JP2017008125A - Composition containing silicon compound and cured film thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material forming a cured film having high antifouling performance and antifouling durability.SOLUTION: There is provide a composition containing at least one kind (Component A) of a silicon compound represented by the formula (1) and at least one kind (Component B) of a monomer capable of constituting an ultraviolet curable resin or a polymer of the monomer. (1), where n is an integer of 0 to 300, Rto Rare each independently H or C1 to 30 alkyl, Xto Xare each independently C1 to 20 linear/branched alkylene and Y is an acryloyl group and a group having an urethane group.SELECTED DRAWING: None

Description

  The present invention relates to a composition that remarkably improves antifouling properties and a cured film thereof, in a film comprising a composition containing a silicon compound.

In recent years, LCD (liquid crystal display) devices that can be carried and used outdoors have been remarkably widespread. Smartphones, mobile devices represented by PND (personal navigation device), and wearable displays represented by Google Glass Take as an example.
Since these products are carried and used, it is necessary to reduce the weight, and a method of switching a part of the member from glass to plastic is used. However, plastics (especially PET, PC, PMMA, cycloolefin, etc.) have features that are lightweight and highly transparent, but have poor antifouling properties. As a means for solving this problem, a method for preventing contamination by surface treatment with a hard coating agent is widely used.

  As a method for imparting antifouling properties, a method of increasing the water repellency and oil repellency of the surface by using a silicone material or a fluorine-based material as an antifouling treatment agent is common. For example, in Patent Document 1, a resin composition in which a polymer having fluorosilsesquioxane and an organopolysiloxane is mixed with a curable resin is applied onto a substrate, and the active energy ray-curable resin is cured to form a coating film. Produces a coating film with high stain resistance. Patent Document 2 describes a radiation curable resin composition containing an ethylenically unsaturated group-containing fluoropolymer, a (meth) acrylate compound, a silicone compound and silica and its use.

International Patent Application Publication No. WO2008 / 072766 International Patent Application Publication WO2006 / 109496

However, since the polymer having fluorine silsesquioxane and organopolysiloxane as described above does not have enough acrylic functional groups contained in the whole polymer, it is not sufficiently fixed to the resin when formed into a coating film. there were. Therefore, the initial antifouling property has a certain level, but the antifouling durability to maintain the antifouling performance is insufficient, and a sufficient number of wiping can be obtained for repeated wiping tests such as a magic ink wiping test. It was not a thing.
An object of the present invention is to provide a material for forming a cured film having high antifouling performance and antifouling durability.

  The present inventors synthesized a silicon compound in which a highly reactive acryloyl group was introduced into a one-terminal hydroxyl-modified silicon compound. Furthermore, by using the composition containing the silicon compound, a highly reactive silicon compound having an acryloyl group is highly immobilized on the base resin by producing a coating, and has high antifouling properties and antifouling durability. We succeeded in producing a cured film.

この様に構成すると、反応性の高いアクリロイル重合性官能基が反応し、シリコーンが櫛形にぶら下がった状態で会合する事により、シリコーンの性質である撥液性が付与され、高い防汚性を有した硬化膜を作製する事ができる。 The composition according to the first aspect of the present invention includes at least one of the silicon compounds represented by the formula (1) (component A) and at least a monomer capable of constituting an ultraviolet curable resin or a polymer of the monomer. It is a composition containing 1 type (component B). In the formula (1), n is an integer of 0 to 300, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or carbon. The number is 1 to 30 alkyl, X ₁ , X ₂ , X ₃ , and X ₄ are each independently a linear or branched alkylene having 1 to 20 carbon atoms, and Y is independently And a group represented by formula (2) or formula (3) having an acryloyl group.

With this configuration, the highly reactive acryloyl polymerizable functional group reacts and associates in a state where the silicone hangs in a comb shape, thereby providing liquid repellency, which is a property of silicone, and having high antifouling properties. A cured film can be produced.

この様に構成すると、反応性の高いアクリロイル重合性官能基が反応し、シリコーンが櫛形にぶら下がった状態で会合する事により、シリコーンの性質である撥液性が付与され、高い防汚性を有した硬化膜を作製する事ができる。 The composition according to the second aspect of the present invention includes at least one monomer (component A) containing at least one silicon compound represented by formula (4) and constituting a UV curable resin or a polymer of the monomer. It is a composition containing 1 type (component B). In the formula (4), n is an integer of 0 to 300, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or carbon number. Is an alkylene having 1 to 30 and Y is a silicon compound which is a group represented by the above formula (2) or (3) having an acryloyl group.

With this configuration, the highly reactive acryloyl polymerizable functional group reacts and associates in a state where the silicone hangs in a comb shape, thereby providing liquid repellency, which is a property of silicone, and having high antifouling properties. A cured film can be produced.

この様に構成すると、反応性の高いアクリロイル重合性官能基が反応し、シリコーンが櫛形にぶら下がった状態で会合する事により、シリコーンの性質である撥液性が付与され、高い防汚性を有した硬化膜を作製する事ができる。 The composition according to the third aspect of the present invention contains at least one of the silicon compounds represented by the formula (5) (component A), and at least a monomer capable of constituting an ultraviolet curable resin or a polymer of this monomer. It is a composition containing 1 type (component B). In the formula (5), n is an integer of 0 to 300, R ₉ and R ₁₀ are alkylene having 1 to 4 carbon atoms, and Y is independently represented by the formula (2) or (3 ) Is a silicon compound having a group having an acryloyl group.

With this configuration, the highly reactive acryloyl polymerizable functional group reacts and associates in a state where the silicone hangs in a comb shape, thereby providing liquid repellency, which is a property of silicone, and having high antifouling properties. A cured film can be produced.

この様に構成すると、式（６）の合成において原料が容易に入手でき、１段階で合成が可能となる。また、反応性の高いアクリロイル重合性官能基が反応し、シリコーンが櫛形にぶら下がった状態で会合する事により、シリコーンの性質である撥液性が付与され、高い防汚性を有した硬化膜を作製する事ができる。 The composition according to the fourth aspect of the present invention contains at least one of the silicon compounds represented by formula (6) (component A), and at least a monomer capable of constituting an ultraviolet curable resin or a polymer of this monomer. It is a composition containing 1 type (component B). In Formula (6), n is a silicon compound that is an integer of 0 to 300.

If comprised in this way, a raw material will be easily obtained in the synthesis | combination of Formula (6), and a synthesis | combination will be attained in one step. In addition, the highly reactive acryloyl polymerizable functional group reacts and associates in a state in which the silicone hangs in a comb shape, thereby imparting liquid repellency, which is a property of silicone, and forming a cured film having high antifouling properties. Can be made.

（７）
この様に構成すると、式（７）の合成において原料が容易に入手でき、１段階で合成が可能となる。また、反応性の高いアクリロイル重合性官能基が反応し、シリコーンが櫛形にぶら下がった状態で会合する事により、シリコーンの性質である撥液性が付与された硬化膜を作製する事ができる。更にアクリロイル官能基数が４個であるため硬化膜の架橋密度を上げる事ができる。 The composition according to the fifth aspect of the present invention comprises at least one silicon compound represented by the following formula (7) (component A), a monomer capable of constituting an ultraviolet curable resin, or a polymer of this monomer: It is a composition containing at least one (component B). In Formula (7), n is a silicon compound that is an integer of 0 to 300.

(7)
If comprised in this way, a raw material will be easily obtained in the synthesis | combination of Formula (7), and a synthesis | combination will be attained in one step. Further, a highly reactive acryloyl polymerizable functional group reacts and associates in a state where the silicone hangs in a comb shape, whereby a cured film imparted with liquid repellency, which is a property of silicone, can be produced. Furthermore, since the number of acryloyl functional groups is 4, the crosslinking density of the cured film can be increased.

In the composition according to the sixth aspect of the present invention, the component B is at least one of a monomer capable of constituting an ultraviolet curable resin having at least one (meth) acryloyl group or a polymer of this monomer. The composition according to any one of the first to fifth aspects.
If comprised in this way, the coupling | bonding of the acryloyl group which a silicon compound (component A) has and the (meth) acryloyl group which an ultraviolet curable resin (component B) has will be attained by ultraviolet irradiation, and a silicon compound (component A) will be ultraviolet-rayed. It can be immobilized on a curable resin (component B).

The composition according to the seventh aspect of the present invention is a resin composition further containing a curing agent in the composition according to the first to sixth aspects of the present invention.
If comprised in this way, it will become easy to advance hardening reaction from a hardening | curing agent.

The composition according to the eighth aspect of the present invention is a composition characterized in that the curing agent according to the seventh aspect of the present invention generates radicals upon irradiation with ultraviolet rays.
If comprised in this way, it will become easy to advance hardening reaction by irradiating an ultraviolet-ray.

The composition according to the ninth aspect of the present invention is a composition further containing an organic solvent in the compositions of the first to eighth aspects of the present invention.
With this configuration, it is possible to adjust to an arbitrary concentration, and it becomes easy to adjust leveling properties and film thickness.

The composition according to the tenth aspect of the present invention contains a thermosetting resin or at least one monomer (component C) constituting the resin in the composition according to the first to ninth aspects of the present invention. It is a composition.
If comprised in this way, hardening reaction can be advanced by applying heat from the outside.

The composition according to the eleventh aspect of the present invention is a composition comprising, in addition to the composition according to the first to tenth aspects of the present invention, at least one of a thermoplastic resin or a monomer constituting the resin (component D). It is.
If comprised in this way, the property of a cured film can be improved by adding arbitrary thermoplastic resins.

The surface treating agent according to the twelfth aspect of the present invention is a surface treating agent obtained using the composition according to the first to eleventh aspects of the present invention.
If comprised in this way, the surface of a base material can be modify | reformed by apply | coating a composition to arbitrary base materials as a surface treating agent.

The cured film which concerns on the 13th aspect of this invention is a cured film, Comprising: It is a cured film obtained using the surface treatment agent of the 1st-11th composition or 12th aspect of this invention.
If comprised in this way, the surface of a base material can be protected by hardening | curing a composition and setting it as a cured film.

The laminate according to the fourteenth aspect of the present invention is a laminate and is a laminate having the cured film of the thirteenth aspect of the present invention.
If comprised in this way, the various functions which were not obtained with the single layer can be provided by laminating | stacking a cured film and various coating films to make a laminated body.

  The composition of the present invention is a composition containing a silicon compound (component A) in which one terminal of a silicone compound is acryloyl-modified, and containing at least one kind of ultraviolet curable resin or a monomer constituting the resin (component B). Thus, a cured film having a significantly improved antifouling property and antifouling durability suitable for a hard coating agent or the like can be obtained.

  Embodiments of the present invention will be described below. In addition, this invention is not restrict | limited to the following embodiment.

The composition according to the first embodiment of the present invention will be described. The composition contains at least one silicon compound (component A) and contains at least one ultraviolet curable resin or a monomer constituting the resin (component B). The content of Component A in the composition is preferably 0.01 to 50% by weight with respect to Component B in the composition. The content of component B is preferably 1 to 70% by weight with respect to the total amount of the composition.
The silicon compound (component A) contained in the composition will be described. The structure of the silicon compound (component A) is as follows.

The silicon compound (component A) includes a silicone chain (a siloxane bond serving as a main chain), and one end thereof is an acrylic modified compound. Since one end has a group containing an acryloyl group as a functional group, it can be classified into a bifunctional acryloyl modified silicon compound and a tetrafunctional acryloyl modified silicon compound depending on the number of functional groups.
The silicon compound (component A) is preferable because the crosslink density of the cured film can be adjusted by changing the number of acryloyl groups to be introduced and adjusting the acryloyl equivalent.

２官能アクリロイル変性ケイ素化合物は、Ｙがアクリロイル基を有する、式（２）の基である化合物である。

４官能アクリロイル変性ケイ素化合物は、Ｙがアクリロイル基を有する、下記式（３）で示される基である化合物である。

The structure which becomes the skeleton of the silicon compound (component A) is shown in the following formula (1). In Formula (1), n is an integer of 0-300.
In addition, since n of a silicone chain | strand can be 0-300, since compatibility and antifouling property of a silicon compound (component A) can be adjusted, it is preferable.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or alkyl having 1 to 30 carbon atoms. X ₁ , X ₂ , X ₃ and X ₄ are each independently a linear or branched alkylene having 1 to 20 carbon atoms. By adjusting these lengths, the leveling property to the substrate and the compatibility in the case of a composition can be adjusted, which is preferable.

The bifunctional acryloyl-modified silicon compound is a compound in which Y is a group of the formula (2) having an acryloyl group.

The tetrafunctional acryloyl-modified silicon compound is a compound in which Y is a group represented by the following formula (3) having an acryloyl group.

  Another component of the composition, at least one monomer (component B) capable of constituting an ultraviolet curable resin or a polymer of this monomer (component B), is a monomer that can be cured by irradiation with ultraviolet rays or the polymerization of this monomer. Product (resin). Hereinafter, Component B is also referred to as “ultraviolet curable resin or monomer constituting this resin”.

  As the ultraviolet curable resin or the monomer constituting this resin, radical polymerization such as urethane (meth) acrylate resin, polyester (meth) acrylate resin, (meth) acrylate monomer, unsaturated polyester resin, epoxy (meth) acrylate resin, etc. Mention may be made of resins or monomers having possible unsaturated bonds. These resins or monomers may be used alone, or a plurality of resins or monomers may be used in combination. More preferred is an ultraviolet curable resin having at least one (meth) acryloyl group or a monomer constituting this resin.

  As urethane (meth) acrylate resin, for example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, further reacting a hydroxyl group-containing (meth) acryl compound and, if necessary, a hydroxyl group-containing allyl ether compound. And a radical-polymerizable unsaturated group-containing oligomer that can be obtained.

  Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and isomers thereof, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate. Nart, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Bernock D-750, Crisbon NK (trade name: manufactured by Dainippon Ink & Chemicals, Inc.), Desmodur L (trade name: Sumitomo) Bayer Urethane Co., Ltd.), Coronate L (trade name: manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate D102 (trade name: manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name: manufactured by Mitsubishi Chemical Corporation) ) And the like.

  Examples of the polyhydroxy compound include polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, and the like. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin- Ethylene oxide-propylene oxide adduct, trimethylol propane-ethylene oxide adduct, trimethylol propane-propylene oxide adduct, trimethylol propane-tetrahydrofuran adduct, trimethylol propane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct , Dipentaerythritol-propylene oxide adduct, dipentaerythritol - tetrahydrofuran adduct, dipentaerythritol - ethylene oxide - propylene oxide adduct and the like.

  Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3- Butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3 -Cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol, etc. .

  Although it does not specifically limit as said hydroxyl-containing (meth) acryl compound, The ester or amide compound of hydroxyl-containing (meth) acrylic acid is preferable, Specifically, for example, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, pentaerythritol Examples include tri (meth) acrylate and hydroxyethyl acrylamide.

  As the polyester (meth) acrylate resin, (1) a terminal carboxyl group polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol contains an α, β-unsaturated carboxylic ester group. (Meth) acrylate obtained by reacting an epoxy compound, (2) obtained by reacting a hydroxyl group-containing acrylate with a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or unsaturated polybasic acid and a polyhydric alcohol (Meth) acrylate, (3) saturated polybasic acid and / or (meth) acrylate obtained by reacting polyester of terminal hydroxyl group obtained from unsaturated polybasic acid and polyhydric alcohol with (meth) acrylic acid. .

  Examples of the saturated polybasic acid used as a raw material for polyester (meth) acrylate include polybasic compounds having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples thereof include acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. Furthermore, as the polyhydric alcohol component, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2- Examples include methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A. .

  Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, polyethylene glycol diacrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri ( (Meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tetramethylolpropanetetra ( Data) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

Unsaturated polyester resin is a product obtained by dissolving a condensation product (unsaturated polyester) in an esterification reaction of polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid as required) in a polymerizable monomer. Is mentioned.
The unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or its anhydride is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane Polyhydric alcohols such as -1,4-dimethanol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are reacted as an alcohol component, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, Such as tetrahydrophthalic acid, adipic acid, sebacic acid Polymerizable not have an unsaturated bond or a polybasic acid anhydrides may include those prepared by adding as an acid component.

  As an epoxy (meth) acrylate resin, there is a polymerizable unsaturated bond generated by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. What dissolved the compound (vinyl ester) which it had in the polymerizable monomer is mentioned.

  The vinyl ester is produced by a known method, and examples thereof include epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.

Various epoxy resins are reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S (trade name): Harima Kasei Co., Ltd.) to impart flexibility. May be.
Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolak glycidyl ethers, and the like.

Ultraviolet rays are energy rays that can decompose active compounds to generate active species. There are various types of active energy rays that can generate active species, but ultraviolet rays are preferable from the viewpoint of handling.

  The composition according to the second embodiment of the present invention will be described. The composition contains at least one kind of silicon compound (component A) and contains at least one kind of ultraviolet curable resin or a monomer constituting the resin (component B).

The silicon compound (component A) contained in the composition will be described. The structure of the silicon compound (component A) is as follows.
The silicon compound (component A) includes a silicone chain (a siloxane bond serving as a main chain), and one end of which is acryloyl-modified. Since one end has a group containing an acryloyl group as a functional group, it can be classified into a bifunctional acryloyl modified silicon compound and a tetrafunctional acryloyl modified silicon compound depending on the number of functional groups.
The silicon compound (component A) is preferable because the crosslink density of the coating film can be adjusted by changing the number of acryloyl groups to be introduced and adjusting the acryloyl equivalent.

２官能アクリル変性ケイ素化合物は、Ｙがアクリロイル基を有する、上記の式（２）の基である化合物である。
４官能アクリロイル変性ケイ素化合物は、Ｙがアクリロイル基を有する、上記の式（３）で示される基である化合物である。 A structure that is a skeleton of the silicon compound (component A) is shown in Formula (4). In Formula (4), n is an integer of 0-300.
In addition, since n of a silicone chain | strand can be 0-300, since compatibility and antifouling property of a silicon compound (component A) can be adjusted, it is preferable.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or alkyl having 1 to 30 carbon atoms. By adjusting these lengths, the leveling property to the substrate and the compatibility in the case of a composition can be adjusted, which is preferable.

A bifunctional acrylic-modified silicon compound is a compound in which Y is a group of the above formula (2) having an acryloyl group.
The tetrafunctional acryloyl-modified silicon compound is a compound in which Y has a acryloyl group and is a group represented by the above formula (3).

  The ultraviolet curable resin or the monomer (component B) constituting this resin is as described above.

  The composition according to the third embodiment of the present invention will be described. The composition contains at least one kind of silicon compound (component A) and contains at least one kind of ultraviolet curable resin or a monomer constituting the resin (component B).

The silicon compound (component A) contained in the composition will be described. The structure of the silicon compound (component A) is as follows.
The silicon compound (component A) includes a silicone chain (a siloxane bond serving as a main chain), and one end thereof is an acrylic modified compound. Since one end has a group containing an acryloyl group as a functional group, it can be classified into a bifunctional acryloyl modified silicon compound and a tetrafunctional acryloyl modified silicon compound depending on the number of functional groups.
The silicon compound (component A) is preferable because the crosslink density of the cured film can be adjusted by changing the number of acryloyl groups to be introduced and adjusting the acryloyl equivalent.

２官能アクリロイル変性ケイ素化合物は、Ｙがアクリロイル基を有する、上記の式（２）の基である化合物である。
４官能アクリロイル変性ケイ素化合物は、Ｙがアクリロイル基を有する、式（３）で示される基である化合物である。 The structure which becomes the skeleton of the silicon compound (component A) is shown in the following formula (4). In Formula (4), n is an integer of 0-300.
In addition, since n of a silicone chain | strand can be 0-300, since compatibility and antifouling property of a silicon compound (component A) can be adjusted, it is preferable.
R ₉ and R ₁₀ are each independently hydrogen or alkyl having 1 to 4 carbon atoms. By adjusting these lengths, the leveling property to the substrate and the compatibility in the case of a composition can be adjusted, which is preferable.

The bifunctional acryloyl-modified silicon compound is a compound in which Y has an acryloyl group and is a group of the above formula (2).
The tetrafunctional acryloyl-modified silicon compound is a compound in which Y has a acryloyl group and is a group represented by the formula (3).

  The ultraviolet curable resin or the monomer (component B) constituting this resin is as described above.

The composition according to the fourth embodiment of the present invention will be described. The composition contains at least one kind of silicon compound (component A) and contains at least one kind of ultraviolet curable resin or a monomer constituting the resin (component B).
The silicon compound (component A) contained in the resin composition will be described. The structure of the silicon compound (component A) is as follows.

  The silicon compound (component A) includes a silicone chain (a siloxane bond serving as a main chain), and one end thereof is an acrylic modified compound. Since one end has a group containing two acryloyl groups as functional groups, irradiation with active energy rays allows the acryloyl groups to react with each other and polymerization proceeds to form a cured film, which is preferable.

A structure that is a skeleton of the silicon compound (component A) is shown in Formula (6). In Formula (6), n is an integer of 0-300.
In addition, since n of a silicone chain | strand can be 0-300, since compatibility and antifouling property of a silicon compound (component A) can be adjusted, it is preferable.

  The ultraviolet curable resin or the monomer (component B) constituting this resin is as described above.

The composition according to the fifth embodiment of the present invention will be described. The composition contains at least one kind of silicon compound (component A) and contains at least one kind of ultraviolet curable resin or a monomer constituting the resin (component B).
The silicon compound (component A) contained in the composition will be described. The structure of the silicon compound (component A) is as follows.
The silicon compound (component A) includes a silicone chain (a siloxane bond serving as a main chain), and one end thereof is an acrylic modified compound. Since one end has a group containing four acryloyl groups as functional groups, irradiation with active energy rays causes acryloyl groups to react with each other and polymerization proceeds to form a coating film, which is preferable.

A structure that is a skeleton of the silicon compound (component A) is shown in Formula (7). In Formula (7), n is an integer of 0-300.
In addition, since n of a silicone chain | strand can be 0-300, since compatibility and antifouling property of a silicon compound (component A) can be adjusted, it is preferable.

  The ultraviolet curable resin or the monomer (component B) constituting this resin is as described above.

A method for synthesizing the silicon compound (component A) according to the present invention is shown below.
As the silicon compound (component A), a hydroxyl group-containing siloxane compound (for example, Silaplane FM-DA series manufactured by JNC Corporation) is used in the presence of a tin catalyst (for example, dibutyltin dilaurate) in the presence of acryloyloxyethyl isocyanate (for example, Showa). A bifunctional acryloyl-modified silicon compound can be obtained by reacting with an isocyanate having an acryloyl group such as Karenz AOI manufactured by Denko Co., Ltd.

  Alternatively, a hydroxyl group-containing siloxane compound (for example, Silaplane FM-DA series manufactured by JNC Co., Ltd.) in the presence of a tin catalyst (for example, dibutyltin dilaurate), 1,1 ′-(bisacryloyloxymethyl) ethyl isocyanate A tetrafunctional acryloyl-modified silicon compound can be obtained by reacting with an isocyanate having an acryloyl group such as Karenz BEI manufactured by Showa Denko KK.

In addition, about the manufacturing method of a hydroxyl group containing siloxane compound, patent 2587226 can be referred.
The catalyst used for the reaction between the hydroxyl-modified silicon compound and the isocyanate having an acryloyl group may be an amine-based catalyst (for example, triethylenediamine), a carboxylate catalyst (for example, lead naphthenate or potassium acetate), a trialkylphosphine catalyst ( For example, triethylphosphine), a titanium-based catalyst (for example, titanium normal butoxide) and the like can be used.

  The composition according to the sixth embodiment of the present invention is an ultraviolet curable resin composition in which component B has at least one (meth) acryloyl group. Examples of the ultraviolet curable resin composition having at least one (meth) acryloyl group are as described above.

  The composition according to the seventh embodiment of the present invention is a composition in which a curing agent is added to the compositions according to the first to sixth embodiments of the present application. It is preferable to use a curing agent because the curing reaction between the resin or monomer and the silicon compound (component A) can proceed smoothly.

As an example, a case where an ultraviolet curable resin is used after being irradiated with ultraviolet rays will be described. The ultraviolet curable resin is preferably one that is cured by irradiating with ultraviolet rays in the presence of a photopolymerization initiator for polymerization. Examples of photopolymerization initiators include various benzoin derivatives, benzophenone derivatives, phenyl ketone derivatives, onium salt photoinitiators, organometallic photoinitiators, metal salt cationic photoinitiators, photodegradable organosilanes, and latent sulfonic acids. And phosphine oxide.
The content of the curing agent is preferably 0.1 to 10 wt%, more preferably 1 to 9 wt%, and particularly preferably 3 to 8 wt% with respect to the total amount of the active energy ray-curable resin.

The composition according to the eighth embodiment of the present invention is a composition characterized in that the curing agent generates radicals upon irradiation with ultraviolet rays.
The polymerization initiator that generates radicals upon irradiation with ultraviolet rays is not particularly limited as long as it is a compound that generates radicals upon irradiation with ultraviolet rays. Specifically, benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropio Phenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino 1- (4-morpholinophenyl) -butanone, ethyl 1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4 ′ -Tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( '-Pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2 -(P-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis ( 2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like. These compounds may be used alone or in combination of two or more.

  Among them, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxy) Carbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (Methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone and the like are preferable.

  The composition according to the ninth embodiment of the present invention is a composition in which an organic solvent is further added to the compositions according to the first to eighth embodiments of the present application. This is preferable because the mixing of the composition can be promoted. Furthermore, the addition of an organic solvent is preferable because the concentration of the composition can be changed as appropriate, and the viscosity can be made suitable for the production of a coating film.

  Examples of the solvent include ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, propylene glycol monomethyl ether, etc.), halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene, etc.), ketone solvents (acetone). , Methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents ( Ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylphenol) Muamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms), perfluorocarbons Solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic Fluorine solvent (α, α, α-trifluorotoluene, hexafluorobenzene) and water are included. These may be used alone or in combination of two or more.

The composition according to the tenth embodiment of the present invention includes at least one thermosetting resin or a monomer constituting the resin (component C) in addition to the composition according to the first to ninth embodiments of the present invention. ).
Examples of the thermosetting resin include phenol resin, alkyd resin, melamine resin, epoxy resin, urea resin, unsaturated polyester resin, urethane resin, thermosetting polyimide, and silicone resin. These resins may be used alone, or a plurality of resins may be used in combination.
Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, polymer type epoxy resin, biphenyl type epoxy resin, etc. Epoxy resins, methylated melamine resins, butylated melamine resins, methyl etherified melamine resins, butyl etherified melamine resins, methylbutyl mixed etherified melamine resins, and other polyisocyanates having two or more isocyanate groups A compound (O = C═N—R—N═C═O) and a polyol compound (HO—R′—OH) having two or more hydroxyl groups, a polyamine (H ₂ N—R ″ —NH ₂ ), or active hydrogen such as water _(-NH 2, -NH, -CONH-, etc.) and the like compounds having a Urethane resins that can be obtained by the above reaction are preferred in terms of processability.
Epoxy resins are heat-resistant, adhesive and chemical resistant, melamine-based resins are heat-resistant, hard and transparent, and urethane-based resins are excellent in adhesion and low-temperature curability, and can be selected and used as appropriate. .

  The thermosetting resin needs to be rapidly cured at a desired curing temperature (80 to 160 ° C.) and time (30 to 180 seconds). Depending on the type of resin, a curing reaction initiator or a curing reaction accelerator may be used. For example, in the case of epoxy resins, aliphatic amines and amines of aromatic amines, polyamide resins, tertiary amines and secondary amines, imidazoles, polymercaptans, acid anhydrides, Lewis acid complexes, melamine resins In the case of a sulfonic acid catalyst and a urethane resin, an organometallic urethanization catalyst and a tertiary amine urethanization catalyst can be exemplified.

  The curing reaction initiator and the curing reaction accelerator may be any compound that can release a substance that initiates cationic polymerization by irradiation with active energy rays or thermal energy. Examples of such curing reaction initiators include carboxylic acids, amines, acid anhydride compounds and acid generators, and preferably double salts or derivatives thereof which are onium salts that release Lewis acids.

Representative examples of the curing reaction initiator include cation and anion salts represented by the following formula (8).
[A] ^{m +} [B] ^m− (8)

In the above formula (8), the cation [A] ^{m +} is preferably an onium ion, and is represented by, for example, the following formula (9).
[(Α) _a Q] ^{m +} (9)

  In said Formula (9), (alpha) is a C1-C60 organic group which may contain how many atoms other than a carbon atom. a is an integer of 1-5. The a α's are independent and may be the same or different. Further, at least one α is preferably an organic group having an aromatic ring.

Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{m +} is q, m = a−q (where N = N is treated as valence 0).

On the other hand, the anion [B] ^m- is preferably a halide complex, for example, represented by the following formula (10).
[LX _b ] ^m− (10)

In the formula (10), L is a metal or metalloid that is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom. b is an integer of 3-7. Further, when the valence of L in the anion [LX _b ] ^m− is p, m = b−p.

Specific examples of the anion [LX _b ] ^{m- represented by} the formula (10) include tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), hexafluoroarce. Nate (AsF ₆ ), hexachloroantimonate (SbCl ₆ ), etc.

Moreover, as an anion [B] ^m- , what is shown by following formula (11) can also be used preferably. L, X, and b are the same as described above.
[LX _b-1 (OH)] ^m− (4)

Examples of the anion [B] ^m- further include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluenesulfonate anion Ions, trinitrobenzenesulfonic acid anions, and the like are also included.

  Among such onium salts, the curing reaction initiator in the present invention is more preferably an aromatic onium salt exemplified by the following (A) to (C). Among these, one of them can be used alone, or two or more of them can be mixed and used.

(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, and (b) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryl iodonium salts such as hexafluorophosphate and di (4-t-butylphenyl) iodonium hexafluorophosphate (c) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thio Phenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxypheny Sulfonium hexafluorophosphate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4, 4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexa Fluorophosphate, 4- [4 '-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4'-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) ) Sulfoni Triarylsulfonium salts such as beam hexafluorophosphate

  Further, the curing reaction initiator in the present invention may be a mixture of an iron arene complex or an aluminum complex and silanols such as triphenylsilanol.

Examples of iron arene complexes include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Hexafluorophosphate and the like, and examples of aluminum complexes include tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and the like.

  Among the above, from the viewpoint of practical use, the curing reaction initiator in the embodiment of the present invention is preferably an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  The content of the curing reaction initiator (preferably an acid generator) is preferably 1 mol with respect to 10 to 300 mol of the epoxy group contained in the epoxy resin.

  The composition according to the eleventh embodiment of the present invention is a composition according to the first to tenth embodiments of the present invention, further comprising at least one thermoplastic resin or a monomer constituting the resin (component D). Is a composition to which is added. When a thermoplastic resin is mixed, the original characteristics (mechanical properties, surface / interface characteristics, compatibility, etc.) of the resin can be modified.

  Examples of thermoplastic resins include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultra high molecular weight polyethylene, poly-4- Methylpentene, Syndiotactic polystyrene, Polyamide (Nylon 6: DuPont brand name, Nylon 6,6: DuPont brand name, Nylon 6,10: DuPont brand name, Nylon 6, T: DuPont brand name, Nylon MXD6 : DuPont brand name), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene oxide, Fluorine resin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: Unitika Ltd. trade name, Vectra: Polyplastics Corp.) Trade name, etc.), polyimide (Kapton: trade name of Toray Industries, Inc., AURUM: trade name of Mitsui Chemicals, etc.), polyetherimide, polyamideimide and the like.

  As the surface treating agent according to the twelfth embodiment of the present invention, it is possible to modify the surface of the substrate using the compositions according to the first to eleventh embodiments. . The surface treatment agent can be used to modify the surface of the substrate by applying it to the surface of the substrate and then forming a cured film.

  The cured resin and the surface treatment agent preferably have weather resistance, low refractive index characteristics, high refractive index characteristics, antifouling characteristics, low wear characteristics, gas barrier characteristics, and scratch resistance as appropriate depending on the application. The following additives and techniques for imparting such characteristics can also be used.

  Examples of the ultraviolet absorber include benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylates, triazines, or dibenzoylrisorcinols. These ultraviolet absorbers may be used alone, or a plurality of ultraviolet absorbers may be used in combination. It is preferable to appropriately select the type and combination of ultraviolet absorbers based on the wavelength of ultraviolet rays to be absorbed.

  Antioxidants include monophenols (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate), bisphenols (2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl- 6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxa Spiro [5,5] undecane, etc.), polymeric phenols (1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2) , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) Propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-) t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc.), sulfur-based antioxidants (dilauryl-3,3′-thiodipropione) , Dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, etc.), phosphites (rephenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris ( Nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2, 4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4 -{2- (octadecyloxyca Bonyl) ethyl} phenyl] hydrogen phosphite), and oxaphosphaphenanthrene oxides (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-) t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide etc.).

These antioxidants can be used alone, but it is particularly preferable to use them in combination with phenolic / sulfuric or phenolic / phosphorous. As commercially available phenolic antioxidants, IRGANOX 1010 (trade name) and IRGAFOS 168 (trade name) manufactured by BASF can be used singly or in combination. .

  As the light stabilizer (HALS), TINUVIN (registered trademark) 5100 (neutral type general-purpose HALS), TINUVIN 292 (compound name: bis (1,2,2,6,6-pentamethyl-4-piperidinyl)) manufactured by BASF Sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN 152 (compound name: 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2, 6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), TINUVIN 144 (compound name: bis (1,2,2,6,6-) Pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl Ronate), TINUVIN 123 (compound name: decanedioic acid, reaction product of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4piperidinyl) ester (1,1-dimethylethyl hydroperoxide and In the presence of octane)), TINUVIN 111 FDL (about 50%, TINUVIN 622, compound name: (butanedioic acid polymer (in the presence of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl) ethanol), about 50%, CHIMASSORB 119, compound name: NN′-N ″ -N ′ ″-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) Amino) triazin-2-yl) -4,7-diazadecane-1,10-diamine) or A Deca made Adekastab LA series, such as LA-52 ((5) -6116), LA-57 ((5) -5555), LA-62 ((5) -5711), LA-67 (( 5) -5755). The numbers in parentheses are existing chemical substance numbers.

  Examples of a method for imparting a low refractive index characteristic include inorganic fine particles such as magnesium fluoride in a cured resin layer, fluorosilsesquioxane, and fluorosilsesquioxane polymers described in WO2008 / 072766 and WO2008 / 072765. It is preferable to mix one or more compounds selected from the group consisting of acrylate compounds containing fluorine atoms.

  Techniques for imparting high refractive index characteristics include metal fine particles such as zirconia, titania and zinc sulfide in the cured resin layer, acrylate compounds and epoxy compounds having a fluorene skeleton, acrylate compounds and epoxy compounds containing sulfur atoms, etc. It is preferable to mix 1 or more types.

  Used for transparent electrode films incorporated into capacitive touch panels by applying a transparent electrode material typified by ITO or silver nanowire on a cured resin layer with high refractive index characteristics and patterning it by etching can do. By using a cured resin layer imparted with a high refractive index characteristic, the conductive pattern of a transparent electrode material such as ITO or silver nanowire can be made invisible.

  Moreover, the 1st cured resin layer which has an antireflection characteristic can be obtained by laminating | stacking the layer which has the said low refractive index characteristic on the cured resin layer to which the high refractive index characteristic was provided.

  Examples of methods for imparting antifouling properties and low friction properties include silicone compounds, fluorine compounds, fluorosilsesquioxanes, and fluorosilsesquioxane polymers described in WO2008 / 072766 and WO2008 / 072765 in a cured resin layer. It is preferable to mix one or more compounds selected from the group consisting of:

  As silicone compounds, BYK-UV3500, BYK-UV-3570 (both trade names: manufactured by Big Chemie), TEGO Rad2100, 2200N, 2250, 2500, 2600, 2700 (both trade names: manufactured by Degussa), X- 22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-2 1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X-22-2426, X-22-164A, X-22-164C (both are trade names: manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  As the fluorine compound, Daikin Industries, Ltd. OPTOOL DAC, OPTOOL DAC-HP, R-1110, R-1210, R-1240, R-1620, R-1820, R-2020, R-5210, R-5410 , R-5610, R-5810, R-7210, R-7310, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-E, Megafuck RS-76-NS, Megafuck RS -77, Megafuck RS-903-3, Megafuck RS-914-2, Megafuck RS-761-3 (all are trade names), and the like.

  As a method for imparting gas barrier properties, it is preferable to mix one or more inorganic components such as layered clay represented by graphene, silica, alumina, and porous glass in the cured resin layer.

  As a technique for imparting scratch resistance, inorganic fine particles are added in order to improve the surface hardness and scratch resistance of a cured film obtained by curing a coating film using the coating agent composition or surface treatment agent of the present invention. May be. Specific examples of inorganic fine particles include aluminum oxide, silicon oxide, rutile type titanium oxide, tin oxide, zirconium oxide, cerium oxide, magnesium fluoride, iron oxide, zinc oxide, copper oxide, antimony oxide, cryolite, firefly Stone), apatite, calcite, gypsum and talc. The amount of the inorganic oxide used is preferably less than 60 wt% with respect to the curable resin (b) in the resin composition of the present application. If it is less than 60 wt%, the favorable adhesiveness with respect to a base material can be maintained.

  Further, the average particle size of the inorganic fine particles is preferably 5 nm to 2 μm, and preferably 5 nm to 500 nm, more preferably 5 nm to 50 nm in consideration of the transparency of the coating film. When it is 5 nm or more, the surface hardness and scratch resistance of the cured film can be improved, and when it is 2 μm or less, the transparency of the cured film is not adversely affected. The average particle diameter of the inorganic fine particles is measured by a dynamic light scattering method using Nikkiso Co., Ltd. MICROTRAC UPA.

  In addition, if necessary, active energy ray sensitizer, polymerization inhibitor, wax, plasticizer, leveling agent, surfactant, dispersant, antifoaming agent, wettability improver, antistatic agent, curing aid, etc. These various additives can be mixed.

  The cured film according to the thirteenth embodiment of the present invention is a cured film obtained by curing the composition according to the first to eleventh embodiments or the surface treatment agent according to the twelfth embodiment. It is a membrane. When the composition or the surface treatment agent is used as a cured film, a substrate may be used as appropriate.

  In the cured film production method of the present invention, first, a composition or a surface treatment agent is uniformly coated to form a coating film. Subsequently, the cured film of the present invention can be formed by heating and drying to obtain a dried coating film, and further irradiating the dried coating film with ultraviolet rays.

  As the coating method, it is preferable to use a wet coating method. As the wet coating method, a gravure coating method, a die coating method, or the like can be used. The resin composition for a coating agent is preferably in a state suitable for coating, and may not contain a solvent or may be a mixture with a solvent.

  In the gravure coating method, a gravure roll with an uneven engraving process on the surface is dipped in the coating liquid, and the coating liquid adhering to the convex part on the surface of the gravure roll is scraped off with a doctor blade, and the liquid is stored accurately in the concave part. And transferring to the base material. A low viscosity liquid can be thinly coated by the gravure coating method.

  The die coating method is a method in which coating is performed while pressurizing and extruding a liquid from a coating head called a die. The die coating method enables highly accurate coating. Further, since the liquid is not exposed to the outside air during application, the concentration of the application liquid is hardly changed by drying.

  Other wet coating methods include spin coating, bar coating, reverse coating, roll coating, slit coating, dipping, spray coating, kiss coating, reverse kiss coating, air knife coating, and curtain coating. Method, lot coat method and the like. The coating method can be appropriately selected according to the required film thickness from these methods.

  The heating / drying method for preparing the dried coating film from the coating film is not particularly limited, but a hot plate or a heating oven can be used. Moreover, although it depends on the film thickness, when the drying is carried out in the temperature range of 50 to 120 ° C. for 10 seconds to 300 seconds, the solvent is effectively evaporated, and a film with less surface stickiness can be obtained.

  Moreover, various plastics and glass which have transparency can be used for the base material to be coated. Examples of plastic materials having transparency include polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, and polyresins. Examples of the resin include vinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, norbornene resin, cycloolefin resin, and polyurethane resin.

  Specifically, polyethylene terephthalate (PET), polyethylene naphthalate, triacetyl cellulose, polyether sulfone, polycarbonate, polyarylate, polyether ether ketone and the like are preferable. Cycloolefin resins are ZEONOR (registered trademark), ZEONEX (registered trademark): manufactured by Zeon Japan, Arton (registered trademark): manufactured by JSR, Apel (registered trademark): manufactured by Mitsui Chemicals, and TOPAS (registered trademark): manufactured by Polyplastics. Is preferred.

  Polyethylene terephthalate and polyethylene naphthalate are more preferred because they are excellent in mechanical strength, dimensional stability, heat resistance, chemical resistance, optical properties, etc., and smoothness and handling properties of the film surface. Polycarbonate is more preferred because it is excellent in transparency, impact resistance, heat resistance, dimensional stability, and flammability. In consideration of price and availability, polyethylene terephthalate is particularly preferable.

  The material of the glass having transparency is not limited as long as the glass is excellent in dimensional stability and optical characteristics used for LCD displays and touch panels. Examples include soda lime glass, alkali-free glass, alkali barium glass, borosilicate glass, alkali borosilicate glass, aluminoborosilicate glass, barium borosilicate glass, aluminosilicate glass, borate glass, silica glass, lead glass, and the like. .

Moreover, the base material may be a base film used for an optical protective film made of the above material, and used in a display unit or a touch panel unit of an electronic device such as a PC, a portable terminal, a car navigation system, or a liquid crystal display. Or a lens such as a camera, glasses or goggles.
Furthermore, the base material to be coated may not be transparent, and may be a housing such as an electronic device, an electric device, or an IT-related device. Thus, the substrate may be any material that requires a hard coating regardless of whether it is transparent or opaque.

The thickness of the substrate is not particularly limited, and varies depending on the article exemplified above. For example, in the case of an optical protective film, the thickness of the substrate is preferably 50 to 300 μm, more preferably 80 to 200 μm. When the thickness of the substrate is 50 μm or more, the mechanical strength of the substrate is sufficient, and a coating can be formed on the substrate. Moreover, when the thickness is 300 μm or less, the thickness of the optical protective film does not become too thick, and a product (for example, an image display device described later) using the film is compact.
The thickness of the cured composition of the coating agent composition or the surface treatment agent formed on the surface of the substrate is not particularly limited, and can be appropriately changed from the article exemplified above.

The base material to which the composition of the present invention is applied is not particularly limited as long as the composition and the surface treatment agent can be applied, and the shape is not limited to a flat plate shape, and may be a curved surface shape. Good.
Moreover, the composition of this invention can be apply | coated on functional films, such as an organic film and an inorganic film, besides apply | coating directly to the said base material. In that case, UV / O3 ashing treatment, oxygen plasma treatment, or the like may be applied in advance in order to improve the coatability of the film. Moreover, you may apply | coat a commercially available primer, a coating material, etc. in the range which does not affect application | coating of the composition of this invention.

  In addition, an antioxidant, a deterioration inhibitor, a filler, an ultraviolet absorber, an antistatic agent, an anti-radiowave agent, etc. are added to the substances constituting these substrates within the range that does not adversely affect the effects of the present invention. An agent may be included.

  Moreover, at least a part of the surface of the base material is subjected to an easy adhesion treatment such as a water repellent treatment, a corona treatment, a plasma treatment or a blast treatment as necessary, or an easy adhesion layer or a hard coat is applied to at least a part of the surface A film may be provided.

  The laminate according to the fourteenth embodiment of the present invention is a film obtained by laminating the cured film according to the thirteenth embodiment. The laminate may be a film obtained by laminating the cured film of the present invention, or may be obtained by laminating the cured film of the present invention and another cured resin layer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

[Example 1]
<Synthesis of bifunctional acryloyl-modified silicon compound A1 (component A)>
One terminal hydroxyl-modified silicon compound (trade name: Silaplane FMDA21, OH value 24.1 mgKOH / g, manufactured by JNC Corporation) 10.1 g, dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) 0.002 g and p- 0.012 g of methoxyphenol was added and heated to 45 ° C. under a nitrogen atmosphere. 0.70 g of acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK) was added dropwise to the solution and stirred at 45 ° C. to 50 ° C. for 2 hours. After confirming disappearance of the raw materials using NMR, the mixture was cooled with ice and methanol (0.24 g) was added dropwise. After confirmation at the same temperature for 30 minutes, a methanol solution (11.0 g, solid content concentration 97 wt%) of the bifunctional acryloyl-modified silicon compound A1 was obtained.

The progress of the reaction was confirmed using ¹ H NMR, and the peak derived from the methylene proton next to oxygen in the raw material Silaplane FMDA21: ¹ H NMR (CDCl ₃ , 500 MHz): 3.35 (2H, t, J = 6.8 Hz), 3.41 (2H, s), 3.59 (2H, d, J = 11 Hz), 3.70 (2H, d, J = 11 Hz) disappeared, and methylene was obtained by urethane acrylate formation. Protons were confirmed to shift to 3.23 (2H, s), 3.3 (2H, t, J = 6.9 Hz), 4.00 (4H, s).

[Example 2]
<Synthesis of bifunctional acryloyl-modified silicon compound A2 (component A)>
One-terminal hydroxyl-modified silicon compound (trade name: Sileplane FMDA11, OH number 94.8 mgKOH / g, manufactured by JNC Corporation), 10.2 g and dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.) 0.005 g, The same method as in Example 1 except that 0.012 g of p-methoxyphenol, 2.86 g of acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK) and methanol (0.97 g) were used. Thus, a methanol solution (14.1 g, solid content concentration 87 wt%) of the bifunctional acryloyl-modified silicon compound A2 was obtained.

The progress of the reaction was confirmed using ¹ H NMR, and the peak derived from the methylene proton next to oxygen in the raw material Silaplane FMDA21: ¹ H NMR (CDCl ₃ , 500 MHz): 3.36 (2H, t, J = 6.8 Hz), 3.41 (2H, s), 3.59 (2H, d, J = 11 Hz), 3.73 (2H, d, J = 11 Hz) disappeared, and methylene protons by urethane acrylate formation Shift to 3.24 (2H, s), 3.29 (2H, t, J = 6.7 Hz), 4.10 (4H, s).

[Example 3]
<Synthesis of bifunctional acryloyl-modified silicon compound A3 (component A)>
One-end hydroxyl-modified silicon compound (trade name: Sileplane FMDA26, OH number 8.1 mgKOH / g, manufactured by JNC Corporation) 10.0 g and dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.0005 g The same method as in Example 1 except that 0.010 g of p-methoxyphenol, 0.24 g of acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK) and methanol (0.10 g) were used. Thus, a methanol solution (10.4 g, solid content concentration 99 wt%) of the bifunctional acryloyl-modified silicon compound A3 was obtained.

The progress of the reaction was confirmed using ¹ H NMR, and the peak derived from the methylene proton next to oxygen in the raw material Silaplane FMDA26: ¹ H NMR (CDCl ₃ , 500 MHz): 3.37 (2H, t, J = 6.9 Hz), 3.41 (2H, s), 3.59 (2H, d, J = 11 Hz), 3.71 (2H, d, J = 11 Hz) disappeared, and methylene protons by urethane acrylate formation Shift to 3.24 (2H, s), 3.30 (2H, t, J = 6.9 Hz), 4.01 (4H, s).

[Example 4]
<Synthesis of tetrafunctional acryloyl-modified silicon compound A4 (component A)>
One-terminal hydroxyl-modified silicon compound (trade name: Sileplane FMDA21, OH value 24.1 mgKOH / g, manufactured by JNC Corporation) 10.0 g and dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.0014 g, Except for using 0.011 g of p-methoxyphenol, 1.1 g of 1,1 ′-(bisacryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI, manufactured by Showa Denko KK), methanol (0.25 g). Gives a methanol solution (11.5 g, solid content concentration 96 wt%) of the bifunctional acryloyl-modified silicon compound A4 in the same manner as in Example 1.

[Comparative Example 1]
<Preparation of surface treatment agent 1>
Aronix M305 (manufactured by Toagosei Co., Ltd.) 334.9 g, urethane prepolymer P7-532 (manufactured by Kyoeisha Chemical Co., Ltd.) 35.1 g, 1,6-hexanediol diacrylate A-HD- 18.6 g of N (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 27.9 g of Irgacure 127 (manufactured by BASF Japan Ltd.) are dissolved in 583.5 g of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a solid content concentration. A 40 wt% surface treating agent was prepared and used as surface treating agent 1.

[Example 5]
<Preparation of surface treatment agent 2>
0.0083 g of the bifunctional acryloyl-modified silicon compound A1 synthesized in Example 1 was added to 20.0 g of the surface treatment agent 1 (solid content concentration: 40 wt%) prepared in the same manner as in Comparative Example 1, and the total amount of solid content was 2 The surface treatment agent of the present invention was prepared so that the functional acryloyl-modified silicon compound A was 0.1 wt%, and this was designated as surface treatment agent 2.

[Example 6]
<Preparation of surface treatment agent 3>
0.0103 g of the bifunctional acryloyl-modified silicon compound A synthesized in Example 1 was added to 50.0 g of the surface treatment agent 1 (solid content concentration 40 wt%) prepared in the same manner as in Comparative Example 1, and the solid content was The surface treatment agent of the present invention was prepared such that the bifunctional acryloyl-modified silicon compound A was 0.05 wt%, and this was designated as surface treatment agent 3.

[Comparative Example 2]
<Preparation of surface treatment agent 4>
0.0080 g of Silaplane FMDA21 (manufactured by JNC Co., Ltd.) is added to 20.0 g of the surface treatment agent 1 (solid content concentration 40 wt%) prepared in the same manner as in Comparative Example 1, and Silaplane FMDA21 is added to the solid content. The surface treatment agent was adjusted to 0.1 wt%, and this was designated as surface treatment agent 4.

[Comparative Example 3]
<Preparation of surface treatment agent 5>
0.0100 g of Silaplane FMDA21 (manufactured by JNC Corporation) is added to 50.0 g of the surface treatment agent 1 (solid content concentration 40 wt%) prepared by the same method as Comparative Example 1, and Silaplane FMDA21 is added to the solid content. The surface treatment agent was adjusted to 0.1 wt%, and this was designated as surface treatment agent 5.

[Example 7]
<Preparation of cured film 1>
PET (product name: Cosmo Shine A4300, A4 size, 100 μm, manufactured by Toyobo Co., Ltd.) was used as the substrate. The surface treatment agent 2 prepared in Example 5 was used to form a dry film thickness of 5 μm on a PET substrate using a bar coater, dried at 80 ° C. for 1 minute, and then 500 mJ / cm ² using a high-pressure mercury lamp. The coating film was photocured under the light irradiation conditions to form a cured film of the present invention.

[Example 8]
<Preparation of cured film 2>
A cured film of the present invention was formed using the same method as in Example 7 except that the surface treating agent 3 prepared in Example 6 was used instead of the surface treating agent 2, and this was used as the cured film 2.

[Comparative Example 4]
<Preparation of cured film 3>
A cured film 3 was produced using the same method as in Example 7 except that the surface treatment agent 4 produced in Comparative Example 2 was used instead of the surface treatment agent 2.

[Comparative Example 5]
<Preparation of cured film 4>
A cured film 5 was produced in the same manner as in Example 7 except that the surface treatment agent 5 produced in Comparative Example 3 was used instead of the surface treatment agent 2.

[Comparative Example 6]
<Preparation of cured film 5>
A cured film 5 was produced in the same manner as in Example 7 except that the surface treatment liquid 1 produced in Comparative Example 1 was used instead of the surface treatment liquid 2.

<Test of cured film>
(1) Magic ink (trade name)
(2) Wiping test (antifouling evaluation)
The surface layer of the cured film was drawn with a black oil marker (manufactured by Sharpie), and the number of times the oil ink was repelled and wiped with Dusper K-3 (manufactured by Ozu Sangyo Co., Ltd.) was evaluated.

  The results of (1) are shown in Table 1 (Magic ink wiping frequency evaluation results).

  Examples 7 to 8 (treatment agent of the present invention to which a bifunctional acryloyl-modified silicon compound (component A) was added and Comparative Examples 4 to 5 (coating agent to which Silaplane FMDA21 was added), Comparative Example 6 (silicon compound was added) In comparison example 6, it was confirmed that the magic ink wiping count was 0 and no antifouling durability, and in comparative examples 4 to 5, the magic ink wiping count was 4 to 4. Although the antifouling durability slightly increased to 11 times, it was insufficient, but in Examples 7 to 8, the magic ink wiping frequency was remarkably improved, and the antifouling durability was improved.

  From the above, the composition of the present invention is applied to a material for forming a cured film having high antifouling performance and antifouling durability required for surface coating materials for portable terminals and wearable displays. It became clear that we could do it.

Claims (14)

A composition comprising at least one of the silicon compounds represented by formula (1) (component A) and at least one monomer (component B) that can constitute an ultraviolet curable resin or a polymer of this monomer.
(In Formula (1),
n is an integer from 0 to 300;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are each independently hydrogen or alkyl having 1 to 30 carbon atoms,
X ₁ , X ₂ , X ₃ , and X ₄ are each independently a linear or branched alkylene having 1 to 20 carbon atoms,
Y is a silicon compound which is a group represented by formula (2) or formula (3) each independently having an acryloyl group. )

2. The composition according to claim 1, comprising at least one of the silicon compounds represented by formula (4) (component A) and at least one monomer (component B) that can constitute an ultraviolet curable resin or a polymer of this monomer. The composition as described.
(In Formula (4),
n is an integer from 0 to 300)
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are each independently hydrogen or alkylene having 1 to 30 carbon atoms,
Y is a silicon compound which is a group represented by the formula (2) or (3) according to claim 1, each independently having an acryloyl group. )

2. A composition comprising at least one silicon compound represented by formula (5) (component A) and at least one monomer (component B) capable of constituting an ultraviolet curable resin or a polymer of this monomer. 2. The composition according to 2.
(In Formula (5),
n is an integer from 0 to 300;
R ₉ and R ₁₀ are alkylene having 1 to 4 carbon atoms,
Y is a silicon compound which is a group represented by the formula (2) or (3) according to claim 1, each independently having an acryloyl group. )

1. A composition comprising at least one silicon compound represented by formula (6) (component A) and at least one monomer (component B) capable of constituting an ultraviolet curable resin or a polymer of this monomer. 4. The composition according to any one of 3 above.
(In Formula (6),
n is a silicon compound which is an integer of 0-300. )

1. A composition comprising at least one silicon compound represented by formula (7) (component A) and at least one monomer (component B) capable of constituting an ultraviolet curable resin or a polymer of this monomer. 4. The composition according to any one of 3 above.
(In Formula (7),
n is a silicon compound which is an integer of 0-300. )

(7)   The composition according to any one of claims 1 to 5, wherein Component B is at least one of a monomer capable of constituting an ultraviolet curable resin having at least one (meth) acryloyl group or a polymer of this monomer. .   Furthermore, the composition of any one of Claims 1-6 containing a hardening | curing agent.   8. The composition according to claim 7, wherein the curing agent generates radicals upon irradiation with ultraviolet rays.   Furthermore, the composition of any one of Claims 1-8 containing an organic solvent.   Furthermore, the composition of any one of Claims 1-9 containing at least 1 sort (s) (component C) of the monomer which comprises a thermosetting resin or this resin.   Furthermore, the composition of any one of Claims 1-10 containing at least 1 sort (s) (component D) of the monomer which comprises a thermoplastic resin or this resin.   The surface treating agent obtained using the composition of any one of Claims 1-11.   The cured film which hardened the coating film formed by apply | coating the composition or surface treating agent of any one of Claims 1-12.   A laminate having the cured film according to claim 13.