KR101922261B1 - Ultraviolet absorbing hardcoated films - Google Patents

Abstract

(assignment)
An ultraviolet ray absorbing hard coat film is provided which has a specific structure of an ultraviolet absorber added to a hard coat layer to avoid deterioration of curl and sufficient weather resistance.
(Solution)
Wherein the ultraviolet ray absorbing hard coat layer comprises (A) 100 parts by mass of an ultraviolet ray hardening type resin, (B) 100 parts by mass of ultraviolet ray absorbing hard coat layer represented by the general formula (1) 1 to 20 parts by mass of an ultraviolet absorber, 0.1 to 10 parts by mass of a photopolymerization initiator (C), and 0.001 to 20 parts by mass of a surface modifier (D).
[Chemical Formula 1]

Description

ULTRAVIOLET ABSORBING HARDCOATED FILMS [0002]

The present invention relates to an ultraviolet absorbent hard coat film having an ultraviolet absorbing hard coat layer.

[0002] In recent years, in the use of decorative materials such as automobiles and construction materials, film products have been remarkably advanced in terms of processability and price, and light weight. These film products are attracting attention for their functionality in that various functions can be imparted to the base film as a base.

In these film products, a transparent base film such as polyethylene terephthalate (PET) is generally used. However, these base films have problems such as poor physical resistance such as surface hardness, scratches caused by hard contact, . Thus, a method of laminating a hard coat layer on a transparent base film to impart physical resistance such as surface hardness to the transparent base film has been conventionally practiced (Patent Document 1).

On the other hand, these film products have many opportunities to be used in places exposed to sunlight (especially ultraviolet rays). However, since the transparent base film and the hard coat layer used in these film products are deteriorated by exposure to sunlight, the adhesion between the transparent base film and the hard coat layer is lowered, and the function imparted to the hard coat layer is lost There was a problem. In order to impart resistance to sunlight, a weather-resistant polyester film laminated with a weather-resistant coat layer on the surface of PET has been proposed (Patent Document 2). Further, in the hard coat film used for an electronic display or the like, a triazine-based ultraviolet absorber is added to the hard coat layer to prevent deterioration due to ultraviolet rays (Patent Document 3). In addition, in the use of the construction material, the addition of a triazine-based ultraviolet absorber to the hard coat layer prevents the deterioration by ultraviolet rays (Patent Document 4).

Japanese Patent Publication No. 2003-184329 Japanese Patent Application Laid-Open No. 2009-226745 Japanese Patent Application Laid-Open No. 2009-294329 Japanese Laid-Open Patent Publication No. 2012-76354

In Patent Document 1, a hard coat layer is laminated on a transparent base film to solve the problem of physical resistance such as surface hardness. However, the problem of deterioration due to sunlight has not been solved.

On the other hand, Patent Document 2 improves the problem of deterioration due to sunlight, but there is no description of physical resistance, so that this problem can not be solved. Patent Document 3 is directed to an electronic display in particular, which solves the problem of deterioration due to sunlight, but the conventional triazine-based ultraviolet absorber is not necessarily satisfactory in terms of performance. Therefore, in order to obtain sufficient weatherability, the added amount of the ultraviolet absorber becomes excessive, and the ultraviolet absorber bleeds. If the thickness of the hard coat layer is excessively increased in order to secure the total amount of the ultraviolet absorber, the hardening and shrinkage of the ultraviolet curable resin as the material of the hard coat layer becomes large, so that the film having the hard coat layer is curled, There is a problem that processability is deteriorated. Patent Document 4 selects a suitable ultraviolet absorber for weatherability, but a primer layer is formed between the base film and the hard coat layer in order to maintain the adhesion between the base film and the hard coat layer, and the cost increases with an increase in the number of processing steps.

It is therefore an object of the present invention to provide a hard coat film obtained by laminating a hard coat layer directly on a transparent base film and also to a hard coat layer coating liquid which has a high light absorbing ability in the ultraviolet region Absorbing hard coat film having a sufficient weather resistance while avoiding deterioration of curling property by realizing a reduction in the addition amount of the ultraviolet absorber and a reduction in the thickness of the hard coat layer.

That is, the ultraviolet absorbing hard coat film of the present invention is as follows.

(1) An ultraviolet absorbing hard coat film having an ultraviolet ray absorbing hard coat layer formed on one side of a transparent base film, wherein the ultraviolet ray absorbing hard coat layer comprises (A) 100 parts by mass of an ultraviolet ray hardening resin, (B) 1 to 20 parts by mass of an ultraviolet absorber represented by the following general formula (1) for absorbing light having a wavelength of 5 to 20 nm, (C) 0.1 to 10 parts by mass of a photopolymerization initiator, and (D) 0.001 to 20 parts by mass of Wherein the hard coat layer coating liquid is a layer having a thickness of 0.5 to 10 mu m which is ultraviolet cured.

[Chemical Formula 1]

(2) The ultraviolet absorbing hard coat layer coating liquid is obtained by radical copolymerizing a compound (e-1) having a quaternary ammonium salt group represented by the following general formula (2) and a compound (e-2) having one ethylenic unsaturated group (E) a quaternary ammonium salt-based copolymer, and (E) a quaternary ammonium salt-based copolymer.

CH ₂ = C (R ¹ ) COZ (CH ₂ ) _k N ⁺ (R ² ) ₃ · X ^- (2)

(Wherein, R ¹ is H or CH _3, R ² are each independently a carbon number of from 1 to 4 or a hydrocarbon group, Z is an oxygen atom or NH group, k is an integer of 1 ~ 10, X ^- is a monovalent anion Lt; / RTI &

(3) The ultraviolet absorbing hard coat film according to (1) or (2), wherein a low refractive index layer having a lower refractive index than that of the ultraviolet absorbing hard coat layer is formed on the ultraviolet absorbing hard coat layer.

(4) The ultraviolet absorbing hard-coated film according to any one of (1) to (3), wherein an adhesive layer is formed on the other surface of the transparent base film.

In the present invention, " xx to xx " indicating the numerical range means a numerical value including the lower limit (xx) and the upper limit (xx). Therefore, when expressed accurately, it becomes "xx or more xx or less".

According to the present invention, it is possible to impart physical resistance and weather resistance (ultraviolet ray absorbing property) by laminating a hard coat layer containing an ultraviolet absorber having a high light absorbing ability in the ultraviolet ray region on a transparent base film, It is possible to provide an ultraviolet absorptive hard coat film which can withstand long-term use without deteriorating the adhesiveness between the transparent substrate film and the hard coat layer even in an environment exposed to the environment.

As the ultraviolet absorber, a hydroxyphenyltriazine type ultraviolet absorber having a specific structure represented by the general formula (1) is used. Since the ultraviolet absorber has a high light absorption ability with respect to light of a short wavelength side (ultraviolet ray region), ultraviolet light can be efficiently absorbed even by adding a small amount. Therefore, the addition amount of the ultraviolet absorber can be reduced, and the film thickness of the hard coat layer can also be reduced. This makes it possible to obtain a hard coat film having a good workability and weather resistance while preventing deterioration of curling or the like. Further, in the present invention, since the hard coat layer is directly laminated on the transparent base film, a primer layer for enhancing the adhesion of the both is unnecessary, and an increase in the number of processing steps can be prevented.

The ultraviolet absorbing hard coat film of the present invention is applied to automobiles and building materials, and at least one surface of the transparent substrate film is provided with an ultraviolet absorbing hard coat layer.

≪ Transparent substrate film &

The transparent base film used in the ultraviolet absorbing hard coat film is not particularly limited as long as it has transparency. Examples of the material for forming such a transparent base film include polyester such as polyethylene terephthalate (PET), polyarylate, triacetyl cellulose (TAC), polyether sulfone and the like. Among them, a polyester film, particularly a polyethylene terephthalate film, is preferable from the viewpoint of easiness of molding.

The thickness of the transparent base film is not particularly limited, but is generally 25 to 400 占 퐉, preferably 50 to 200 占 퐉. When the thickness of the transparent base film is thinner than 25 占 퐉 or thicker than 400 占 퐉, handling properties during production and use of the ultraviolet absorbing hard coat film are lowered. The transparent base film may contain various additives. Such additives include, for example, ultraviolet absorbers, antistatic agents, stabilizers, plasticizers, lubricants and flame retardants.

≪ Ultraviolet ray absorbing hard coat layer >

The ultraviolet absorbing hard coat layer is composed of (A) an ultraviolet curable resin, (B) a hydroxyphenyltriazine based ultraviolet absorber represented by the general formula (1), (C) a photopolymerization initiator, and (D) The absorbent hard coat layer is a layer formed by ultraviolet curing the coating liquid. The ultraviolet ray absorbing hard coat layer is formed by directly applying the ultraviolet ray absorbing hard coat layer coating liquid containing each of the above components onto a transparent base film and then curing by irradiating ultraviolet rays.

The thickness of the ultraviolet ray absorbing hard coat layer is 0.5 to 10 mu m, preferably 1 to 6 mu m. If the thickness of the ultraviolet absorbing hard coat layer is less than 0.5 탆, the content of the ultraviolet absorbing agent in the ultraviolet absorbing hard coat layer is also limited. As a result, the amount of the ultraviolet absorbing agent in the ultraviolet absorbing hard coat layer formed becomes relatively small, A sufficient ultraviolet absorbing effect can not be obtained. On the other hand, if it exceeds 10 탆, the curl in curing of the ultraviolet ray absorbing hard coat layer can not be reduced.

The ultraviolet ray absorbing hard coat layer may contain an antistatic agent for the purpose of preventing adhesion of foreign matter such as dust generated during processing or in actual use. Examples of such an antistatic agent include (E) a quaternary ammonium salt-based copolymer, and the like.

The refractive index of the ultraviolet ray-absorbing hard coat layer may be about 1.45 to 1.70, and the ultraviolet ray absorbing hard coat layer may contain a refractive index adjusting agent such as a metal oxide as needed in order to adjust the refractive index of the ultraviolet ray absorbing hard coat layer . The kind of the metal oxide used for adjusting the refractive index is not particularly limited as long as it is added to the ultraviolet ray absorbing hard coat layer coating liquid for the purpose of raising the refractive index. Examples of such metal oxides include zirconium oxide, zinc oxide, titanium oxide, cerium oxide, tin oxide, aluminum oxide, silane oxide, and indium tin oxide.

The method of forming the ultraviolet ray absorbing hard coat layer on the transparent base film is not particularly limited as long as the ultraviolet ray absorbing hard coat layer coating liquid is applied directly by the wet coating method and then irradiated with ultraviolet rays, For example, conventionally known coating methods such as a gravure coating method, a spin coating method and a die coating method may be employed.

≪ (A) UV curable resin >

The ultraviolet curing type resin forming the ultraviolet ray absorbing hard coat layer is not particularly limited as long as it is a known resin which is generally used conventionally in this kind of hard coat film and causes a curing reaction by irradiation with ultraviolet rays. Examples of such a resin include monofunctional (meth) acrylate, polyfunctional (meth) acrylate, epoxy resin, urethane resin, silicone resin and the like. In the present specification, (meth) acrylate means a generic term including both acrylate and methacrylate. The same applies also to the (meth) acrylic acid, (meth) acrylic, and (meth) acryloyl groups.

≪ (B) Ultraviolet absorber >

The ultraviolet absorber absorbs light having a wavelength of 300 to 350 nm and is obtained by reacting [2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) Bis (4-phenylphenyl) -1,3,5-triazine].

(2)

The content of the ultraviolet absorber (B) is preferably from 1 to 20 parts by mass, more preferably from 5 to 20 parts by mass, per 100 parts by mass of the ultraviolet curable resin (A). When the content of the ultraviolet absorber is more than 20 parts by mass, the ultraviolet ray hardening property of the ultraviolet absorbing hard coat layer coating liquid tends to be lowered, and the visible light transmittance of the ultraviolet absorbing hard coat film may be lowered. On the other hand, if it is less than 1 part by mass, the ultraviolet ray absorbing property of the ultraviolet absorbing hard coat film can not be sufficiently exhibited.

When the ultraviolet absorber contains a predetermined amount of the ultraviolet absorber represented by the above general formula (1) that absorbs light having a wavelength of 300 to 350 nm, an ultraviolet absorber capable of absorbing light of other wavelengths can be used. In addition, stabilizers such as inorganic ultraviolet absorbers, hindered amine light stabilizers (HALS) and antioxidants may be used in combination.

As the inorganic ultraviolet absorber, conventionally known ones can be used. For example, cerium oxide, zinc oxide, titanium oxide, and the like.

Conventionally known hindered amine light stabilizers may be used. For example, the reaction product of decane diacid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester 1,1-dimethylethyl hydroperoxide with octane, bis 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate with methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, a mixture of 2,4- Bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4- yl) amino] -6- (2-hydroxyethylamine) 3,5-triazine), and the like.

<(C) Photopolymerization initiator>

The photopolymerization initiator contained in the ultraviolet absorbing hard coat layer coating liquid is not particularly limited as long as it can initiate the polymerization reaction by ultraviolet rays. It is preferable to absorb light having a wavelength of 220 to 400 nm, More preferably in the range of 300 to 350 nm. When the wavelength of light used for curing exceeds 400 nm, there is a possibility that the manifestation of the photopolymerization initiating ability is insufficient. When the wavelength of light is less than 220 nm, ozone is liable to be generated, which is not preferable. When the maximum absorption wavelength of the photopolymerization initiator is in the range of 300 to 350 nm, ultraviolet light is absorbed in the ultraviolet absorber, and there is a fear that the photopolymerization initiating ability of the photopolymerization initiator is not sufficiently manifested.

Examples of the photopolymerization initiator that absorbs light having a wavelength of 220 to 400 nm include 1-hydroxy-cyclohexyl-phenyl-ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2- -1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one. Among these, 1 -hydroxy-cyclohexyl-phenyl-ketone is preferred.

The content of the photopolymerization initiator (C) is 0.1 to 10 parts by mass based on 100 parts by mass of the ultraviolet curable resin (A). When the content of the photopolymerization initiator is less than 0.1 part by mass, the polymerization hardening of the ultraviolet absorbing hard coat layer becomes insufficient. When the content of the photopolymerization initiator exceeds 10 parts by mass, the photopolymerization initiator remains in the ultraviolet absorbing hard coat layer, There is a possibility that the visible light transmittance of the absorbent hard coat film is lowered.

<(D) Surface Conditioner>

The surface modifier is used for the purpose of imparting a sliding property to the surface of the ultraviolet ray absorbing hard coat layer. Examples of the surface modifier include, but are not limited to, a polyether-modified polydimethylsiloxane having an acryl group, a polyether-modified dimethylsiloxane, a polyester-modified dimethylsiloxane having an acryl group, a polyether-modified polydimethylsiloxane, Dimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, and the like. Among them, a polyether-modified polydimethylsiloxane having an acryl group is preferable from the viewpoint of slidability.

(D) the content of the surface control agent is 0.001 to 20 parts by mass based on 100 parts by mass of the ultraviolet-curable resin (A). When the content of the surface modifier is less than 0.001 parts by mass, the slidability of the surface can not be sufficiently imparted and the physical resistance is lowered. When the content of the surface control agent is 20 parts by mass or more, when the ultraviolet ray absorbing hard coat layer coating liquid is applied to the transparent base film, the transparent base film repels the ultraviolet ray absorbing hard coat layer coating liquid, It can not be uniformly formed.

<(E) Quaternary ammonium salt-based copolymer>

(E) quaternary ammonium salt-based copolymer may be used in order to impart antistatic ability to the ultraviolet ray-absorbing hard coat layer. The quaternary ammonium salt-based copolymer is composed of a compound (e-1) having a quaternary ammonium salt group represented by the following general formula (2) and a compound (e-2) having one ethylenic unsaturated group.

CH ₂ = C (R ¹ ) COZ (CH ₂ ) _k N ⁺ (R ² ) ₃ · X ^- (2)

(Wherein, R ¹ is H or CH _3, R ² are each independently a carbon number of from 1 to 4 or a hydrocarbon group, Z is an oxygen atom or NH group, k is an integer of 1 ~ 10, X ^- is a monovalent anion Lt; / RTI &

The amount of the (E) quaternary ammonium salt-based copolymer is preferably 1 to 20 parts by weight, more preferably 3 to 10 parts by weight per 100 parts by weight of (A) the ultraviolet curable resin. If the amount is less than 1 part by weight, sufficient antistatic properties can not be obtained. If the amount is more than 20 parts by weight, scratch resistance of the formed ultraviolet absorbent hard coat layer is lowered.

<Compound (e-1) having quaternary ammonium group>

The compound (e-1) having a quaternary ammonium group is not particularly limited as long as it is a (meth) acrylate represented by the above-mentioned formula (2) and containing a quaternary ammonium salt in its structure. Examples of such a compound include (meth) acrylates and (meth) acrylamides having an amino group.

The hydrocarbon group having 1 to 4 carbon atoms represented by R ² in the general formula (2) may be a substituted or unsubstituted hydrocarbon group. When the number of carbon atoms of R ² is more than 5, hydrophobicity of the produced (E) quaternary ammonium salt copolymer becomes high. As a result, hygroscopicity of the ultraviolet absorbent hard coat layer containing the quaternary ammonium salt copolymer (E) A good antistatic performance may not be obtained.

R ² in the general formula (2) is preferably an unsubstituted hydrocarbon group, more preferably an unsubstituted alkyl group. As the unsubstituted alkyl group, both branched and unbranched alkyl groups can be used. The unsubstituted alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and it is preferable that the alkyl group is a methyl group, an ethyl group, or the like since it is easy to obtain.

Examples of the (meth) acrylates having an amino group for forming the compound (e-1) in which Z in the general formula (2) has a quaternary ammonium salt group of an oxygen atom include dimethylaminoethyl (meth) acrylate chloride Methyl quaternary salt, and dimethylaminopropyl (meth) acrylate methyl chloride quaternary salt.

Examples of the (meth) acrylamides having an amino group for forming the compound (e-1) having a quaternary ammonium group in which Z in the general formula (2) is an NH group include dimethylaminoethyl (meth) acrylamide methyl chloride Quaternary salt, dimethylaminopropyl (meth) acrylamide, methyl chloride quaternary salt, and the like.

<Compound (e-2) having one ethylenically unsaturated group>

The compound (e-2) having one ethylenic unsaturated group is not particularly limited as long as it is a monomer containing one ethylenic unsaturated group. As such compounds, there may be mentioned, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate. The compound (e-2) may be used in combination of two or more.

The (E) quaternary ammonium salt-based copolymer can be obtained by radical copolymerization of the compounds (e-1) and (e-2). The amount of each of the compounds (e-1) and (e-2) is preferably 30 to 70 parts by mass from the viewpoint of the antistatic property of the compound (e-1) in 100 parts by mass of the total amount of the quaternary ammonium salt- , And the compound (e-2) is preferably 70 to 30 parts by mass for the purpose of controlling the antistatic property and the solubility of the resulting (E) quaternary ammonium salt-based copolymer.

<Low Refractive Index Layer>

The ultraviolet absorbing hard coat film of the present invention preferably has a low refractive index layer on its surface in order to prevent reflection or non-reflection of external light such as sunlight or fluorescent lamp. The low refractive index layer is a layer having a refractive index lower than that of the ultraviolet ray absorbing hard coat layer and is formed on the ultraviolet ray absorbing hard coat layer (surface side).

As a material for forming the low refractive index layer, a known material which forms a low refractive index layer in this kind of hard coat film can be used if the refractive index is in the range of 1.20 to 1.50 and lower than the refractive index of the ultraviolet absorbing hard coat layer . For example, it is possible to use a binder resin in which low refractive index inorganic fine particles such as hollow silica or magnesium fluoride which lowers the refractive index are added, or a fluororesin. As the binder resin, the same (meth) acrylate as the ultraviolet curable resin (A) forming the ultraviolet absorbing hard coat layer can be used. The low refractive index layer can be formed by applying and curing the low refractive index layer coating liquid onto the ultraviolet ray absorbing hard coat layer in the same manner as the ultraviolet ray absorbing hard coat layer. The low refractive index layer may have other functions as long as it does not impair its function, and one or two or more functions such as antistatic property, antifouling property, slip property and ultraviolet ray absorption may be imparted by adding an additive or the like have.

<Adhesive Layer>

The ultraviolet-absorbing hard-coat film of the present invention preferably has an adhesive layer on the surface opposite to the surface on which the ultraviolet-absorbing hard-coat layer is laminated so as to give an adhesive function to the object to be laminated. The adhesive layer is formed on the other surface of the transparent base film. The material for forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, silicone pressure-sensitive adhesives, and urethane pressure-sensitive adhesives, but acrylic pressure-sensitive adhesives are preferable from the viewpoint of adhesiveness.

The method of forming the pressure-sensitive adhesive layer is not particularly limited, but a conventionally known method of obtaining a cured film by heat curing, ultraviolet curing, electron beam curing or the like after forming a coating film by a wet coating method can be used. The adhesive layer may have other functions as long as it does not impair the function. For example, a function of blocking light in a specific wavelength range, improving contrast, correcting color tone, etc., Or two or more of them may be imparted.

[Example]

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.

(Preparation of Quaternary Ammonium Salt-Based Copolymer)

(E) quaternary ammonium salt copolymers (E1 to E4) were obtained by copolymerizing (e-1) and (e-2) with the composition shown in Table 1 below. The specific materials shown in Table 1 are as follows.

? 1: dimethylaminoethyl acrylate methyl chloride

R ¹ = CH ₃ , R ² = CH ₃ , Z = O, k = 2, X ^- = Cl ^-

? 2: dimethylaminopropylacrylamide methyl chloride

(1): R ¹ = H, R ² = CH ₃ , Z = NH group, k = 3, X ^- = Cl ^-

? 1: butyl methacrylate

? 2: benzyl methacrylate

(Preparation of Ultraviolet Absorptive Hard Coat Layer Coating Liquid)

The ultraviolet absorbing hard coat layer coating liquid comprises (A) an ultraviolet curable resin, (B) an ultraviolet absorber of the general formula (1), (C) a photopolymerization initiator, (D) Based copolymer were mixed as shown in the following Table 2, and isopropyl alcohol (IPA) was mixed so as to have a solid content concentration of 40% by mass to obtain an ultraviolet ray absorbing hard coat layer coating liquid. The specific materials shown in Table 2 are as follows.

A1: DPHA (dipentaerythritol hexaacrylate)

B1: BASF Japan Co., Ltd. Product name: Tinuvin 479 [2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) 3,5-triazine]

B2: bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester 1,1-dimethylethyl hydrobromide (manufactured by BASF Japan Co., Reaction product of roper oxide and octane]

C1: BASF Japan Co., Ltd. Product name: Irgacure 184

C2: BASF Japan Co., Ltd. Product name: Irgacure 907

D1: Polyether-modified polydimethylsiloxane having an acrylic group (BYK3500, product of Big Chem Japan Co., Ltd.)

D2: Polyether-modified polydimethylsiloxane (trade name: BYK3510, manufactured by Big Chem Japan Co., Ltd.)

(Preparation of low refractive index layer coating liquid 粒 1)

60 parts by mass of hollow silica fine particles having a particle diameter of 60 nm, 40 parts by mass of dipentaerythritol hexaacrylate (DPHA), and 10 parts by mass of a photopolymerization initiator [product name: Irgacure 907 manufactured by BASF Japan Co., Ltd. ] Was obtained by mixing isopropyl alcohol (IPA) so as to have a solid content concentration of 5 mass%.

(Preparation of adhesive layer coating liquid δ1)

94.6 parts by mass of n-butyl acrylate, 4.4 parts by mass of acrylic acid, 1 part by mass of 2-hydroxyethyl methacrylate, 0.4 parts by mass of azobisisobutyronitrile, 90 parts by mass of ethyl acetate and 60 parts by mass of toluene were mixed, Under the atmosphere, the mixture was heated to 65 DEG C and polymerization reaction was carried out for 10 hours to prepare an acrylic resin composition. One part by mass of Colonate L (polyisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) and 99 parts by mass of ethyl acetate were added to 99 parts by mass of the acrylic resin composition so that the solid content concentration of the adhesive resin composition was 20 mass% % Of the pressure-sensitive adhesive layer coating solution? 1.

(Production of Ultraviolet Absorbent Hard Coat Film)

<Examples 1-1 to 1-12>

The ultraviolet absorbing hard coat layer coating liquid for each of the examples shown in Table 2 was coated on one side of the polyethylene terephthalate film so as to have a dry film thickness of 0.5, 1 or 10 占 퐉 by a gravure coating method, UV-absorbing hard coat films of Examples 1-1 to 1-12 were prepared by irradiating ultraviolet rays at an output of 400 mJ / cm &lt; 2 &gt; under a nitrogen atmosphere and curing.

&Lt; Examples 2-1 to 2-6 >

The ultraviolet-absorbing hard coat layer coating liquid for each of the examples in which the (E) quaternary ammonium salt-based copolymer described in Table 3 was added to one side of a polyethylene terephthalate film was coated by a gravure coat method to a dry film thickness of 1 占 퐉 UV-absorbing hard coat films of Examples 2-1 to 2-6 were prepared by drying and curing by irradiation with ultraviolet rays at an output of 400 mJ / cm 2 under a nitrogen atmosphere.

&Lt; Examples 3-1 and 3-2 >

The low refractive index layer coating solution? 1 was coated on the ultraviolet ray absorbing hard coat layer prepared in Examples 1-1 and 2-1 so that the optical film thickness after curing became k? / 4 (k: 1,? / 550 nm) The ultraviolet absorbing hard coat films of Examples 3-1 and 3-2 were prepared by applying the coating composition by a coating method, drying and then curing by irradiation with ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere.

&Lt; Examples 4-1 to 4-4 >

The pressure-sensitive adhesive layer coating solution? 1 was coated on a separator film made of PET using an auto-applicator so that the thickness after drying was 25 占 퐉, dried at 90 占 폚 for 2 minutes, Absorbing hard coat layer formed on the polyethylene terephthalate film by using the ultraviolet ray absorbing hard coat layer film formed in 3-2 and the other side opposite to the surface on which the ultraviolet absorbing hard coat layer of the polyethylene terephthalate film was formed and stored at 30 DEG C for 5 days, UV-absorbing hard coat films of 4-1 to 4-4 were prepared [Table 3].

&Lt; Comparative Example 1 &

An ultraviolet absorptive hard coat film was prepared in the same manner as in Example 1-1 except that the ultraviolet absorber (B) was removed from the ultraviolet absorptive hard coat layer coating liquid.

&Lt; Comparative Example 2 &

An ultraviolet absorptive hard coat film was prepared in the same manner as in Example 1-1 except that the thickness of the ultraviolet light absorptive hard coat layer was 0.1 mu m.

&Lt; Comparative Example 3 &

An ultraviolet absorptive hard coat film was produced in the same manner as in Example 1-1 except that the thickness of the ultraviolet absorptive hard coat layer was changed to 15 mu m.

&Lt; Comparative Example 4 &

An ultraviolet absorptive hard coat film was prepared in the same manner as in Example 1-1 except that (D) the surface modifier was removed from the ultraviolet absorptive hard coat layer coating liquid.

The surface hardness, scratch resistance, adhesiveness after the weather resistance test, curl, surface resistivity, visibility reflectance, and adhesiveness of the ultraviolet absorbing hard coat films of the obtained examples and comparative examples were evaluated. The results are also shown in Tables 2 and 3. The measurement method of each item is as follows.

(I) Surface hardness

The pencil hardness was measured according to JIS K 5600-5-4 using a pencil hardness tester manufactured by Yasuda Kogyo Co., Ltd.

(II) scratch resistance

A steel wool of # 0000 was fixed to the tip of an eraser abrasion tester manufactured by Honko Corporation and a load of 2.5 N (250 gf) was applied to the surface of the ultraviolet ray absorbing hard coat film after 10 times reciprocating rubbing. The scratches were observed with naked eyes and evaluated in six stages A to E below.

A: No scratches, A ': 1 to 3 scratches, B: Scratches 4 to 10, C: Scratches 11 to 20, D: Scratches 21 to 30, E: 31 or more

(III) Weatherability test I

<Super Xenon Test>

A test was conducted for 100 hours under the test conditions of an irradiation illuminance of 180 W / m 2, a wavelength of irradiation light of 300 to 400 nm and a BPT temperature of 63 1 캜 using a Super Xenon Weather Meter SX75 (manufactured by Suga Test Instruments Co., Ltd.) A crosscut peeling tape test was carried out in accordance with JIS D 0202-1998. And then adhered to the ultraviolet ray absorbing hard coat layer or the low refractive index layer of the ultraviolet ray absorbing hard coat film using a cellophane tape (CT24, manufactured by Nichiban Co., Ltd.), and then peeled off. The weatherability was evaluated as adhesion, and the number of peeled peelings out of 100 peeled peelings was expressed as 占 / 100. For example, 100/100 when no peeling was observed, and 0/100 when peeling was completely peeled off.

(IV) Weatherability test II

<Sunshine Weatherometer Test>

Using a Sunshine Weatherometer S80 (manufactured by Suga Test Instruments Co., Ltd.), the test conditions of the irradiation intensity (255 W / m 2), the wavelength of the irradiation light 300 to 400 nm, the BP temperature 63 賊 1 캜, After the test, the crosscut peel tape test conducted in the weather resistance test I was carried out.

(V) Curling test

An ultraviolet ray absorbing hard coat film having a size of 10 cm x 10 cm was prepared and the curl heights at four corners when placed on a horizontal plane were measured and judged according to the following criteria.

?: Curl height of less than 20 mm

DELTA: Curl height of 20 mm or more and less than 50 mm

X: Curl height of 50 mm or more

(Ⅵ) Surface resistivity

(SM-8220, manufactured by TOA DKK CO., LTD.) According to JIS K 6911-1995.

(VII) Visible reflectance

The ultraviolet-absorbing hard coat film having the back surface thereof roughened with sandpaper and completely coated with black paint was applied to the surface of the measurement surface by a spectrophotometer (trade name: U-best560, manufactured by Nippon Bunko KK) 5 ° and -5 ° specular reflection spectra of 380 nm to 780 nm were measured. Using the obtained spectral reflectance of 380 nm to 780 nm and the relative spectral distribution of the CIE standard Illuminant D65, the tristimulus value Y of the object color due to reflection in the XYZ color system assumed in JIS Z 8701 is used as the visibility reflectance ( %).

From the results shown in Table 2, the ultraviolet absorbing hard-coat films of the respective Examples had physical resistance and good adhesiveness after the weather resistance test. Also, the curl was good. On the other hand, the ultraviolet-absorbing hard coat film of Comparative Example 1 had (B) no ultraviolet absorber contained in the ultraviolet-absorbing hard coat layer, so that the adhesiveness after the weathering test remarkably deteriorated. The ultraviolet absorbing hard coat film of Comparative Example 2 can not sufficiently inhibit the deterioration of the ultraviolet absorbing hard coat film due to ultraviolet rays due to the decrease in the content of the ultraviolet absorbing agent (B) accompanying the thinning of the film thickness of the ultraviolet absorbing hard coat layer, The adhesion after weathering test deteriorated. In the ultraviolet absorbing hard coat film of Comparative Example 3, the curl was deteriorated because the film thickness of the ultraviolet ray absorbing hard coat layer was too thick. In the ultraviolet absorbing hard coat film of Comparative Example 4, since the surface adjusting agent (D) was not added, the slidability of the surface was lowered and the physical resistance was lowered.

From the results shown in Table 3, it is evident that in Examples 2-1 to 2-6, 3-2, 4-3, and 4-4, the ultraviolet absorbent hard coat layer contains the (E) quaternary ammonium salt-based copolymer as an antistatic agent The antistatic ability was given. In Examples 3-1, 3-2, 4-2 and 4-4, since the low refractive index layers are laminated, the visibility reflectance can be lowered, and even if the low refractive index layers are laminated, . Further, in Examples 4-1 to 4-4, adhesive properties were obtained because the adhesive layers were laminated.

Claims (4)

An ultraviolet ray absorbing hard coat film having an ultraviolet ray absorbing hard coat layer formed on one side of a transparent base film,
The ultraviolet-absorbing hard coat layer is a layer
(A) 100 parts by mass of dipentaerythritol hexaacrylate,
(B) 1 to 20 parts by mass of an ultraviolet absorber represented by the following general formula (1) for absorbing light having a wavelength of 300 to 350 nm,
(C) 0.1 to 10 parts by mass of a photopolymerization initiator,
(D) 0.001-20 parts by mass of a polyether-modified polydimethylsiloxane,
(E) a quaternary ammonium salt-based copolymer obtained by radical copolymerization of a compound (e-1) having a quaternary ammonium group represented by the following general formula (2) and a compound (e-2) having one ethylenically unsaturated group
Wherein the ultraviolet absorbing hard coat layer is a layer having a thickness of 0.5 to 10 占 퐉 obtained by ultraviolet curing the coating liquid.

CH ₂ = C (R ¹ ) COZ (CH ₂ ) _k N ⁺ (R ² ) ₃ · X ^- (2)
(Wherein, R ¹ is H or CH _3, R ² are each independently a carbon number of from 1 to 4 or a hydrocarbon group, Z is an oxygen atom or NH group, k is an integer of 1 ~ 10, X ^- is a monovalent anion Lt; / RTI & delete The method according to claim 1,
And a low refractive index layer having a refractive index lower than that of the ultraviolet absorbing hard coat layer is formed on the ultraviolet absorbing hard coat layer. The method according to claim 1 or 3,
And an adhesive layer is formed on the other surface of the transparent base film.