JP5142075B2 - Active energy ray curable resin, active energy ray curable resin composition, and article having a hard coat layer obtained using the same - Google Patents

Description

  The present invention relates to an active energy ray-curable resin, an active energy ray-curable resin composition, and an article having a hard coat layer obtained by using these.

Active energy ray-curable resin compositions that are radically polymerized by irradiation with active energy rays such as ultraviolet rays and electron beams, and are instantly cured, can form a high hardness film, such as various plastics, glass, paper, etc. It is useful as a hard coat agent for forming a protective layer on these articles by coating on the surface of the substrate.

However, in recent years, with the widespread use of electronic devices using touch panels such as mobile phones and notebook computers, the application field of hard coating agents has expanded, and the hard coating agents used for them are hard to impart conventional scratch resistance. In addition to the coating properties, it is required to provide antifouling properties such as the difficulty of attaching dirt to the dirt that occurs in our lives and the ease of wiping when dirt is attached. ing.
However, in order to have antifouling properties in addition to hard coat properties, it is necessary to form a coating film having antifouling properties after applying a hard coat agent that forms a hard coating film. There was a tendency to increase the cost and the cost (Patent Document 1).
Therefore, in order to solve the above-described problems, a one-component coating material having both hard coat properties and antifouling properties has been demanded, and various proposals have been made. For example, a curable composition comprising a polyfluoroalkyl group-containing polymerizable monomer, a copolymer of a photocurable functional group-containing polymerizable monomer, and a compound containing at least one active energy ray-curable polymerizable functional group. (Patent Document 2) has been proposed, but since the polyfluoroalkyl group-containing polymerizable monomer is expensive, it can be said that it is not sufficient as a solution for the above-mentioned high cost.
In addition, as an antifouling component, a polyorganosiloxane group, a polyorganosiloxane-containing graft polymer, a polyorganosiloxane-containing block polymer, and an acrylate compound having a bifunctional or higher polymerizable functional group containing a fluorinated alkyl group is UV-curable. Although the proposal (patent document 3) using the composition mix | blended with resin is also made | formed, it is enough from a viewpoint of compatibility with various acrylic resins and other resin, and an organic solvent, and coexistence of hard-coat property and antifouling property. The physical properties were not satisfied.
In addition, a combination of a compound having antifouling properties such as a polyorganosiloxane compound or a polyfluoroalkyl compound and inorganic oxide fine particles such as colloidal silica (Patent Document 4, Patent Document 5) or a hydrophilic polymer in a hydrophobic polymer. Although proposals (Patent Document 6) to disperse the functional particles have been made, it has not yet been achieved to satisfy sufficient physical properties.

International Publication No. 2003/081296 Pamphlet JP 2002-241446 A JP 2007-264281 A JP 2006-160802 A International Publication No. 2004/047095 Pamphlet JP 2006-328196 A

The present invention has both a hard coat property that protects the surface of an article due to impact and the like from damage and scratches, dirt adhesion to the article surface, and antifouling property that can easily remove the attached dirt, and is transparent. It is an object of the present invention to provide an active energy ray-curable resin capable of forming a hard coat layer excellent in appearance protection performance on the surface of an article, the resin composition, and a hard coat agent containing them.

As a result of intensive studies to solve the above problems, the present inventor has obtained a copolymer containing an epoxy group-containing (meth) acrylate , polysiloxane mono (meth) acrylate and fluoroalkyl mono (meth) acrylate , It reacts with α, β-unsaturated carboxylic acid, has polysiloxane mono (meth) acrylate and fluoroalkyl mono (meth) acrylate and α, β-unsaturated functional group in the side chain, and specifies (meth) acrylic equivalent A hard coat layer excellent in both hard coat properties and antifouling properties is formed by using an active energy ray-curable resin composition containing a specific average particle size silica as an inorganic resin and an acrylic resin adjusted to the range of The present inventors have found that a hard coat agent that can be used is produced, and have completed the present invention.
That is, the present invention provides an α, β-unsaturated carboxylic acid as a polymerization component to a copolymer containing an epoxy group-containing (meth) acrylate , polysiloxane mono (meth) acrylate and fluoroalkyl mono (meth) acrylate. An active energy ray-curable resin composition containing an active energy ray-curable resin having an acrylic equivalent of 200 to 700 g / eq and silica having an average particle size of 40 to 200 nm obtained by reacting an acid; A hard coat agent containing a resin composition ; It relates to an article having a hard coat layer obtained by curing the active energy ray-curable resin composition .

According to the present invention, it has high hardness and prevents the adhesion of dirt on the article surface and hard coat property that protects the article surface from damage or scratches due to impact, etc., and even if it adheres easily Provided is an active energy ray curable resin capable of forming a hard coat layer (cured film) having a removable antifouling property on the surface of an article, the resin composition, and a hard coat agent containing the resin or resin composition can do. By using the hard coat agent containing the resin or resin composition of the present invention, the conventional hard coat layer and antifouling layer can be produced in a single process without being separately applied and cured. A hard coat layer having antifouling properties can be efficiently formed on the surface of the article.

  The active energy ray-curable resin of the present invention comprises, as polymerization components, (meth) acrylate (a) (hereinafter referred to as component (a)) containing an epoxy group, and polysiloxane mono (meth) acrylate (b) ( Hereinafter, it is obtained by reacting a copolymer containing (b) component) with an α, β-unsaturated carboxylic acid.

The component (a) used in the copolymer of the present invention is a (meth) acrylate compound having an epoxy group in the molecule ((meth) acrylate refers to acrylate and / or methacrylate. (Meth) refers to Are the same meanings), and specific examples include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of production cost and availability.

The component (b) used in the copolymer of the present invention is a compound having one (meth) acryloyl group as a radical polymerizable functional group in one molecule and an organopolysiloxane unit, and represented by the following general formula: It is.

式（１）中、Ｒ_１とＲ_２は同一でも、異なっていてもよく、それぞれ、水素原子、またはメチル基を示す。ｎは０〜６までの整数、ｍは1〜２７０までの整数を示す。

In formula (1), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom or a methyl group. n represents an integer from 0 to 6, and m represents an integer from 1 to 270.

The presence of the component (b) imparts water repellency to the surface of the hard coat layer (cured film) obtained. (B) Component (meth) acryloyl group which is a polymerizable functional group in the molecule is limited to one, and when (b) component has two or more (meth) acryloyl groups, By incorporating the polysiloxane unit into the copolymer, an active energy ray-curable resin having excellent hard coat characteristics cannot be obtained.

Although the weight average molecular weight of (b) component is not specifically limited, It is preferable that it is about 500-20,000 by polystyrene conversion value by a gel permeation chromatography method, and it is more preferable that it is 500-2,000. When a material having a weight average molecular weight of less than 500 is used, water repellency is insufficient, and the antifouling property of the resulting hard coat layer may be insufficient, and a material having a weight average molecular weight exceeding 20,000 is used. In such a case, the compatibility between the component (a) and the component (b) is deteriorated, the random copolymerization reaction is difficult to proceed, and the hard coat property of the obtained cured film may not be sufficiently exhibited.

(B) As an ingredient, brand name "X-22-2426" (made by Shin-Etsu Silicone), brand name "X-22-174D" (made by Shin-Etsu Chemical Co., Ltd.), brand name "Silaplane FM-0711". ”(Manufactured by Chisso Corporation) or the like.

Component (a) and component (b) are generally used in an amount of 1 to 100 parts by weight, preferably 3 to 50 parts, based on 100 parts by weight of component (a). When the proportion of the component (b) is less than 1 part, the antifouling property of the hard coat layer tends to be insufficient, and when it exceeds 100 parts, the wettability with various substrates deteriorates and the appearance of the hard coat layer There is a tendency that defects are likely to occur.

In addition to the components (a) and (b), as optional components, fluoroalkyl mono (meth) acrylate (c) (hereinafter referred to as component (c)) and alkyl mono (meth) acrylate (d) component (Hereinafter referred to as component (d)) can also be used. By adding the component (c) as a copolymer component, the oil repellency of the resulting hard coat layer can be improved. By adding the component (d) as a copolymer component, the surface of the hard coat layer can be improved. Lipophilicity can be imparted.

  The component (c) used in the present invention has one (meth) acryloyl group and a fluoroalkyl group capable of radical polymerization in one molecule, and is represented by the following general formula.

式（３）中、Ｒ_３は水素原子またはメチル基、Ｒｆは炭素数１〜２０のフルオロアルキル。ｐは０〜６までの整数。ただし、基中の水素原子の１個以上が水酸基またはハロゲン原子に置換されていてもよく、炭素−炭素結合間にエーテル性酸素原子またはチオエーテル性硫黄原子が挿入されていてもよい。

In Formula (3), R ₃ is a hydrogen atom or a methyl group, and Rf is a fluoroalkyl having 1 to 20 carbon atoms. p is an integer from 0 to 6. However, one or more hydrogen atoms in the group may be substituted with a hydroxyl group or a halogen atom, and an etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds.

  More preferably, Rf is preferably a fluoroalkyl group having 3 to 14 carbon atoms, and particularly preferably a linear perfluoroalkyl group having 3 to 14 carbon atoms in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

The component (c) is an alkyl (meth) acrylate having one (meth) acryloyl group as a radical polymerizable functional group in one molecule, and specific examples include 2,2,2-trifluoroethyl ( (Meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) Examples include acrylates. The component (c) can be easily obtained as a trade name “V-8FM” (Osaka Organic Chemical Industry Co., Ltd.), a trade name “R-1820” (Daikin Chemicals Sales Co., Ltd.), or the like.

  The component (d) used in the present invention has one (meth) acryloyl group capable of radical polymerization in one molecule and an alkyl group having 12 to 22 carbon atoms, and is represented by the following general formula. is there.

式（３）中、Ｒ_４およびＲ_５は、水素原子またはメチル基を示す。ｑは、１２〜２２の整数を示し、好ましくは18以上のステアリル（メタ）アクリロイル、ベヘニル（メタ）アクリロイルが好ましい。（ｄ）成分は、商品名「ブレンマーＳＭＡ」（日油（株））等として容易に入手することができる。

In formula (3), R ₄ and R ₅ represent a hydrogen atom or a methyl group. q represents an integer of 12 to 22, preferably stearyl (meth) acryloyl or behenyl (meth) acryloyl of 18 or more. The component (d) can be easily obtained as a trade name “Blemmer SMA” (Nippon).

The proportion of component (c) and / or component (d) used is in the range of about 2 to 50% by weight (component (c) and component (d), based on the total amount of components used for copolymerization). When the components are used in combination, the total amount of the component (c) and the component (d) is preferably in the range of 2 to 50% by weight (hereinafter the same), and preferably in the range of 3 to 25% by weight. Is more preferable. When the amount used is less than 2% by weight, the properties expected of each additional component tend to be insufficient, and when it exceeds 50% by weight, the cured product has a low crosslink density and is a sufficient hard coat. There is a risk that the sex will not be obtained.

The polymerization method of each polymerization component including the component (a) and the component (b) or, if necessary, the component (c) and the component (d) is not particularly limited, and may be performed by a known method. For example, a solvent serving as a common solvent is mixed with each of these copolymer components, and a uniform mixture solution having a total component content of 20 to 60% by weight is used as a reaction solution, and dropped at a temperature of 80 to 140 ° C. By carrying out polymerization, (a) component, (b) component (when (c) component or (d) component is added, all components (a) to (d) are copolymerized randomly) A polymer can be obtained.
The solvent used for the polymerization reaction is not particularly limited, but generally includes toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, cyclohexanone, ethylene dichloride, carbon tetrachloride and the like.

The active energy ray-curable resin of the present invention can be obtained by reacting an α, β-unsaturated carboxylic acid with a copolymer obtained by polymerizing the above components.
This reaction is a reaction in which an epoxy group in a polymer is ring-opened and an α, β-unsaturated carboxylic acid is added thereto.

  As the α, β-unsaturated carboxylic acid, various known ones can be used without particular limitation. Specifically, for example, α, β-unsaturated monocarboxylic acid such as (meth) acrylic acid, (meth) acrylic acid dimer, maleic anhydride, maleic acid, crotonic acid, itaconic acid, fumaric acid, muconic acid, citracone Examples include α, β-unsaturated dicarboxylic acids such as acids. Among these, (meth) acrylic acid is preferable from the viewpoint of the photopolymerization reactivity of the generated active energy ray-curable resin and the hard coat property of the cured product.

The reaction between the copolymer and the α, β-unsaturated carboxylic acid is not particularly limited, and various known methods can be employed. Usually, a copolymer and an α, β-unsaturated carboxylic acid are mixed, and if necessary, a solvent that does not react with each component and has good compatibility may be used. Furthermore, in the addition reaction of α, β-unsaturated carboxylic acid, the reaction in the temperature range of 80 to 120 ° C. suitably proceeds. Considering the temperature range of the reaction, the solvent used preferably has a boiling point of 120 ° C. or higher, for example, methyl isobutyl ketone and butyl acetate. In this addition reaction, a catalyst can be used for the purpose of shortening the reaction time. Specific examples of the catalyst include basic catalysts such as pyridine, pyrrole, triethylamine, diethylamine, amines such as dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine, copper naphthenate, and naphthenic acid. Examples thereof include metal catalysts such as cobalt, zinc naphthenate, tributoxyaluminum, and tetrabutoxytrititanium, Lewis acids such as aluminum chloride, and organic tin compounds such as dibutyltin dilaurate.

The active energy ray-curable resin thus obtained needs to have a (meth) acrylic equivalent adjusted to a range of 200 to 700 g / eq. When the (meth) acrylic equivalent is less than 200, the antifouling property is insufficient, and when it exceeds 700 g / eq, the crosslinking density is insufficient and the hard coat property tends to be lowered. The weight average molecular weight of the active energy ray-curable resin is preferably about 10,000 to 100,000, preferably 15,000 to 50,000 in terms of polystyrene converted by gel permeation chromatography. More preferred.
When the weight average molecular weight exceeds 100,000, the handling property and leveling property as a coating agent tend to deteriorate.

The active energy ray-curable resin composition of the present invention may contain an inorganic filler to form an active energy ray-curable resin composition. By blending an inorganic filler, fine irregularities are formed on the surface of the resulting hard coat layer, making it difficult for oil stains such as sebum to adhere, and even if attached, can be easily wiped off (improved wiping performance) Further, the antifouling property of the cured film can be made more excellent.

As the inorganic filler, known ones such as silica and metal oxide fine particles can be used without limitation. Examples of the metal oxide fine particles include titanium oxide, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, and indium oxide. These may be used alone or in combination of two or more. Of these, at least one selected from the group consisting of silica, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide is preferred because it is commercially available, easily available, and inexpensive. It is preferable to use an inorganic filler having an average particle diameter adjusted to about 40 to 200 nm (by laser diffraction / scattering method). When the average particle size is less than 40, the antifouling property of the resulting hard coat layer tends to be insufficiently improved, and when the average particle size exceeds 200 nm, the antifouling property is improved but cured. Whitening of the film is likely to occur, and optical characteristics such as haze and transmission efficiency may be impaired. In particular, application in applications that require optical characteristics such as display is difficult.

The amount of inorganic filler used is the active energy ray-curable resin composition (in terms of solid content) from the viewpoint of ensuring the hard coat properties (high hardness, scratch resistance, etc.) and optical properties (transparency, etc.) of the cured film obtained. ) To about 3 to 20% by weight.

The active energy ray-curable resin or the active energy ray-curable resin composition of the present invention can be blended with an organic solvent or the like as necessary, and mixed with an organic solvent to form a hard coat agent. Other curing components include pentaerythritol tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth). ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, urethane (meth) acrylate, poly (meth) ester acrylate, and the like. In addition, you may mix | blend these individually or in combination of 2 or more types. The use ratio of the other curing component is not particularly limited, but is preferably 80 parts by weight or less, more preferably 60 parts by weight or less, with respect to 100 parts by weight of the active energy ray-curable resin or resin composition. is there. This is because if it exceeds 80 parts by weight, high antifouling properties may not be sufficiently secured.

Moreover, the hard coat agent of the present invention may further contain various additives such as a leveling agent, an antifoaming agent, a slip agent, and a photosensitizer as necessary.

When the hard coat agent of the present invention is cured with ultraviolet rays, a photopolymerization initiator can be used. The photopolymerization initiator is not particularly limited as long as it can be decomposed by ultraviolet rays to generate radicals to initiate polymerization, and known ones can be used. Specifically, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6- Examples include trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like. These may be used alone or in combinations of two or more. It can be used Te. The usage-amount of a photoinitiator is about 0.1-10 weight part with respect to 100 weight part of active energy ray hardening-type resin compositions.

As a method of forming a hard coat layer (cured film) on the article surface using the hard coat agent of the present invention, the hard coat agent is applied to the article surface by a known method and dried, and then irradiated with active energy rays. This is done by curing. Examples of the method for applying the hard coating agent include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. The coating amount is not particularly limited, but is usually within a range where the weight after drying is 0.1 to 20 g / m ² , preferably 0.5 to 10 g / m ² .

  The article (base material) on which the hard coat layer can be formed using the hard coat agent (active energy ray-curable resin composition) of the present invention is not particularly limited, and examples thereof include plastics (polycarbonate, polymethyl methacrylate, Polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin), metal, wood, paper, glass, slate, and the like.

Since the hard coat layer (cured film) formed using the hard coat agent (active energy ray-curable resin) of the present invention contains the component (b), the surface of the cured film having a low surface energy is present. It is formed and has both a high hard coat property and an antifouling effect. Furthermore, by blending an inorganic filler, a fine uneven surface (surface roughness of about several nanometers to several tens of nanometers) is formed on the surface of the cured film, so that the surface area having low surface energy is increased, and the effect It is thought that the improvement of the level will be further improved.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to each of these examples. In each example, all parts and% are based on weight unless otherwise specified (Synthesis Example 1). A synthesis stirrer, thermometer, air bubbling device and reflux condenser, and dropping funnel of active energy ray-curable resin 1 are 2 In a flask equipped with 270 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA), 30 parts by weight of polysiloxane methacrylate (FM-0721; manufactured by Chisso Corporation), 1.6 parts by weight of lauryl mercaptan, methyl isobutyl ketone (hereinafter referred to as MIBK). ) 1000 parts by weight and 7.5 parts by weight of azobisisobutyronitrile (hereinafter referred to as AIBN) were charged, and the temperature was raised to 90 ° C. over 1 hour with stirring in a nitrogen atmosphere. Reacted for hours. After the reaction for 1 hour, a mixed solution composed of 630 parts by weight of GMA, 4.4 parts by weight of lauryl mercaptan, and 22.5 parts by weight of AIBN and 70 parts by weight of FM-0721 were simultaneously added dropwise over 2 hours, and then reacted at 100 ° C. for 3 hours. I let you. Thereafter, 10 parts by weight of AIBN was added and reacted at 100 ° C. for 1 hour, and then heated to around 120 ° C. and kept warm for 2 hours. Cool to 60 ° C, switch to air bubbling from a nitrogen atmosphere, add 456 parts by weight of acrylic acid and 2 parts by weight of p-methoxyphenol, raise the temperature to 110 ° C with stirring, and hold for 8 hours to react. It was. Then, after cooling to 80 ° C., 1.4 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine were added, kept at 80 ° C. for 30 minutes, and then cooled to room temperature. The obtained resin had an acrylic equivalent of 280 g / eq and a weight average molecular weight of 18,000. In addition, the weight average molecular weight was calculated | required as a polystyrene conversion value by gel permeation chromatography (The Tosoh company make, HLC8120, use column: TSKgel SuperHM-Lx3, developing solvent: Tetrahydrofuran, flow rate 0.60 ml / min).

(Synthesis Example 2) A synthetic stirrer of active energy ray-curable resin 2, a thermometer, an air bubbling device and a reflux condenser, a flask equipped with two dropping funnels, 34 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA), 44 parts by weight of polysiloxane methacrylate (FM-0721; manufactured by Chisso Corporation), 1.6 parts by weight of lauryl mercaptan, 1000 parts by weight of methyl isobutyl ketone (hereinafter, MIBK), and azobisisobutyronitrile (hereinafter, AIBN) 7.5 parts by weight was charged, and the temperature was raised to 90 ° C. over 1 hour with stirring in a nitrogen atmosphere, followed by reaction at 90 ° C. for 1 hour. After the reaction for 1 hour, a mixed solution composed of 101 parts by weight of GMA, 4.4 parts by weight of lauryl mercaptan, and 22.5 parts by weight of AIBN and 132 parts by weight of FM-0721 were dropped simultaneously over 2 hours, and then reacted at 100 ° C. for 3 hours. I let you. Thereafter, 10 parts by weight of AIBN was added and reacted at 100 ° C. for 1 hour, and then heated to around 120 ° C. and kept warm for 2 hours. Cool to 60 ° C, switch to air bubbling from nitrogen atmosphere, add 69 parts by weight of acrylic acid and 2 parts by weight of p-methoxyphenol, stir and warm to 110 ° C, then hold for 8 hours to react. It was. Then, after cooling to 80 ° C., 1.4 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine were added, kept at 80 ° C. for 30 minutes, and then cooled to room temperature. The obtained resin had an acrylic equivalent of 497 g / eq and a weight average molecular weight of 13,000. In addition, the weight average molecular weight was calculated | required as a polystyrene conversion value by gel permeation chromatography (The Tosoh company make, HLC8120, use column: TSKgel SuperHM-Lx3, developing solvent: Tetrahydrofuran, flow rate 0.60 ml / min).

(Synthesis Example 3) Synthesis of Active Energy Ray-Curable Resin 3 A flask equipped with a stirrer, a thermometer, an air bubbling device and a reflux condenser, and two dropping funnels, 270 parts by weight of GMA, FM-0721 (FM-0721) Manufactured by Chisso Corporation) 15 parts by weight, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate 15 parts by weight, lauryl mercaptan 1.6 parts by weight, MIBK 1000 parts by weight, and AIBN 7.5 parts by weight were charged with nitrogen. The mixture was heated to 90 ° C. over 1 hour with stirring under an atmosphere, and then reacted at 90 ° C. for 1 hour. After reacting for 1 hour, a mixed solution consisting of 630 parts by weight of GMA, 35 parts by weight of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 4.4 parts by weight of lauryl mercaptan, 22.5 parts by weight of AIBN, and 35 parts by weight of FM-0721 The portions were added dropwise simultaneously over 2 hours, and then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts by weight of AIBN was added and reacted at 100 ° C. for 1 hour, and then heated to around 120 ° C. and kept warm for 2 hours. Cool to 60 ° C, switch to air bubbling under nitrogen atmosphere, add 355 parts by weight of acrylic acid and 2 parts by weight of p-methoxyphenol, stir and warm to 110 ° C, then hold for 8 hours to react. It was. Then, after cooling to 80 ° C., 1.4 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine were added, kept at 80 ° C. for 30 minutes, and then cooled to room temperature. The acrylic equivalent of the obtained resin was 280 g / eq, and the weight average molecular weight was 18,000. The weight average molecular weight was determined by the same method as in Synthesis Example 1.

(Synthesis Example 4) Synthesis of active energy ray-curable resin 4
In a flask equipped with a stirrer, thermometer, air bubbling device and reflux condenser, and two dropping funnels, 270 parts by weight of GMA, 30 parts by weight of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, lauryl mercaptan 6 parts by weight, MIBK 1000 parts by weight, and AIBN 7.5 parts by weight were charged, and the temperature was raised to 90 ° C. over 1 hour with stirring in a nitrogen atmosphere, followed by reaction at 90 ° C. for 1 hour. After the reaction for 1 hour, a mixed solution consisting of 630 parts by weight of GMA, 70 parts by weight of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 4.4 parts by weight of lauryl mercaptan, and 22.5 parts by weight of AIBN was added dropwise over 2 hours. And then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts by weight of AIBN was added and reacted at 100 ° C. for 1 hour. Cool to 60 ° C, switch to air bubbling under nitrogen atmosphere, add 456 parts by weight of acrylic acid and 2 parts by weight of p-methoxyphenol, and raise the temperature to 110 ° C with stirring, then hold for 8 hours to react. It was. Then, after cooling to 80 ° C., 1.4 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine were added, kept at 80 ° C. for 30 minutes, and then cooled to room temperature. The acrylic equivalent of the obtained resin was 280 g / eq, and the weight average molecular weight was 18,000. The weight average molecular weight was determined by the same method as in Synthesis Example 1.

(Synthesis Example 5) Synthesis of active energy ray-curable resin 5
In a flask equipped with a stirrer, thermometer, air bubbling device and reflux condenser, two dropping funnels, 150 parts by weight of GMA, 150 parts by weight of stearyl methacrylate, 1.6 parts by weight of lauryl mercaptan, 1000 parts by weight of MIBK, and Then, 7.5 parts by weight of AIBN was charged, the temperature was raised to 90 ° C. over 1 hour with stirring in a nitrogen atmosphere, and the mixture was reacted at 90 ° C. for 1 hour. After reacting for 1 hour, a mixture of 350 parts by weight of GMA, 350 parts by weight of stearyl methacrylate, 4.4 parts by weight of lauryl mercaptan, and 22.5 parts by weight of AIBN was added dropwise over 2 hours, and then reacted at 100 ° C. for 3 hours. . Thereafter, 10 parts by weight of AIBN was added and reacted at 100 ° C. for 1 hour, and then heated to around 120 ° C. and kept warm for 2 hours. Cool to 60 ° C, switch to air bubbling from a nitrogen atmosphere, add 253 parts by weight of acrylic acid and 2 parts by weight of p-methoxyphenol, raise the temperature to 110 ° C with stirring, hold for 8 hours and hold for 8 hours Reacted. Then, after cooling to 80 ° C., 1.4 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine were added, kept at 80 ° C. for 30 minutes, and then cooled to room temperature. The obtained resin had an acrylic equivalent of 320 g / eq and a weight average molecular weight of 20,000. The weight average molecular weight was determined by the same method as in Synthesis Example 1.

(Synthesis Example 6)
In a flask equipped with a stirrer, thermometer, air bubbling device and reflux condenser, and two dropping funnels, 75 parts by weight of glycidyl methacrylate (hereinafter referred to as GMA) and polysiloxane methacrylate (FM-0721; manufactured by Chisso Corporation) 225 parts by weight, 1.6 parts by weight of lauryl mercaptan, 1000 parts by weight of methyl isobutyl ketone (hereinafter referred to as MIBK), and 7.5 parts by weight of azobisisobutyronitrile (hereinafter referred to as AIBN) are charged and stirred in a nitrogen atmosphere. Then, the temperature was raised to 90 ° C. over 1 hour, and then reacted at 90 ° C. for 1 hour. After the reaction for 1 hour, a mixture of 175 parts by weight of GMA, 4.4 parts by weight of lauryl mercaptan, and 22.5 parts by weight of AIBN and 525 parts by weight of polysiloxane methacrylate (FM-0721; manufactured by Chisso Corporation) were added over 2 hours. After dripping simultaneously, it was made to react at 100 degreeC for 3 hours. Thereafter, 10 parts by weight of AIBN was added and reacted at 100 ° C. for 1 hour, and then heated to around 120 ° C. and kept warm for 2 hours. After cooling to 60 ° C., air bubbling was switched from under a nitrogen atmosphere, 127 parts by weight of acrylic acid and 2 parts by weight of p-methoxyphenol were added, the temperature was raised to 110 ° C. with stirring, and the reaction was allowed to proceed for 8 hours. Then, after cooling to 80 ° C., 1.4 parts by weight of p-methoxyphenol and 1.4 parts by weight of triphenylphosphine were added, kept at 80 ° C. for 30 minutes, and then cooled to room temperature. The obtained resin had an acrylic equivalent of 860 g / eq and a weight average molecular weight of 14,000. The weight average molecular weight was determined by the same method as in Synthesis Example 1.

(Preparation of hard coat agent)
Each active energy ray-curable resin obtained by the above synthesis was used as a paint to prepare a hard coat agent.

Example 1
100 parts by weight of the polysiloxane-containing polymer acrylate obtained in Synthesis Example 1 is blended with 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, and methyl ethyl ketone so that the nonvolatile content is 40%. Was diluted and mixed uniformly.

(Example 2)
50 parts by weight of the polysiloxane-containing polymer acrylate obtained in Synthesis Example 1, 50 parts by weight of pentaerythritol tetraacrylate, and 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator were blended, and the nonvolatile content was The mixture was diluted with methyl ethyl ketone so as to be 40% and mixed uniformly.

(Example 3)
50 parts by weight of the polysiloxane-containing polymer acrylate obtained in Synthesis Example 2, 50 parts by weight of pentaerythritol tetraacrylate, and 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator were blended, and the nonvolatile content was The mixture was diluted with methyl ethyl ketone so as to be 40% and mixed uniformly.

Example 4
50 parts by weight of a polymer acrylate containing both 1H, 1H, 2H, 2H-heptadecafluorodecyl group obtained in Synthesis Example 3 and polysiloxane, 50 parts by weight of pentaerythritol tetraacrylate, Irgacure 184 ( 3 parts of Ciba Specialty Chemicals Co., Ltd. were blended, diluted with methyl ethyl ketone so that the nonvolatile content was 40%, and mixed uniformly.

(Example 5)
40 parts by weight of a polymer acrylate containing both 1H, 1H, 2H, 2H-heptadecafluorodecyl group obtained in Synthesis Example 3 and polysiloxane, 40 parts by weight of pentaerythritol tetraacrylate, silica sol (particle size 10 nm, 70% MEK Solution) 20 parts by weight, 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator were blended, diluted with methyl ethyl ketone so that the nonvolatile content was 40%, and mixed uniformly.

(Example 6)
40 parts by weight of a polymer acrylate containing both 1H, 1H, 2H, 2H-heptadecafluorodecyl group obtained in Synthesis Example 3 and polysiloxane, 40 parts by weight of pentaerythritol tetraacrylate, silica sol (particle diameter 50 nm 70% MEK Solution) 20 parts by weight, 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator were blended, diluted with methyl ethyl ketone so that the nonvolatile content was 40%, and mixed uniformly.

(Example 7)
40 parts by weight of polymer acrylate containing both 1H, 1H, 2H, 2H-heptadecafluorodecyl group obtained in Synthesis Example 3 and polysiloxane, 40 parts by weight of pentaerythritol tetraacrylate, silica sol (particle size: 300 nm, 70% MEK) Solution) 20 parts by weight, 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator were blended, diluted with methyl ethyl ketone so that the nonvolatile content was 40%, and mixed uniformly.

(Comparative Example 1)
100 parts by weight of 1H, 1H, 2H, 2H-heptadecafluorodecyl group-containing polymer acrylate obtained in Synthesis Example 4 and 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator were blended. The solution was diluted with methyl ethyl ketone so that the non-volatile content was 40% and mixed uniformly.

(Comparative Example 2)
In 100 parts by weight of the stearyl-containing polymer acrylate obtained in Synthesis Example 5, 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) is blended as a photopolymerization initiator, and methyl ethyl ketone is used so that the nonvolatile content is 40%. Diluted and mixed uniformly.

(Comparative Example 3)
100 parts by weight of pentaerythritol tetraacrylate, 2 parts by weight of FM-0721 and 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator are blended, and methyl ethyl ketone is used so that the nonvolatile content is 40%. Diluted and mixed uniformly.

(Comparative Example 4)
100 parts by weight of pentaerythritol tetraacrylate, 2 parts by weight of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, and 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator are blended and nonvolatile. The mixture was diluted with methyl ethyl ketone so that the content was 40% and mixed uniformly.

(Comparative Example 5)
50 parts by weight of the polymer acrylate obtained in Synthesis Example 6 and 50 parts by weight of pentaerythritol tetraacrylate were combined with 3 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, and the nonvolatile content was 40%. The mixture was diluted with methyl ethyl ketone and mixed uniformly.

(Evaluation of hard coat film)
Using the hard coat agent obtained as described above, a substrate surface hard coat film was formed by the following method, and the evaluation test was performed. The results are shown in Tables 1 and 2.
It was coated on a polyethylene terephthalate film having a thickness of 100 μm with a bar coater # 12 and dried in a circulating dryer at 80 ° C. for 1 minute, and then a high-pressure mercury lamp 80 W / cm (one lamp), an irradiation distance 10 cm, and a belt speed 10 m A coating film was formed under the condition of an integrated irradiation amount of 250 mJ / cm ^{2 under} the condition of / min.

<Appearance>
The appearance of the coating film was visually evaluated for leveling (smoothness), presence of defects on the skin, and pinholes.
○ = Excellent × = Bad

<Haze>
It measured according to JIS-K-7361.

<Pencil hardness>
Evaluation was performed according to the test method of JIS-K-5600.

<Abrasion resistance>
The surface of the coating film was rubbed 50 times with a weight of 500 g per cubic centimeter of grade 0000 steel wool, and the presence or absence of scratches on the coating film surface was visually observed.

<Oil dirt repellency>
As the oil stain, oil-based magic ink (No700-T1 manufactured by Kurodanishi Chemical Co., Ltd.) was used, and the oil-based magic ink was applied linearly to the cured coating, and the repellency of the oil-based magic ink was visually evaluated.
○ = Repelling occurred and lines could not be written.
Δ = Slight repellency, but I could draw a line.
X = Repelling did not occur and lines could be written.

<Oil dirt wipeability>
Use oil-based magic ink (No700-T1 Kurodera Nishi Chemical Co., Ltd.) as oil stain, apply oil-based magic ink linearly to the cured coating, dry for 5 minutes, wipe with Kimwipe, and wipe in the following 4 steps The takeability was evaluated.
◎ = Lightly wiping light and no wiping traces ○ = No wiping traces △ = The wiping traces can be confirmed thin × = No wiping

<Wipeability after ethanol rubbing>
After rubbing the surface of the cured coating 50 times with a Kim wipe containing ethanol, oil-based magic ink (No700-T1 Kurodanishi Chemical Co., Ltd.) was applied linearly, dried for 5 minutes and wiped with Kim Wipe. Wipeability was evaluated in four stages.
◎ = Wiping is especially light and no wiping traces ○ = No wiping traces △ = Wiping traces can be checked thinly × = No wiping is possible Further, after repeating this operation three times, repeat the same procedure as above. The wipeability was evaluated.

＊：塗膜成分が分離していたため、測定することができなかった。

*: Since the coating film component was separated, it could not be measured.

Claims (5)

As a polymerization component, a copolymer containing (meth) acrylate (a) containing an epoxy group , polysiloxane mono (meth) acrylate (b) and fluoroalkyl mono (meth) acrylate (c) is added to α, β- An active energy ray-curable resin composition comprising an active energy ray-curable resin having an acrylic equivalent of 200 to 700 g / eq and silica having an average particle size of 40 to 200 nm , obtained by reacting an unsaturated carboxylic acid. The active energy ray-curable resin composition according to claim 1, wherein the active energy ray-curable resin has a weight average molecular weight of 10,000 to 100,000. A hard coat agent containing the active energy ray-curable resin composition according to claim 1 . Furthermore, the hard-coat agent of Claim 3 containing a polyfunctional (meth) acrylate component. An article having a hard coat layer obtained by curing the hard coat agent according to claim 3 or 4 .