanurate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate and pentaerythritol tetra (meth) acrylate are preferable.

The various hydrocarbon monomers illustrated above may be used individually by 1 type, and may mix and use 2 or more types.

In addition, content of the sum total with respect to these preferable content in a composition is not specifically determined unless it deviates from the meaning of this invention, Especially when using as a composition which requires a high hardness, the weight ratio of a hydrocarbon type monomer / polymer is It is desirable to have more polymers than 99.9 / 0.1, especially more polymers than 99/1, less polymers than 50/50, further less polymers than 80/20, especially less polymers than 85/15. It is preferable. By making a polymer below this upper limit, higher hardness can be maintained with respect to the hardened | cured material obtained, and it is preferable. By making it more than this minimum, more favorable stain resistance can be expressed with respect to the hardened | cured material obtained.

<1-3. Saturated Hydrocarbons ＞

Although the well-known thing can be employ | adopted widely as the saturated hydrocarbon which is an essential component of the resin composition (A) which concerns on this invention, a C5-C18 thing is preferable. Those having less than 5 carbon atoms are gas at room temperature, those having 18 or more carbon atoms are solid at room temperature, and handling is difficult. Preferred examples include hexane, heptane, octane, cyclohexane, cycloheptane and the like.

Moreover, it is preferable that the resin composition (B) which concerns on this invention also contains a saturated hydrocarbon. Although a well-known thing can be employ | adopted widely, similarly to the case of the resin composition (A) which concerns on this invention, a saturated hydrocarbon has the thing of 5-18.

Although content of the saturated hydrocarbon in the resin composition (A) which concerns on this invention is 0.01-25 weight%, Preferably it is 0.5 weight% or more, More preferably, it is 1 weight% or more.

Although content of the saturated hydrocarbon in the resin composition (B) which concerns on this invention changes also with the use of a composition, the kind of polymer used, and the composition of another containing component, Preferably it is 0.01 weight% or more, More preferably, 0.5 weight % Or more, More preferably, it is 1 weight% or more, Preferably it is 25 weight% or less, More preferably, it is 23 weight% or less, Especially preferably, it is 20 weight% or less. If the content of the polymer is less than this lower limit, antifoaming is not imparted. If the content of the polymer is greater than this upper limit, the polymer may be precipitated.

Moreover, in the resin composition of this invention, it is preferable that the polymer which is an essential component, and saturated hydrocarbon are 5: 1: 1: 20 by weight ratio. It is because the bubble generation property of a resin composition is easy to be suppressed by the interaction of both components, and such defoaming property is easy to be improved because such a ratio is this range.

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

A well-known thing can be employ | adopted widely for the fluorine group containing oligomer whose surface tension decreasing ability which is an essential component of the resin composition (B) which concerns on this invention is 2 mN / m or more. Here, surface tension decreasing ability is the amount of decrease in the surface tension of PGMAc (1-methoxypropyl-2-propanol) when 1 mass% of fluorine group containing oligomers are melted ("surface tension reducing ability" = "surface of PGMAc"). Tension "-" surface tension of 1% PGMAc solution ").

The surface tension lowering ability of the fluorine group-containing oligomer is not particularly limited as long as it is 2 mN / m or more, but the upper limit is preferably 15 mN / m or less, more preferably 12 mN / m or less, particularly preferably 10 mN / m. m or less. Moreover, as a lower limit, Preferably it is 2 mN / m or more, More preferably, it is 3.5 mN / m or more, Especially preferably, it is 5 mN / m or more. If it is below this upper limit, since compatibility is favorable, it is preferable, and if it is above this lower limit, since defoaming property is favorable, it is preferable. In addition, the said surface tension decreasing ability is the value computed using the surface tension meter ("Drop Master series" by Kyowa Interface Chemical). In addition, the surface tension reducing ability is a numerical value determined by the molecular structure of the additive. When the structure has a fluorine atom or a Si atom, the surface tension reducing ability tends to increase, and when a large amount of polar groups is contained, the surface tension reducing ability tends to decrease. It is determined by this.

The fluorine group-containing oligomer is not particularly limited as long as the surface tension lowering ability is 2 mN / m or more, but the lower limit of the weight average molecular weight is preferably 5000 or more, more preferably 6000 or more, particularly preferably 7000 That's it. Moreover, as an upper limit, Preferably it is 40000 or less, More preferably, it is 20000 or less, Especially preferably, it is 15000 or less. If it is below this upper limit, since compatibility with other components is favorable, it is preferable. If it is more than this lower limit, since defoaming property is favorable, it is preferable. Here, a weight average molecular weight says what was measured using GPC ("HLC-8120GPC" by the Tosoh Corporation), and using tetrahydrofuran as a solvent and polystyrene as a standard sample.

Moreover, it is preferable that a fluorine group containing oligomer does not contain acryloyl group because foaming property is favorable.

Moreover, it is preferable that a fluorine-group containing oligomer is nonionic from the point which is excellent in defoaming property. Specifically, FUTAZENTO 710FM of Neos Corporation, Megapak F-555 by DIC Corporation, NS-9013 by Daikin Corporation, etc. are mentioned, for example. Two or more said oligomers may be mixed and used.

Although preferable content of the fluorine-group containing oligomer in the resin composition (B) which concerns on this invention is not specifically determined unless it deviates from the meaning of this invention, It is 0.005-10 weight% of the whole resin composition (B) which concerns on this invention. It is preferable and it is more preferable that it is 0.01 to 5 weight%. When such content is less than 0.005 weight%, the bubble generation of a resin composition may not be suppressed, and when larger than 10 weight%, defects, such as a stripe and a crater, may arise at the time of application | coating of a resin composition.

It is preferable that the resin composition (A) which concerns on this invention also contains a fluorine group containing oligomer, and it is preferable to contain a nonionic fluorine group containing oligomer. This is for further improving the bubble generation prevention of the resin composition.

As a nonionic fluorine-group containing oligomer, it is preferable that it is 5000-20000, and, as for a polymerization average molecular weight, it is more preferable that it is 5000-10000. For example, Futagento 710FM manufactured by Neos, Megapak F-554, Megapak F-555, Megapak F-556, Megapak RS-75, Daikin Corporation NS-9013, DSN-403N, etc. Although it is mentioned, Preferably it is futazenta 710FM, Megapak F-555, NS-9013. Here, a polymerization average molecular weight says what was measured using GPC ("HLC-8120GPC" by the Tosoh Corporation), and using tetrahydrofuran as a solvent and polystyrene as a standard sample.

Although content of the nonionic fluorine group containing oligomer in the resin composition (A) which concerns on this invention is not specifically limited, It is preferable that it is 0.005-10 weight% of the whole resin composition (A) which concerns on this invention, and it is 0.01-5 weight% It is more preferable that it is and it is especially preferable that it is 0.1 to 2 weight%. When such content is less than 0.005 weight%, the bubble generation of a resin composition may not be suppressed, and when larger than 10 weight%, defects, such as a stripe and a crater, may arise at the time of application | coating of a resin composition.

<1-5. Solvent

Although the solvent which is an essential component of the resin composition of this invention is an SP value of 10.0 or less, Preferably it is 9.5 or less, More preferably, it is 9.3 or less, Especially preferably, it is 9.0 or less. If it is below this upper limit, since defoaming property is favorable, it is preferable. Moreover, as a lower limit, Preferably it is 7.5 or more, More preferably, it is 7.8 or more, More preferably, it is 8.0 or more, Especially preferably, it is 8.2 or more, Most preferably, it is 8.5 or more. If it is more than this lower limit, since compatibility is favorable, it is preferable.

The SP value represents the solubility parameter, which is calculated by the method proposed by the Fedors. Specifically, POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 147 to 154). In addition, SP value is a physical-property value determined by content of a hydrophobic group and a hydrophilic group of a molecule | numerator, and when using a mixed solvent, it is also possible to mix suitably a solvent with a small 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, the hydrophilic group is increased, so colloids are formed easily, and bubbles are easily generated. When a solvent having a low SP value is used, bubbles can be prevented. . However, in order to raise the solubility of the polymer which is an essential component of the resin composition of this invention, since a uniform solution can be obtained using the solvent with a high SP value to some extent, it is preferable. Therefore, what has SP value in the said range is used as a solvent in this invention.

As a solvent in this invention, if SP value exists in the said range, a well-known thing can be employ | adopted widely, but ketone solvents, such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK); ethanol, methanol Alcohol solvents such as isopropyl alcohol (IPA) and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl Ester solvents, such as acetate; Aromatic-hydrocarbon solvents, such as toluene, etc. are mentioned as a preferable example. Among these, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) of a ketone solvent are more preferable from the viewpoint of low bubble generation and high compatibility with the polymer of the present invention.

These solvent may be used individually by 1 type, and may mix and use 2 or more types.

When the resin composition of this invention is used for application | coating use especially as mentioned later, when it contains these organic solvents, its solid content concentration is 10 weight% or more, especially 20 weight% or more, 90 weight% or less, It is preferable to be prepared especially at 70 weight% or less.

<1-6. Radical Polymerizable Photoinitiator>

It is preferable that the resin composition of this invention contains a radically polymerizable initiator in addition to the said essential component. This is for performing hardening of a resin composition efficiently. Usually, although hardening of a resin composition is performed by irradiating an active energy ray, when irradiation energy is very strong like an electron beam (EB), it can be abbreviate | omitted when addition of a radically polymerizable initiator is not needed.

As a radically polymerizable photoinitiator, well-known thing can be employ | adopted widely, Preferably, it is an alkyl phenone type compound ((alpha) -hydroxy acetophenone type, (alpha)-amino acetophenone type, benzyl ketal type, etc.), an acyl phosphine oxide. Type compounds, oxime ester compounds, oxyphenylacetic acid esters, benzoin ethers, phenyl formic acid esters, ketone / amine compounds and the like. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxy acetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclo Hexylphenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propaneone, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, methylbenzoylformate, mihilerketone, N, N-dimethylaminobenzoic acid isoamyl, 2-chlorothioxanthone, 2 , 4-diethyl thioxanthone and the like are preferable.

These radically polymerizable photoinitiators may be used individually by 1 type, and may mix and use 2 or more types.

Although content of the radically polymerizable photoinitiator in the resin composition of this invention can be suitably determined according to the kind of radically polymerizable photoinitiator to be used, Inorganic oxide microparticles | fine-particles which have a polymer in a composition and colloidal silica mentioned later as a main component- Organic-inorganic composite having a (meth) acryloyl group bonded through an O—Si—R— bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms.), A radically polymerizable organic (meth 10 weight% or less is preferable with respect to the sum total of the polymerizable components in compositions, such as an acrylate compound and / or a radically polymerizable organic (meth) acrylamide compound and the polymer which has a radically polymerizable group other than the polymer of this invention, 8 The weight% or less is more preferable, and 0.5 weight% or more is preferable. If there is less content of a radically polymerizable photoinitiator than this range, hardening will become inadequate, and when there is much, the fall of hardness and the fall of a fouling resistance may arise.

Moreover, as a radically polymerizable photoinitiator, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1- propane, 2-benzyl-2- dimethylamino-1- (4-morpholin) Α-aminoacetophenone initiators such as nophenyl) -butan-1-one, Chiba Specialty Chemicals Co., Ltd. oxime ester initiators such as Irgacure OXE-01, 1-hydroxycyclohexylphenyl ketone and Michler's ketone When one or two or more kinds of a mixture of an α-hydroxyketone-based initiator and a benzophenone-based sensitizer, such as 20% by weight or more in the radically polymerizable photoinitiator component, is used, the inhibition of polymerization by oxygen is more reduced. Further improvement of surface curability and thin film curability can be seen, and it may be especially preferable.

<1-7. Other optional ingredients>

In the resin composition of this invention, in order to adjust the coating film physical properties, such as hardness, and liquid physical properties, such as the viscosity of a composition, when a composition is made into a coating film, it further has radically polymerizable groups other than the polymer of this invention. The (meth) acryl bonded to the inorganic oxide fine particles containing a polymer and colloidal silica as a main component via -O-Si-R- bond (R represents a C2-C10 linear or branched alkylene group). You may contain 1 type (s) or 2 or more types chosen from the organic-inorganic composite which has a diary, and an inorganic fine particle.

Although these content is not specifically defined unless it deviates from the meaning of this invention, It is preferable that it is 0.1-50 weight% of the whole resin composition, and it is more preferable that it is 1-30 weight%. If the content is less than 0.1% by weight, it is difficult to obtain the effect of praying with the addition of these additional components (for example, improving the hardness of the coating film, suppressing curl, etc.), and if the content is higher than 50% by weight, the coating film properties such as fouling resistance. This may fall.

Here, as polymers other than the polymer of this invention, Preferably, (meth) acrylate type polymers other than the polymer of this invention which have radical polymerizable groups, such as acryloyl group and methacryloyl group, in a side chain, such a polymer And copolymers of other radical polymerizable monomers such as styrene. Specifically, glycidyl acrylate, glycidyl methacrylate, 3, 4- epoxycyclohexyl acrylate, 3, 4- epoxycyclohexyl methacrylate, 3, 4- epoxycyclohexyl methyl acrylate, 3 The polymer which has a (meth) acryloyl group in the side chain obtained by adding (meth) acrylic acid to the polymer superposed | polymerized as a main component of 4, 4- epoxycyclohexyl methyl methacrylate is preferable. Of course, it does not exclude anything other than these. These may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, in addition to the component mentioned above, the resin composition of this invention can mix | blend another component with the objective of providing various functionalities.

For example, when a ultraviolet absorber and a hindered amine light stabilizer are mix | blended, weather resistance will improve remarkably and may be preferable. As a ultraviolet absorber, a benzotriazole type, a benzophenone type, a salicylic acid type, a cyanoacrylate type, a triazine type ultraviolet absorber etc. are mentioned as a preferable example. In addition, for the purpose of improving the coating film properties, this kind of fouling resistance imparting agents such as antioxidants (for example, hindered phenol-based, sulfur-based, phosphorus-based antioxidants, etc.), antiblocking agents, slip agents, leveling agents, and the like You may mix | blend the various additives mix | blended with. As a compounding quantity of these additives, it is preferable to set it as 0.01 weight% or more and 2 weight% or less with respect to another solid content, respectively.

Moreover, you may mix | blend the inorganic oxide microparticles used for the organic-inorganic composite (C2) mentioned above untreated with the resin composition of this invention for the purpose of further improving hardness, blocking resistance, etc.

Moreover, you may contain auxiliary antifoamers, such as a silicone type compound, auxiliary.

<1-8. Defoaming

The resin composition of the present invention has excellent antifoaming properties. Therefore, when used as a coating paint, cratering does not arise in a coating film, and it becomes the thing excellent in the leveling property of the cured film obtained from this coating film.

Here, what is excellent in defoaming property is an essential component of a resin composition so that solid content (polymer and a hydrocarbon monomer which are essential components of a resin composition) is 50 weight%, and the ratio of the polymer in solid content is 5 weight%. The phosphorus saturated hydrocarbon (10 wt% of the total solution) and 15 ml of the solution dissolved in the solvent, which is an essential component, were placed in a 30 ml volume of a user cylindrical container having an internal diameter of 1.5 cm, 20 times in 5 seconds. The shaking was stopped and stopped, and the time until the bubbles on the surface of the generated liquid disappeared was visually measured. It is preferable that the bubble of the liquid surface disappear in less than 15 minutes, and more preferable in less than 2 minutes.

<1-9. Why the present invention is effective>

The reason for the effect of the present invention is estimated as follows. In general, in a solvent having a high SP value, a polymer having a hydroxyl group and a fluoroalkyl group, that is, a polymer having a hydrophilic group and a hydrophobic group, forms a bubble of a solution by arranging the hydrophobic group to the outside. Therefore, in the first aspect of the present invention, by using a solvent whose SP value is equal to or less than a specific value, by adding a saturated hydrocarbon, the hydrophobicity of the solvent is increased, and the antifoaming property is improved by inhibiting the polymer from forming bubbles. It is inferred that a hydrocarbon becomes the origin of a vesicle by demolishing the arrangement | sequence of the molecule | numerator in the solution of the polymer which has the hydrophilic and hydrophobic group which forms a bubble, and exhibits the effect of this invention. Moreover, similarly, in the 2nd aspect of this invention, by using the solvent whose SP value is below a specific value, and adding the additive more than fixed which has surface tension decreasing ability, it raises the hydrophobicity of a solvent and suppresses that a polymer forms air bubbles. When defoaming becomes good and a fluorine-group containing oligomer breaks down the arrangement | sequence of the molecule in the solution of the polymer which has the hydrophilic and hydrophobic group which forms a bubble, it becomes a starting point of a defoaming, and exhibits the effect of this invention. Inferred.

<2. Cured product ＞

By hardening the resin composition of this invention, the cured film which shows the outstanding physical property mentioned later can be obtained.

After apply | coating the resin composition of this invention, after forming a coating film by solvent drying, the polymeric component in a composition is polymerized by irradiating an active energy ray, and a cured film can be obtained. As a coating method, a spin coat, a dip coat, a flow coat, a spray coat, a bar coat, a gravure coat, a roll coat, a blade coat, an air knife coat, etc. are mentioned as a preferable example. The thickness of the film obtained by apply | coating, drying, superposition | polymerization, and hardening is not specifically determined, For example, 5 micrometers or more may be sufficient and 2 micrometers or less may be sufficient. That is, the resin composition of this invention is very meaningful in that both thin film formation and thick film formation are possible. The thickness of the cured film is particularly preferably 0.01 µm or more and 50 µm or less, particularly preferably 2 µm or more and 20 µm or less when the hardness is important, and particularly preferably 0.04 µm when the hardness is not relatively important. The above is 2 micrometers or less.

As the active energy ray irradiation, ultraviolet rays generated from light sources such as xenon lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, or electron beams usually extracted from particle accelerators of 20 to 2000 kV. active energy rays such as?,?,? and? rays can be used, and these active energy rays are irradiated onto the coating film and cured to form a cured film.

The cured film formed by irradiation with such an active energy ray is excellent in the balance of productivity and a physical property, and it is especially preferable.

Although it is a thing formed by irradiating an active energy ray to the resin composition of this invention mentioned above with the hardened | cured material of this invention, and polymerizing the polymerizable component in a composition, it is preferable to satisfy especially the following suitable physical properties. Moreover, hardening of the coating film containing the resin composition of this invention is not limited to an ultraviolet-ray, Active energy rays, such as an electron beam, (alpha) rays, (beta) rays, (gamma) rays, can be used, and the "active energy ray in this invention is used. Irradiation and polymerization "includes photoradical polymerization or photocationic polymerization as preferable examples. In addition, below, all ultraviolet irradiation is normally performed in oxygen concentration atmosphere.

<2-1. Properties of Cured Product>

The hardened | cured material obtained by hardening the resin composition of this invention has the following physical properties.

<2-1-1. Hardness ＞

The hardened | cured material of this invention shows high hardness. Here, high hardness means pencil hardness of HB or more under the conditions of the pencil hardness JISK-5400 standard. In addition, pencil hardness is set to 6B, 5B, ..., B, HB, F, H, 2H, 3H, ... 9H in order from a soft thing.

The resin composition of this invention was apply | coated on 188 micrometer-thick easy adhesion | attachment PET base material, and the ultraviolet-ray of wavelength 254nm was integrated into 500 mJ / cm <2> quantity of ultraviolet rays with a wavelength of 254 nm using the high pressure mercury lamp of the output density of 120 W / cm for the obtained coating film. It is preferable that the pencil hardness of the cured film with a film thickness of 5 micrometers formed by irradiating so that it may be B or more, especially HB or more.

When the resin composition of this invention contains dipentaerythritol hexaacrylate especially, it is apply | coated on 188 micrometer-thick easy adhesion | attachment PET base material, using the high pressure mercury lamp of 120 W / cm of output density to the obtained coating film. It is preferable that the pencil hardness of the cured film with a film thickness of 5 micrometers formed by irradiating the ultraviolet-ray with a wavelength of 254 nm so that it may be accumulated light quantity of 500 mJ / cm <2> is 3H or more.

However, the composition used for evaluation of this pencil hardness uses only 1-hydroxycyclohexylphenyl ketone as a radically polymerizable photoinitiator, and, with respect to 100 weight part of solid content other than 1-hydroxycyclohexylphenyl ketone, 2.5 weight part of 1-hydroxycyclohexyl phenyl ketones are mix | blended.

<2-1-2. Water Repellent Oil Repellent>

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

Here, the excellent water / oil repellency is that the resin composition of the present invention is coated on a 188 μm-thick easily adhered PET substrate, and a high pressure mercury lamp having an output density of 120 W / cm is used for the obtained coating film, which has a wavelength of 254 nm. The contact angle with respect to the water of the surface of the cured film with a film thickness of 5 micrometers formed by irradiating an ultraviolet-ray to the accumulated light amount of 500 mJ / cm <2> is 100 degree | times or more, 120 degrees or less, especially 102 degrees or more and 115 degrees or less, and hexadecane The contact angle with respect to can be evaluated by being 50 degrees or more and 90 degrees or less, especially 52 degrees or more and 75 degrees or less. In addition, this measuring method of a contact angle demonstrates the detail in the Example mentioned later.

<2-1-3. Pollution Resistance and Durability>

The cured product of the present invention is excellent in fouling resistance and excellent in durability of its properties. In particular, it shows excellent antifouling property against oil-based contamination.

It is excellent in stain resistance, when black magic adheres to the hardened | cured material of the resin composition or cured film of this invention, and wipes off with tissue paper by 200g load, Wiping operation within 3 round trips, More preferably, 2 It can evaluate by what is very fingerprint-proof which can remove a fingerprint completely by operation within reciprocation.

In addition, the excellent durability of the stain resistance can be evaluated by not removing the fingerprint removal property even if the wiping operation of attaching black magic and performing three reciprocating wiping with tissue paper at 200 g load is repeated five times. It is a larger characteristic of the hardened | cured material of this invention.

Even if a fouling imparting agent that is wiped off with a small number of wiping times is used, the conventional ones have insufficient hardness or are not fixed to the membrane surface. A flaw occurred, fingerprint (or artificial fingerprint liquid) entered in the gap, or the stain resistance imparting agent itself disappeared from the surface, and durability of fingerprint removal property was inferior. On the other hand, since the resin composition of the present invention has a high hardness after curing and is fixed to the film surface, even if the operation is repeated five or more times, preferably ten or more times, the wiping property of black magic does not decrease very much. It has the characteristic of having high wiping performance durability.

<3. Molded article having a cured film>

As mentioned above, the hardened | cured material formed by irradiating an active energy ray to the resin composition of this invention and polymerizing the polymerizable component in a composition is excellent in characteristics, such as pollution resistance and hardness.

Therefore, the article which has on the surface the cured film obtained by irradiating an active energy ray to the resin composition of this invention is excellent in characteristics, such as a contamination resistance and hardness.

After apply | coating the resin composition of this invention on the surface of an article main body, this cured film may be formed by irradiating an active energy ray and superposing | polymerizing, and after forming separately the formed cured film which irradiated and polymerized an active energy ray, it laminate | stacks on an article It may be formed by.

Hereinafter, the hardened | cured material of this invention, especially the article provided with a cured film is demonstrated.

The cured film of the present invention can be applied to various articles, but for example, a transparent film of an optical recording medium, an optical display, or an agricultural vinyl house (since it is necessary to effectively take in sunlight, a pollution-resistant function is required. ), Solar cell surface protection transparent film (pollution-resistant function is necessary to prevent deterioration of battery efficiency), reflex reflection mark transparent film for surface protection (easy to show the mark letters even with relatively dark light of head lamp light or outside light) In order to be transparent and stain resistant), an optical lens, an optical prism, a prism sheet, a window member of an automobile, a window member of a building, an eyeglass lens, and the like. In particular, it is preferable to apply to the optical article which requires high transparency.

The resin composition of this invention is preferably used in order to apply | coat, dry, and harden on various base materials, and to form a hard-coat layer. In this case, although the kind of base material is not specifically limited, The base material which consists of resin from a high adhesiveness etc. is preferable. The resin substrate may be any of a plate, a sheet, and a film, or may be a molded article of any shape. Moreover, a part of laminated body may be sufficient as a base material, and another layer may be interposed between a base material and a cured film.

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

As the thermoplastic resin, for example, polyester such as polyethylene terephthalate (PET) or polyethylene naphthalate, methyl polymethacrylate (PMMA), methyl methacrylate (MMA) -containing copolymer (methyl methacrylate-styrene copolymerization) Resin (MS resin)), polycarbonate (PC), triacetylcellulose, acrylonitrile-butadiene-styrene copolymer (ABS resin), modified polyolefin resin, fluorine resin (e.g. vinylidene fluoride resin (PVDF), Vinyl fluoride resins (PVF) and the like, hydrogenated polystyrene resins, and cycloolefin-based resins (for example, Aton manufactured by JSR, Zeonex manufactured by Nippon Xeon, Zeanoa, Arpel manufactured by Mitsui Chemical), and the like.

As cured resin, hardened | cured material, such as an epoxy resin, a urethane resin, hardened | cured material of thermosetting or photocurable acrylic resin, thermosetting or photocurable organic-inorganic hybrid resin, etc. are mentioned, for example.

These base materials may be a film | membrane formed itself, for example, and the molded article by various shaping | molding methods may be sufficient as them.

Since the cured film of this invention is excellent in transparency, excellent in stain resistance, and hardness, it is very useful when applied to the optical article which requires high transparency. At this time, when the base material is also required to be transparent, the base material is preferably formed by any one of a coating method, a melt extrusion molding method, and a solvent cast method. Moreover, when a base material contains a functional group which can harden | cure an active energy ray or heat, it may be more preferable if it hardens | cures by active energy ray irradiation or heating. Moreover, in order to raise the hardness of a base material or to reduce hardening shrinkage, it is preferable to contain an inorganic oxide fine particle and / or urethane acrylate. In addition, generally transparent means that the transmittance | permeability of the light of the target wavelength is 80% or more.

The cured film of the present invention can also be suitably used as a stain resistant hard coat layer of an optical recording medium.

The resin composition of this invention can be used suitably also for an optical display use. In particular, it is preferable as an antifouling agent to the surface of a display panel of flat panel displays (liquid crystal display, plasma display, rear projection display, screen for front projector, inorganic EL display, organic EL display, etc.), and among them, car navigation system, portable It can be preferably used as a hard coat layer on the surface of a flat screen TV (especially a liquid crystal television) which is widely used in homes, or a display having a touch panel input function in a telephone, a mobile information terminal (PDA etc.), a PC monitor, or the like.

When applying the resin composition of this invention to the laminated body used for such an optical recording medium or a display, an active energy ray is used for the resin composition of this invention on the at least one outermost surface of a laminated body using a transparent resin base material. It is preferable to form the cured film formed by irradiating and superposing | polymerizing.

The hardened | cured material formed by irradiating and polymerizing an active energy ray to the resin composition of this invention is excellent in characteristics, such as pollution resistance and hardness.

The article which has the film | membrane formed on the surface of the resin composition of this invention by irradiating an active energy ray and superposing | polymerizing is excellent in characteristics, such as a contamination resistance and hardness. After apply | coating a composition to the surface of an article, you may irradiate and superpose | polymerize by irradiating an active energy ray, and you may laminate | stack the film | membrane irradiated and polymerized by active energy ray to an article.

Example

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary deviates from the summary.

An Example is given to the following and this invention is demonstrated to it further more concretely. The materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below.

In addition, "part" and "%" in an example mean "weight part" and "weight%", respectively.

<Synthesis example 1: synthesis | combination of a polymer (A-01)>

55 g perfluorohexylethyl methacrylate, lauryl methacrylate 11 g, glycidyl methacrylate 34 g, dodecyl mercaptan 0.9 g (M (a1) / M (a3) = 1.78), 1- 200 g of methoxy-2-propanol was added and the internal temperature was heated up to about 60 degreeC under nitrogen stream. Then, 2,2'- azobis (2, 4- dimethylvaleronitrile) (V65) was divided | segmented into 2 times, 1.2 g in total was added, and stirring was continued at 65 degreeC for 6 hours. Thereafter, the internal temperature was raised to 80 ° C to completely deactivate V65, and then returned to room temperature. Solid content concentration was about 34%.

Next, after heating at 90 degreeC in 7% oxygen atmosphere, 0.5 g of p-methoxyphenols and 4.6 g of triphenylphosphines 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. The liquid temperature was maintained at 90-105 degreeC during this time. The liquid temperature was raised to 110 degreeC after that, and it hold | maintained at this temperature for 12 hours, and then returned to room temperature. Solid content was 35% (A-01).

In addition, content of the fluorine atom computed from the injection weight was 12.3 weight%, and content of the hydroxyl group was 1.6 weight%.

<Synthesis example 2: synthesis | combination of a polymer (A-02)>

50 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), 30 g glycidyl methacrylate, dodecyl 0.9 g of mercaptans and 200 g of 1-methoxy-2-propanol were added, and the internal temperature was heated up to about 60 degreeC under nitrogen stream. Then, 2,2'- azobis (2, 4- dimethylvaleronitrile) (V65) was divided | segmented into 2 times, 1.2 g in total was added, and stirring was continued at 65 degreeC for 6 hours. Thereafter, the internal temperature was raised to 80 ° C to completely deactivate V65, and then returned to room temperature. Solid content concentration was about 34%.

Next, after heating at 90 degreeC in 7% oxygen atmosphere, 0.5 g of p-methoxyphenols and 4.6 g of triphenylphosphines 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. The liquid temperature was maintained at 90-105 degreeC during this time. The liquid temperature was raised to 110 degreeC after that, and it hold | maintained at this temperature for 12 hours, and then returned to room temperature. Solid content was 30% (A-02).

<Synthesis example 3: synthesis of a polymer (A-03)>

50 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), 30 g glycidyl methacrylate, dodecyl 0.9 g of mercaptans and 200 g of 1-methoxy-2-propanol were added, and the internal temperature was heated up to about 60 degreeC under nitrogen stream. Then, 2,2'- azobis (2, 4- dimethylvaleronitrile) (V65) was divided | segmented into 2 times, 1.2 g in total was added, and stirring was continued at 65 degreeC for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and V65 was completely deactivated, and then returned to room temperature. Solid content concentration was about 34%.

Next, after heating at 90 degreeC in 7% oxygen atmosphere, 0.5 g of p-methoxyphenols and 4.6 g of triphenylphosphines 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. The liquid temperature was maintained at 90-105 degreeC during this time. Thereafter, the liquid temperature was raised to 110 ° C, held at this temperature for 12 hours, and then returned to room temperature. Solid content was 35% (A-03).

In addition, content of the fluorine atom computed from the injection weight was 12.1 weight%, and content of the hydroxyl group was 1.5 weight%.

<Synthesis example 4: synthesis of a polymer (A-04)>

50 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of polydimethylsiloxane-containing methacrylate (number average molecular weight 1000, Chissosa, FM0711), 30 g glycidyl methacrylate, dode 0.9 g of silmercaptan and 200 g of 1-methoxy-2-propanol were added, and the internal temperature was heated up to about 60 degreeC under nitrogen stream. Then, 2,2'- azobis (2, 4- dimethylvaleronitrile) (V65) was divided | segmented into 2 times, 1.2 g in total was added, and stirring was continued at 65 degreeC for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and V65 was completely deactivated, and then returned to room temperature. Solid content concentration was about 34%.

Next, after heating at 90 degreeC in 7% oxygen atmosphere, 0.5 g of p-methoxyphenols and 4.6 g of triphenylphosphines 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. The liquid temperature was maintained at 90-105 degreeC during this time. Thereafter, the liquid temperature was raised to 110 ° C, held at this temperature for 12 hours, and then returned to room temperature. Solid content was 35% (A-04).

In addition, content of the fluorine atom computed from the injection weight was 12.1 weight%, and content of the hydroxyl group was 1.5 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 are added, and the internal temperature is raised to about 60 ° C. under a nitrogen stream. Elevated temperature. Thereafter, 2,2'-azobis (2,4-dimethylvaleronitrile) (V65) was divided into two portions, and 1.5 g in total was added, and stirring was continued at 65 ° C for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and V65 was completely deactivated, and then returned to room temperature. Solid content concentration was about 34%.

Next, after heating to 90 degreeC in air atmosphere, 0.1 g of p-methoxyphenols and 0.5 g of triphenylphosphines 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. The liquid temperature was maintained at 90-105 degreeC during this time. Thereafter, the liquid temperature was raised to 110 ° C, held at this temperature for 12 hours, and then returned to room temperature. Solid 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, 200 g of 1-methoxy-2-propanol were added, and the internal temperature was It heated up to about 60 degreeC under nitrogen stream. Then, 2,2'- azobis (2, 4- dimethylvaleronitrile) (V65) was divided | segmented into 2 times, 1.2 g in total was added, and stirring was continued at 65 degreeC for 6 hours. Thereafter, the internal temperature was raised to 80 ° C, and V65 was completely deactivated, and then returned to room temperature. Solid content concentration was about 34% (X-02).

[Examples 1-1 to 1-11]

<Preparation and Evaluation of Resin Composition>

In the compounding (weight ratio) shown in Table 1, the resin composition of Examples 1-1 to 1-11 and Comparative Examples 1-9 was prepared.

※ 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 added to the SP value of a solvent.

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

M-313 ： Isocyanuric acid EO modified di and triacrylate ("Aronix M-313" made by Toa synthesis company)

irg184: Hydroxycyclohexyl phenyl ketone ("irgacure 184" made by BASF Corporation)

Mega pack F-555 ： Mega pack F-555 made by DIC Corporation

Futagento 710 FM ： Neos Corporation "Futazento 710 FM"

MIBK ： Methyl isobutyl ketone

MEK ： Methyl ethyl ketone

PGM ： 1-methoxy-2-propanol

PGMAc: 1-methoxypropyl-2-acetate

Antifoaming property was evaluated about the resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1-9 which were prepared as mentioned above.

The evaluation method is as follows. 15 ml of the resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1 to 9 were each placed in a 30 ml volume of a user cylindrical container having an internal diameter of 1.5 cm, and shaken 20 times for 5 seconds (amplitude 10 to 20). cm) and then stop. The time required until the bubbles on the liquid surface disappear is visually measured, and the "foaming property" is measured in three steps (◎: less than 3 minutes, ○: 3 minutes or more and less than 20 minutes, × : 20 minutes or more). Moreover, transparency and uniformity of the liquid before shaking were observed, and it evaluated in two steps ((circle:: transparent, x: there is cloudiness, and precipitation) as an "appearance"). The results are shown in Table 2.

※ The numbers in parentheses indicate the time until the bubbles on the surface of the liquid disappear.

As shown in Table 2, the resin composition of Examples 1-1 to 1-9 showed the outstanding defoaming property. On the other hand, in the resin composition of Comparative Examples 1-7, foam | bubble was easy to generate | occur | produce, and foam | bubble hardly disappeared. In particular, in Comparative Example 3, the liquid was cloudy and difficult to observe, and thus, the anti-foaming property could not be evaluated. In addition, as shown in the comparative example 8 which used the polymer which has a hydroxyl group and does not have a fluoroalkyl group, and the comparative example 9 which used the polymer which does not have a hydroxyl group and has a fluoroalkyl group, the bubble of a resin composition has the hydroxyl group which exists in a polymer, and It originates in a fluoroalkyl group.

<Production and Evaluation of Cured Film>

The resin compositions of Examples 1-4, 1-5, 1-7 and 1-9 and Comparative Example 2 prepared as described above were formed on the PET substrate (thickness 188 μm) so as to form a cured film having a thickness of 3 to 4 μm. It apply | coated and dried at 80 degreeC after that, the solvent was removed, and the dry film was formed. The coating film was irradiated and cured in a normal oxygen concentration atmosphere using a high-pressure mercury lamp having an output density of 120 W / cm in a normal oxygen concentration atmosphere so as to have an accumulated light amount of 500 mJ / cm 2.

About the cured film produced as mentioned above, the following items (1)-(6) were evaluated.

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

(2) Hardness: It measured based on the conditions of JISK-5400 using the JIS conformity pencil hardness meter (made by the Thai oil base company), and showed by the number of the hardest pencils with which a flaw does not occur.

(3) Water repellent and oil repellent: After the cured film was stopped for 24 hours in a constant temperature room at a temperature of 23 ° C. and a humidity of 60% RH, and the condition was adjusted, the cured film was contacted with a contact angle meter (Drop Master DM500 manufactured by Kyowa Interface Science). 0.002 ml of pure water or hexadecane was added dropwise thereto, and after 1 minute, the contact angle with respect to water and the contact angle with respect to hexadecane were measured using a contact angle meter (Drop Master 500 manufactured by Kyowa Interface Science). Unit; degrees).

(4) Adhesiveness: It tested by the cross cut method of JISK5400. 100 checkerboard scales were put into the cured film at 1 mm space | interval, and it tested using the cellophane tape (made by Nichi-reflection). The same operation was repeated five times (the cellophane tape always used a new one), and no defects or peelings occurred at all,? Evaluated.

(5) Magic-resistant: ： Draw a line on the cured film with an oil-based magic marker (fine zebra care ultrafine (black)), and after 30 seconds, if the line turns out, ○, if not It evaluated as two steps as x.

(6) Magic wiping durability ： To the cured film, draw a line with an oil-based magic marker (the zebra-made Mackie care ultrafine (black)), and after 10 seconds, wipe the surface with tissue paper (manufacturer: Cresia), The operation was repeated, and 8 to 5 times were evaluated in three steps with ○, 4 to 2 times as △ and 1 time as × from the number of times until it was not wiped off.

Table 3 shows the evaluation results of the cured film.

The cured film obtained by hardening the resin composition of this invention was favorable also in any of transparency, hardness, water / oil repellency, adhesiveness, stain resistance, and stain resistance durability.

By the said Example, it was shown that the resin composition of this invention is small in bubble generation property and excellent in leveling property. Moreover, by hardening the resin composition of this invention, it was shown that hardened | cured material which is high in hardness, and excellent in contamination resistance, its durability, water / oil repellency, and adhesiveness was realized.

[Examples 2-1 to 2-25]

<Preparation and Evaluation of Resin Composition>

In the compounding (weight ratio) shown in Table 4, the resin composition of the Example and the comparative example was prepared. Specifically, the polymer and polyfunctional acrylate synthesized in Synthesis Example described above were mixed in 100 parts by weight in total at the ratios shown in Table 4, and the initiator and the additive were added to 100 parts by weight of the mixture of the polymer and the polyfunctional acrylate. Were mixed at the ratio of Table 4, respectively. A solvent was added there by the weight ratio of Table 4, and in Example 2-4, 2-5, 2-10, 2-11, 2-15-2-18, saturated hydrocarbon was also added and the resin composition was prepared. .

※ 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 added to the SP value of a solvent.

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

M-313 ： Isocyanuric acid EO modified di and triacrylate ("Aronix M-313" made by Toa synthesis company)

irg184: Hydroxycyclohexyl phenyl ketone ("irgacure 184" made by BASF Corporation)

Mega pack F-555 ： Mega pack F-555 made by DIC Corporation

Mega pack F-477 ： Mega pack F-477 made by DIC Corporation

Mega pack F-444 ： Mega pack F-444 made by DIC Corporation

Futagento 710 FM ： Neos Corporation "Futazento 710 FM"

Futagento 208G ： Neos Corporation "Futagento 208G"

Futagento 215M ： Neos Corporation "Futagento 215M"

Futagento 245F ： Neos Corporation "Futagento 245F"

MIBK ： Methyl isobutyl ketone

PGM ： 1-methoxy-2-propanol

PGMAc: 1-methoxypropyl-2-acetate

In addition, the measuring method of the physical property value of the additive used by the Example and the comparative example is as follows. The SP value of the solvent used the literature value (IUPAC Gold Book-solubility parameter).

The surface tension reducing ability measured the surface tension of the 1% PGMAc solution of the fluorine group-containing oligomer using a surface tension meter (Drop Master series manufactured by Kyowa Interfacial Chemical Co., Ltd.), and said "surface tension reducing ability = surface tension of PGMAc. -Surface tension of 1% PGMAc solution ".

The weight average molecular weight says what was measured using GPC ("HLC-8120GPC" by the Tosoh Corporation), and using tetrahydrofuran as a solvent and polystyrene as a standard sample. Moreover, the measurement result of the physical property of an oligomer is shown in Table 5.

The antifoaming property was evaluated about the resin composition of the Example and comparative example which were prepared as mentioned above.

The evaluation method is as follows. 15 ml of the resin composition of the Example and the comparative example were put into the user cylindrical container of the 30 ml volume of 1.5 cm inside, respectively, and shaken for 20 times (amplitude 10-20 cm) for 5 second, and stopped still, and the bubble of the liquid surface The time required until the disappearance was visually measured. The thing of 15 minutes or more was made into the comparative example since productivity was bad actually. Moreover, transparency and uniformity of the liquid before shaking were observed, and it evaluated in two steps ((circle:: transparent, x: there is cloudiness, and precipitation) as an "appearance"). The results are shown in Table 6.

As shown in Table 6, the resin composition of the Example showed the outstanding antifoaming property. On the other hand, the resin composition of the comparative example was easy to generate | occur | produce a bubble, and the bubble did not disappear easily.

<Production and Evaluation of Cured Film>

Examples 2-2, 2-4, 2-8 and 2-10 and Comparative Example 10 prepared as described above were used to form a cured film having a thickness of 3 to 4 µm on a PET substrate (thickness 188 µm), respectively. It apply | coated and dried at 80 degreeC after that, the solvent was removed, and the dry film was formed. The coating film was irradiated and cured in a normal oxygen concentration atmosphere using a high-pressure mercury lamp having an output density of 120 W / cm in a normal oxygen concentration atmosphere so as to have an accumulated light amount of 500 mJ / cm 2.

About the cured film produced as mentioned above, the following items (1)-(6) were evaluated.

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

(2) Hardness: It measured based on the conditions of JISK-5400 using the JIS conformity pencil hardness meter (made by the Thai oil base company), and represented by the number of times of the hardest pencil which a flaw does not produce.

(3) Water repellent oil repellency: After the cured film was stopped for 24 hours in a constant temperature room at a temperature of 23 ° C. and a humidity of 60% RH, after adjusting the state, the cured film was contacted with a contact angle meter (Drop Master DM500 manufactured by Kyowa Interface Science). 0.002 ml of pure water or hexadecane was added dropwise thereto, and after 1 second, the contact angle with respect to water and the contact angle with respect to hexadecane were measured using a contact angle meter (Drop Master 500 manufactured by Kyowa Interface Science Co., Ltd.) ( Unit; degrees).

(4) Adhesiveness: It tested by the cross cut method of JISK5400. 100 checkerboard scales were put into the cured film at 1 mm space | interval, and it tested using the cellophane tape (made by Nichi-reflection). The same operation was repeated five times (the cellophane tape always used a new one), and evaluated that no scratches or peelings occurred at all, and that cracks and peelings of 10% or less occurred in △, and other than × were evaluated in three steps. did.

(5) Magic resistance ： Draw a line on the cured film with an oil-based magic marker (the zebra-made Mackie care ultra-fine (black)), and after 30 seconds, if the line turns out, o Evaluated by stages.

(6) Magic wiping durability ： To the cured film, draw a line with an oil-based magic marker (the zebra-like Mackie care ultrafine (black)), and after 10 seconds, wipe the surface with tissue paper (manufacturer: Cresia), The operation was repeated, and 8 to 5 times were evaluated as three steps, with (circle) and 4 times as (triangle | delta) and 1 time as x from the frequency | count until it will not be wiped off.

Table 7 shows the evaluation results of the cured film.

The cured film obtained by hardening the resin composition of this invention was favorable also in any of transparency, hardness, water / oil repellency, adhesiveness, stain resistance, and stain resistance durability.

By the said Example, it was shown that the resin composition of this invention is small in bubble generation property and excellent in leveling property. Moreover, by hardening the resin composition of this invention, it was shown that hardened | cured material which is high in hardness, and excellent in contamination resistance, its durability, water / oil repellency, and adhesiveness was realized.

Industrial availability

The present invention provides a resin composition having a small bubble generation property and excellent in defoaming property even if bubbles may be generated, and thus less likely to cause defects in the formed coating film. Moreover, when it is apply | coated thinly on the surface of articles, etc., it hardens | cures, The cured film which provides the hardness etc. which are excellent in the article etc., damage resistance, transparency, stain resistance, and durability are provided. Therefore, the resin composition of this invention is suitable for a wide range of uses, such as protection of the surface of an optical recording medium, optical displays, such as a touch panel and a flat panel display, mobile phone casing, automobile transparent parts protection, and the protection of transparent parts, such as an agricultural vinyl house. It is very useful in industry because it can be applied.

Claims (19)

A polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of at least 1000,
A hydrocarbon monomer containing one or two or more selected from a (meth) acryloyl group and a vinyl group,
0.01-25 wt% of saturated hydrocarbons,
SP value contains 10.0 or less solvent,
The weight ratio of the polymer and the saturated hydrocarbon is 5: 1 to 1:20,
The sum total of the said polymer, a hydrocarbon type monomer, a saturated hydrocarbon, and a solvent does not exceed 100 weight%. The method of claim 1,
The resin composition whose carbon number of the said saturated hydrocarbon is 5-18. A polymer having a hydroxyl group and a fluoroalkyl group and having a weight average molecular weight of at least 1000,
A hydrocarbon monomer containing one or two or more selected from a (meth) acryloyl group and a vinyl group,
A fluorine group-containing oligomer having a surface tension lowering ability of 2 mN / m or more,
Saturated hydrocarbons having 5 to 18 carbon atoms,
SP value contains 10.0 or less solvent,
The resin composition whose weight ratio of the said polymer and the said saturated hydrocarbon is 5: 1: 1: 20. The method according to any one of claims 1 to 3,
The resin composition whose content of the hydroxyl group in the said polymer is 0.2-5.0 weight%. The method according to any one of claims 1 to 3,
The resin composition whose content of the fluorine atom in the said polymer is 1.0-34.0 weight%. The method according to any one of claims 1 to 3,
The resin composition in which the said polymer has unsaturated double bond group in a side chain. The method according to any one of claims 1 to 3,
The resin composition in which the polymer has a polysiloxane structure. The method of claim 7, wherein
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 method according to any one of claims 1 to 3,
The resin composition whose said hydrocarbon type monomer is polyfunctional (meth) acrylate which has three or more (meth) acryloyl groups in 1 molecule. The method of claim 3, wherein
The resin composition whose weight average molecular weight of the said fluorine-group containing oligomer is 5000 or more. The method of claim 3, wherein
The resin composition in which the said fluorine group containing oligomer is nonionic. The method of claim 3, wherein
The resin composition whose content of the fluorine-group containing oligomer in a resin composition is 0.005-10 weight% of the whole resin composition. The method according to any one of claims 1 to 3,
The resin composition whose said solvent is at least 1 sort (s) of solvent chosen from the group which consists of a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, and an aromatic hydrocarbon solvent. The method according to any one of claims 1 to 3,
Resin composition containing a radically polymerizable photoinitiator. Hardened | cured material obtained by hardening | curing the composition in any one of Claims 1-3. The method of claim 15,
Hardened | cured material obtained by irradiating an active energy ray to the said composition. The molded article which has a hardened | cured material of Claim 15. The method of claim 17,
Molded article used for optics. The method of claim 18,
A molded article that is a laminate for an optical recording medium or an optical display.