KR20160025505A - Resin compositions for forming hard coating layer - Google Patents

Abstract

An object of the present invention is to provide a resin composition for forming a hard coat layer which is capable of forming a hard coat layer excellent in antifouling property and slipperiness and excellent in scratch resistance. The resin composition for forming a hard coat layer of the present invention comprises (meth) acrylate monomer (A) containing urethane (meth) acrylate (A1) having at least three (meth) acryloyloxy groups per molecule, (B) having a (meth) acryloyloxy group and a silicone grafted acrylic polymer (C) having a (meth) acryloyloxy group having a glass transition temperature of 0 or less, a photopolymerization initiator (D) Is a resin composition for forming a hard coat layer containing an organic solvent (E).

Description

[0001] Resin compositions for forming a hard coat layer [0002]

The present invention relates to a resin composition for forming a hard coat layer.

In recent years, a number of products having a touch panel attached to a flat panel display such as a personal computer, a mobile phone, a portable game device, or an ATM have started to be commercialized.

It is known that such a touch panel is provided with a hard coat layer on its surface for the purpose of imparting antifouling properties, slipperiness, and scratch resistance.

For example, Patent Document 1 discloses a hard coat film having a base sheet and a hard coat layer formed on at least one surface of the base sheet,

Wherein the hard coat layer comprises a hard coat layer comprising a fluorine-based compound having a (meth) acryloyl group at a terminal, a polysiloxane-based compound having a (meth) acryloyl group at a terminal, a polyfunctional (meth) acrylic monomer, Wherein the curable composition is a cured product obtained by curing the composition with an active energy ray,

When the peak intensities of the K alpha lines of the fluorine atom and the silicon atom obtained by the fluorescent X ray (XRF) analysis of the hard coat film are respectively a and b,

0.01? A / b? 0.5 (1)

Hard coat film ".

Japanese Unexamined Patent Application Publication No. 2012-240266

The present inventor has studied the hard coat layer (hard coat film) described in Patent Document 1, and found that the antifouling property and slipperiness are good, but there is room for improvement in resistance to abrasion.

It is therefore an object of the present invention to provide a hard coat layer-forming resin composition which is capable of forming a hard coat layer having excellent antifouling property and slipperiness and excellent in resistance to damage.

The inventor of the present invention has conducted intensive studies to solve the above problems. As a result, the present inventors have found that a resin composition containing a predetermined fluorine compound and a silicone grafted acrylic polymer exhibiting a specific glass transition temperature together with a polyfunctional urethane (meth) The present inventors have found that a hard coat layer having excellent antifouling property and slippery property can be obtained and excellent durability can be formed.

That is, it has been found that the above problems can be solved by the following constitutions.

(Meth) acrylate monomer (A) comprising a polyfunctional urethane (meth) acrylate (A1) having at least three (meth) acryloyloxy groups in one molecule,

A fluorine compound (B) having a (meth) acryloyloxy group,

(C) having a glass transition temperature of 0 占 폚 or less and having a (meth) acryloyloxy group,

A photopolymerization initiator (D)

A resin composition for forming a hard coat layer containing an organic solvent (E).

(2) The resin composition for forming a hard coat layer according to the above item (1), wherein the fluorine compound (B) has a siloxane bond in a molecule.

(3) The hard coat layer forming resin according to the above (1) or (2), wherein the content of the fluorine compound (B) is 0.3 to 3 parts by mass relative to 100 parts by mass of the (meth) acrylate monomer Composition.

(4) The silicone rubber composition according to any one of (1) to (3), wherein the content of the silicone grafted acrylic polymer (C) is 1 to 5 parts by mass relative to 100 parts by mass of the (meth) acrylate monomer Resin composition for forming a coat layer.

(5) A laminate having a substrate and a hard coat layer provided on the substrate,

Wherein the hard coat layer is formed using the resin composition for forming a hard coat layer according to any one of (1) to (4).

According to the present invention, it is possible to provide a resin composition for forming a hard coat layer which is excellent in antifouling property and slipperiness and capable of forming a hard coat layer excellent in durability.

1 is a cross-sectional view schematically showing an example of a laminate of the present invention.

[Resin composition for hard coat layer formation]

(Hereinafter, simply referred to as " composition of the present invention ") of the present invention is a polyfunctional urethane (meth) acrylate having three or more (meth) acryloyloxy groups in the molecule (Meth) acryloyloxy group, a fluorine compound (B) having a (meth) acryloyloxy group, a silicone having a (meth) acryloyloxy group having a glass transition temperature of 0 ° C or lower, Is a resin composition for forming a hard coat layer containing a graft acryl polymer (C), a photopolymerization initiator (D), and an organic solvent (E).

In the present invention, the (meth) acrylate monomer (A) containing the polyfunctional urethane (meth) acrylate (A1) and the fluorine compound (B) and the silicone grafted acrylic polymer By using the resin composition, antifouling property and slipperiness are improved, and a hard coat layer excellent in durability can be formed.

This is not clear in detail, but is estimated to be approximately as follows.

That is, by containing the fluorine compound (B), it is considered that fluorine is arranged (bleed) on the outermost surface of the hard coat layer after curing to exhibit excellent antifouling property and durability. Further, the silicon graft acrylic polymer C), it is believed that silicon is unevenly distributed in the vicinity of the surface (surface layer) of the hard coat layer after curing, thereby exhibiting excellent slipperiness.

This effect (in particular, resistance to shock) can be confirmed by using a comparative example described later, particularly Comparative Example 6 using a silicon graft polymer having a glass transition temperature higher than 0 deg. C, or a graft polymer having a (meth) acryloyl group at its terminal It is an unexpected effect because it is an effect that is not exhibited in Comparative Examples 7 and 8 using silicon which does not correspond to silicon.

The (meth) acrylate monomer (A), the fluorine compound (B), the silicone graft acrylic polymer (C), the photopolymerization initiator (D) and the organic solvent (E) will be described in detail below.

[(Meth) acrylate monomer (A)]

The (meth) acrylate monomer (A) contained in the composition of the present invention has a urethane bond and has 3 or more, preferably 4 or more, more preferably 6 to 10 (meth) acryloyl Is not particularly limited as long as it is a monomer component containing at least the polyfunctional urethane (meth) acrylate (A1) having a silyl group and a monooxy group.

(Meth) acryloyloxy group means acryloyloxy group (CH ₂ = CHCOO-) or methacryloyloxy group (CH ₂ = C (CH ₃ ) COO-) Methacrylate "means acrylate or methacrylate.

≪ Polyfunctional urethane (meth) acrylate (A1) >

Examples of the polyfunctional urethane (meth) acrylate (A1) include those having a urethane bond in the main chain and three or more (meth) acryloyloxy groups bonded to the terminal or side chain of the main chain.

Specifically, as the polyfunctional urethane (meth) acrylate (A1), a polyol compound (a1) having at least two hydroxyl groups in one molecule, a polyisocyanate compound (a2) Reactive organisms of hydroxy (meth) acrylate (a3) having an acryloyloxy group; A polyisocyanate compound (a2), and a hydroxy (meth) acrylate (a3) having a hydroxyl group and a (meth) acryloyloxy group in a molecule; And the like.

The reactive organisms of the polyol compound (a1), the polyisocyanate compound (a2) and the hydroxy (metha) acrylate (a3) react with the polyol compound (a1) and the polyisocyanate compound (a2) to form an isocyanate group Is a product obtained by reacting hydroxy (meth) acrylate (b3) after producing a so-called urethane prepolymer.

On the other hand, the reactive organisms of the polyisocyanate compound (a2) and the hydroxy (meth) acrylate (a3) are obtained by reacting the isocyanate group of the polyisocyanate compound (a2) with the hydroxyl group of the hydroxy (meth) Is the product obtained.

(Polyol compound (a1))

The polyol compound (a1) is not particularly limited as long as it has two or more hydroxyl groups.

Examples of the polyol compound include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl- 3-dimethyloheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol (PTMG), polycarbonate diol, lactone-based diol, etc. These may be used singly or in combination , Or two or more of them may be used in combination.

(Polyisocyanate compound (a2))

The polyisocyanate compound (a2) is not particularly limited as long as it has two or more isocyanate groups in the molecule.

Specific examples of the polyisocyanate compound include TDI (e.g., 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI) ), MDI (for example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triisobutylene diisocyanate Aromatic polyisocyanates such as phenylmethane triisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate and norbornane diisocyanate (NBDI); Trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), alicyclic such as dicyclohexylmethane diisocyanate (H ₁₂ MDI) (脂環Polyisocyanate; These carbodiimide-modified polyisocyanates; These isocyanurate-modified polyisocyanates; These may be used singly or two or more of them may be used in combination.

Of these, aliphatic polyisocyanates and alicyclic polyisocyanates are preferable, and HDI, IPDI, hydrogenated XDI and hydrogenated MDI are more preferable.

(Hydroxy (meth) acrylate (a3))

The hydroxy (meth) acrylate (a3) is not particularly limited as long as it is a hydroxy (meth) acrylate having a hydroxyl group and a (meth) acryloyloxy group. Examples thereof include 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and compounds wherein the skeleton is mono or polypentaerythritol. These compounds may be used singly, Two or more species may be used in combination.

Specific examples of the compound in which the skeleton is mono or polypentaerythritol include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ) Acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Of these, from the viewpoints of easiness to obtain, reactivity, compatibility and the like, 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate, Hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the like can be suitably used.

≪ Other (meth) acrylate monomers >

Examples of the (meth) acrylate monomer (A) other than the polyfunctional urethane (meth) acrylate (A1) include compounds having three or more (meth) acryloyloxy groups in one molecule Urethane (meth) acrylate (except for those corresponding to urethane (meth) acrylate (A1)).

Specific examples of the compound having three (meth) acryloyloxy groups in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri ) Acrylate, and the like.

Specific examples of the compound having four (meth) acryloyloxy groups per molecule include pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra ) Acrylate, and the like.

Specific examples of the compound having 5 or more (meth) acryloyloxy groups per molecule include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, tripentaerythritol penta (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (metha) acrylate, tripentaerythritol octa (metha) acrylate and the like.

In the present invention, the content of the polyfunctional urethane (meth) acrylate (A1) in the (meth) acrylate monomer (A) is preferably 10 (based on the total mass of the (meth) To 100% by mass, and more preferably from 20% to 80% by mass.

Incidentally, the term "100 mass%" means that only the polyfunctional urethane (meth) acrylate (A1) is used as the (meth) acrylate monomer (A).

[Fluorine compound (B)]

The fluorine compound (B) contained in the composition of the present invention is not particularly limited as long as it is a fluorine compound having a (meth) acryloyloxy group.

The content of the fluorine atom contained in the fluorine compound (B) is preferably from 10 to 50 mass% of one molecule of the fluorine compound (B) because the fluorine compound (B) has excellent optical characteristics, excellent initial adhesion, abrasion resistance and high hardness , More preferably from 30 to 50 mass%.

The (meth) acryloyloxy group of the fluorine compound (B) is preferably one to three from the viewpoint of excellent optical properties, excellent initial adhesion, abrasion resistance, and high hardness.

The structure of the fluorine compound (B) other than the fluorine atom and the (meth) acryloyloxy group is not particularly limited. For example, a hydrocarbon group which may have a hetero atom such as an oxygen atom, a nitrogen atom, Specific examples thereof include polymers such as hydrocarbon polymers and polyethers.

Among them, those having a siloxane bond in the molecule are preferred for the reason that the hard coat layer formed using the composition of the present invention has better slidability.

Specific examples of such a fluorine compound (B) include SUA1900L series (manufactured by Shin Nakamura Kagaku Co., Ltd.), UT-3971 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ), Megapack RS series and Defensa TF3000 series (manufactured by DIC Corporation), Wrightpro Coat AFC3000 (manufactured by Kyoeisha Kagaku Co., Ltd.), off-tool DAC-HP (Manufactured by DAIKIN INDUSTRIES, Ltd.), KSN5300 (manufactured by Shin-Etsu Chemical Co., Ltd.), KY-1203 (manufactured by Shin-Etsu Chemical), UVHC series (GE Toshiba Silicones Co., Ltd.) can be used.

Of these, KY-1203 (Shin-Etsu Chemical Co., Ltd.) having a siloxane bond in the molecule is preferably used.

In the present invention, the content of the fluorine compound (B) is preferably 0.3 to 3 parts by mass, more preferably 0.5 to 2 parts by mass, per 100 parts by mass of the (meth) acrylate monomer (A).

[Silicone Graft Acrylic Polymer (C)]

The silicone grafted acrylic polymer (C) contained in the composition of the present invention is a silicone grafted acrylic polymer having a glass transition temperature of 0 占 폚 or less and a (meth) acryloyloxy group.

Here, the glass transition temperature refers to the glass transition temperature (Tmg) determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC).

The "silicon grafted acrylic polymer" refers to a polymer obtained by grafting a silicon skeleton to a polymer chain of an acrylic polymer. Incidentally, the silicone macromer (A) represented by the following formula (1) described in Japanese Patent Application Laid-Open No. 2003-34784 does not correspond to an acrylic polymer and therefore, As shown in Comparative Example 7 using a compound represented by the following formula (1) in which R ¹ = methyl group, R ² = propylene chain, h = 2, j = 11 and R ³ = butyl group. The optical characteristic (haze) is lowered, and also the durability is deteriorated.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a bivalent aliphatic group having 1 to 6 carbon atoms which may contain an ether group, R ³ represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group, Or a hydroxyl group, h represents 0, 1 or 2, and j represents a number of 0 to 500).

The silicone grafted acrylic polymer (C) is not particularly limited as long as it is a silicone grafted acrylic polymer having a (meth) acryloyloxy group. The skeleton thereof may be a comb-like structure synthesized by copolymerization of a silicone macromonomer with a (meth) It is more preferable that the graft polymer is a comb type graft polymer composed of a silicon macromonomer in which the stem portion is a (meth) acrylic polymer and the branch portion accounts for 30 to 40 mass% of the total.

Examples of the silicone macromonomer include a monomer having a vinyl group at one end of a siloxane skeleton of polydimethylsiloxane, and specifically, a compound represented by the following formula can be cited.

Specific examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (Meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl acrylate, isooctyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl , Dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, hydrogenated products thereof, isobonyl (meth) acrylate, methoxyethyl (Meth) acrylate, ethoxy (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl acrylate, (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl And monofunctional (meth) acrylate monomers such as acryloylmorpholine.

The method of copolymerizing the silicone macromonomer and the (meth) acrylic monomer is not particularly limited. For example, the skeleton of the silicone grafted acrylic polymer (C) may be synthesized by radical polymerization using a photopolymerization initiator .

On the other hand, the silicone grafted acrylic polymer (C) may be a silicone grafted acrylic polymer having a hydroxyl group (Saima (registered trademark) US-270, Toagosei Co., Ltd.) as shown in Examples described later, ), And introducing an acryloyloxy group by reacting the hydroxyl group with an isocyanate group such as 2-isocyanatoethyl acrylate.

In the present invention, the content of the silicone grafted acrylic polymer (C) is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the (meth) acrylate monomer (A) , And more preferably 1 to 3 parts by mass.

[Photopolymerization initiator (D)]

The photopolymerization initiator (D) contained in the composition of the present invention is not particularly limited as long as it can polymerize the above-mentioned (meth) acrylate monomer (A) or the like by light.

Examples of the photopolymerization initiator (D) include alkylphenone-based photopolymerization initiators, acetophenones, benzophenones, Michler's benzoyl benzoate,? -Amyloxime esters, tetramethyl Thiuram monosulfide, benzoin, benzoin methyl ether, thioxanthones, propiophenones, benzyls and acylphosphine oxides. These may be used singly or in combination of two or more kinds. It may be used in combination.

Of these, an alkylphenon-based photopolymerization initiator is preferable from the viewpoints of light stability, high efficiency of light cleavage, surface hardening property, compatibility, low volatility and low odor.

Specific examples of the alkylphenon-based photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl- 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.

In the present invention, the content of the photopolymerization initiator (D) is preferably 1 to 20 parts by mass, more preferably 5 to 10 parts by mass, per 100 parts by mass of the (meth) acrylate monomer (A).

[Organic solvent (E)]

The organic solvent (E) contained in the composition of the present invention is not particularly limited, and specific examples thereof include alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, dodecylbenzene and methylnaphthalene; Halides such as methylene chloride, chloroform, ethylene chloride and chlorobenzene; Ethers such as THF, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether and dioctyl ether; Esters such as ethyl acetate, butyl acetate, butyl acrylate, methyl methacrylate, hexamethylene diacrylate and trimethylolpropane triacrylate; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Glycol ethers such as propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, propylcellosolve and butyl cellosolve; These may be used singly or two or more of them may be used in combination.

[Other additives]

The composition of the present invention may be added to the composition of the present invention so long as the object of the present invention is not impaired, for example, a filler, an antioxidant, an antistatic agent, a flame retardant, , Dyes, pigments, and the like.

[Manufacturing method]

The method for producing the composition of the present invention is not particularly limited and includes, for example, a method in which the above-mentioned essential components and optional components are added to a reaction vessel and the mixture is thoroughly mixed using a stirrer such as a mixing mixer under reduced pressure.

[Laminate]

The laminate of the present invention is a laminate having a base material and a hard coat layer provided on the base material, and the hard coat layer is a laminate formed using the composition of the present invention.

Here, the substrate is not particularly limited, and for example, plastic, rubber, glass, metal, ceramics and the like can be used as the material. Among them, plastic is preferably used.

The plastic may be a thermosetting resin or a thermoplastic resin, and specific examples thereof include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate Adhesive resin such as a resin, an ABS resin, a polyester resin, and a polyamide resin.

Next, the laminate of the present invention will be described with reference to the accompanying drawings.

1 is a cross-sectional view schematically showing a cross section of an example of the laminate of the present invention.

1, the layered product 100 has a hard coat layer 102 and a base material 104. The hard coat layer 102 is made of,

Here, the thickness of the hard coat layer 102 is not particularly limited, but is preferably 1 to 20 占 퐉, more preferably 1 to 10 占 퐉.

The method for producing the layered product of the present invention is not particularly limited, and can be produced, for example, by applying the composition of the present invention described above on the substrate and curing it after drying.

Here, the method of application is not particularly limited, and known coating methods such as brush coating, bleeding coating, dip coating, spray coating, spin coating and the like can be adopted.

The method of drying is not particularly limited, and in the case of using a plastic substrate as the substrate, for example, it is preferable that the polycarbonate substrate is dried at 70 DEG C for 3 minutes and the PMMA substrate at 70 DEG C for 10 minutes Do.

Furthermore, the method of curing is not particularly limited, and for example, a curing method using ultraviolet rays can be mentioned. When the composition of the present invention is cured by irradiation with ultraviolet rays, the dose of ultraviolet rays used when curing the composition of the present invention is preferably 500 to 3,000 mJ / cm ² from the viewpoint of quick curability and workability.

Example

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.

<Silicon Graft Acrylic Polymer: Synthesized (1)>

, 3.3 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko K.K.), 2 g of methyl ethyl ketone 3.7 (trade name, manufactured by Showa Denko KK) g, and a tin catalyst were added, and the mixture was reacted at 50 DEG C for 6 hours.

The silicon grafted acrylic polymer (1) having an acryloyloxy group having a solid content of 30% was confirmed by observing the disappearance of the peak of NCO derived from 2-isocyanatoethyl acrylate by Fourier transform infrared spectroscopy (FT-IR) &Lt; / RTI &gt;

Incidentally, the obtained glass transition temperature (Tg) of the silicone grafted acrylic polymer (1) was -50 占 폚.

<Silicon Graft Acrylic Polymer: Synthetic (2)>

100 g of a hydroxyl group-containing silicone grafted acrylic polymer (Regetta GS1015, manufactured by Toagosei Co., Ltd.), 13.6 g of 2-isocyanatoethyl acrylate (Carens AOI, Showa Denko Kosei), 81.7 g of methyl ethyl ketone, And reacted at 50 DEG C for 6 hours.

A silicon grafted acrylic polymer (2) having an acryloyloxy group having a solid content of 30% was confirmed by the Fourier transform infrared spectroscopy (FT-IR) that the peak of NCO derived from 2-isocyanatoethyl acrylate disappeared. .

Incidentally, the glass transition temperature (Tg) of the obtained silicone grafted acrylic polymer (2) was 13 占 폚.

[Examples 1 to 6 and Comparative Examples 1 to 8]

Each of the components shown in the following Table 1 was mixed in an amount (unit: parts by mass) shown in the same table using a stirrer to obtain resin compositions of the respective examples (hereinafter, simply referred to as "composition").

〔evaluation〕

Each obtained composition (solid content: 60% by mass) was applied on one side of a PET film (Lamier U46, manufactured by Toray Industries, Inc., thickness: 125 탆) using Bar Coater No. 5.

Subsequently, after drying at 80 ° C for 1 minute, UV irradiation was performed using a GS UV SYSTEM manufactured by Nippon Battery Co., Ltd. so that the peak intensity was 300 mW / cm ² and the accumulated light quantity was 300 mJ / cm ² A hard coat layer (thickness: 5 m) was formed, and a sample for evaluation was prepared.

Using these samples for evaluation, the respective characteristics were evaluated by the following methods. The results are shown in Table 1 below.

&Lt; Initial adhesion &

100 sheets (1 x 10 mm) of 1 mm checkerboard were made on the hard coat layer of the evaluation sample thus prepared, the cellophane adhesive tape (width 18 mm) was completely adhered on the checkerboard eye, and one end of the tape was immediately While holding it at right angles, it was instantly peeled off, and the number of checkerboards left without peeling completely was examined. Incidentally, in the following Table 1, &quot; 100/100 &quot; indicates that all checkered eyes are not peeled off and &quot; 0/100 &quot; indicates that all checkered eyes are peeled off.

&Lt; Adhesion resistance against wet heat &

The evaluation sample thus prepared was allowed to stand under the environment of 85 캜 and 85% RH for 500 hours, and then evaluated in the same manner as the initial adhesion.

<Transparency (haze)>

(HM150, manufactured by Murakami Shikisai Jujutsu Kagaku Koen) under the condition that the sample for evaluation produced in this manner was cut into a square (30 mm x 30 mm) according to JIS K7361-1: 1997 And the haze ratio was measured.

<Slipperiness>

The surface of the hard coat layer of the evaluation sample thus prepared was slid using a Ben Coat.

As a result, it was evaluated as &quot; A &quot;, the thing which slipped extremely well was evaluated as &quot; B &quot;

<Antifouling property>

The surface of the hard coat layer of the evaluation sample thus prepared was drawn with a planetary pen (made by Mackie, ZEBRA CO., LTD.) And the number of times of wiping until wiping with a Ben Coat was measured.

<Tolerance>

(Exterior)

The hard coat layer of the evaluation sample thus prepared was subjected to a load of 1 kg / cm ² , a stroke of 3 cm, and a 1000 reciprocating motion using a steel wool of BONSTAR # 0000 (manufactured by NIHON STEEL WOOL Co., Ltd.) , And the presence or absence of scratches in the hard coat layer was visually confirmed.

(Magic wipe)

The hard coat layer of the evaluation sample thus prepared was rubbed and reciprocated 1,000 times under a load of 1 kg / cm ² , a stroke of 3 cm, and 1000 times using a steel wool of BONSTAR # 0000 (Nippon Steel Wool Co., Ltd.).

Thereafter, a line was drawn on the surface of the hard coat layer with an oil-based pen (Mack, Zebra) and the number of times of wiping until wiping with a Ben Coat was measured. In addition, in the following first table, it is evaluated as "x" about thing which we can not wipe at all even if we wipe it several times (we do not support it).

The components shown in the first table are as shown below.

(Meth) acrylate: dipentaerythritol hexaacrylate (Miramer M600, manufactured by Miwon)

(Meth) acrylate: HDI polyfunctional urethane (meth) acrylate (NX103-211, (meth) acryloyloxy group: 12, manufactured by Asia Industry Co., Ltd.)

(Meth) acrylate: IPDI polyfunctional urethane (meth) acrylate (KRM8200AE, (meth) acryloyloxy group: 6 or more, manufactured by Daicel-Cytec Company Ltd.)

(Meth) acrylate: H12MDI type polyfunctional urethane (meth) acrylate (NX103-112VE, (meth) acryloyloxy group: 6,

· Fluorine compound: Off-tool DAC-HP ((meth) acryloyloxy group: present, siloxane bond: none, Daikinsha)

· Fluorine compound: KY-1203 ((meth) acryloyloxy group: present, siloxane bond: available, Shin-Etsu Chemical)

Fluorine compound: Megapack F-555 ((meth) acryloyloxy group: none, siloxane bond: none,

· Silicon Graft Acrylic Monomer: Synthesis (1)

Silicone graft acrylic monomer: Cymac US270 ((meth) acryloyloxy group: available from Toagosei Co., Ltd.)

· Silicon Graft Acrylic Monomers: Synthetic (2)

Silicone compound: Silaplane FM-0711 (one end methacryloyl group, manufactured by CHISSO CORPORATION)

· Silicone compound: X-22-1602 (both terminal acryloyl groups, Shin-Etsu Chemical Co., Ltd.)

Photopolymerization initiator: 1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)

· Organic solvent: methyl isobutyl ketone

From the results shown in Table 1, it was found that Comparative Example 1, which was prepared without blending the fluorine compound (B), was inferior in antifouling property and anti-image resistance.

Further, it was found that Comparative Example 2 prepared without blending the silicone graft acrylic polymer (C) had poor slidability.

In addition, it was found that all of Comparative Examples 3 and 4 in which a fluorine compound having no (meth) acryloyl group or a silicone grafted acrylic polymer having no (meth) acryloyl group were blended had poor resistance.

Further, it was found that Comparative Example 5, which was prepared without mixing the polyfunctional urethane (meth) acrylate (A1) as the (meth) acrylate monomer (A), was poor in anti-wet heat adhesion.

In addition, it was found that Comparative Example 6 in which a silicone graft acrylic polymer having a Tg higher than 0 ° C was blended was poor in durability.

It was also found that Comparative Examples 7 and 8 in which a silicone compound was blended in place of the silicone graft acrylic polymer (C) all had poor optical characteristics (haze) and resistance to scratches.

On the other hand, a polyfunctional urethane (meth) acrylate (A1) having three or more (meth) acryloyloxy groups per molecule, a fluorine compound (B) having a (meth) acryloyloxy group, Examples 1 to 6, in which the silicone grafted acrylic polymer (C) having a temperature of 0 占 폚 or less and a (meth) acryloyloxy group was blended, all exhibited excellent antifouling properties and slipperiness, Can be formed.

In particular, it was found that Examples 2 to 6 using the fluorine compound (B) having a siloxane bond in the molecule had better slidability than Example 1.

From the comparison of Example 2 and Example 6, it was found that the content of the silicone grafted acrylic polymer (C) having a (meth) acryloyloxy group was 1 to 5 parts by mass based on 100 parts by mass of the (meth) acrylate monomer It was found that the antifouling property and the shrinkage resistance were better when it was in the mass part.

100:
102: hard coat layer
104: substrate

Claims (5)

(Meth) acrylate monomer (A) comprising a polyfunctional urethane (meth) acrylate (A1) having at least three (meth) acryloyloxy groups per molecule,
A fluorine compound (B) having a (meth) acryloyloxy group,
(C) having a glass transition temperature of 0 占 폚 or less and having a (meth) acryloyloxy group,
A photopolymerization initiator (D)
A resin composition for forming a hard coat layer containing an organic solvent (E). The method according to claim 1,
The resin composition for forming a hard coat layer, wherein the fluorine compound (B) has a siloxane bond in a molecule. 3. The method according to claim 1 or 2,
Wherein the content of the fluorine compound (B) is 0.3 to 3 parts by mass based on 100 parts by mass of the (meth) acrylate monomer (A). 4. The method according to any one of claims 1 to 3,
Wherein the content of the silicone grafted acrylic polymer (C) is 1 to 5 parts by mass based on 100 parts by mass of the (meth) acrylate monomer (A). A laminate having a base material and a hard coat layer provided on the base material,
Wherein the hard coat layer is formed by using the resin composition for forming a hard coat layer according to any one of claims 1 to 4.

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