JP2010158898A - Resin laminate for surface protection and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin laminate for surface protection enabling print decoration without a decrease of hard coat characteristics, such as flaw resistance, abrasion resistance, and optical properties such as transmittance, haze and the like and capable of excellently preventing a foul due to adherence of a sebum film. <P>SOLUTION: In the resin laminate for surface protection composed of a resin plate and a hard coat layer applied on either or both of front and back surfaces of the resin plate, the hard coat layer is composed of a cured substance of an ultraviolet-curable compound (A), the content of at least one compound selected from a fatty acid, an ester of the fatty acid, or a derivative thereof (B) is 0.01 to 8 pts.wt. based on 100 pts.wt. of the ultraviolet-curable compound (A), and there is a recess with a diameter of ≤1.3 μm on the surface of the hard coat layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a surface protective resin laminate and a liquid crystal display.

Mobile phones, digital cameras, digital video cameras, liquid crystal televisions, personal computers, portable game machines, GPS (Global Positioning System), touch panel liquid crystal displays, goggles, CDs (compact discs) and DVDs (digital video) A resin laminate is used to protect the surface of the disk), and the surface of the resin laminate is usually subjected to a hard coat treatment for the purpose of preventing scratches and abrasion of the resin laminate. Since the outermost hard coat layer is in contact with the skin when using the above-mentioned member, the surface of the hard coat layer is contaminated by the adhesion of a sebum film formed by secretory components (sebum and sweat) from the skin. There was a problem.
Conventionally, as a technique for preventing dirt, a technique has been disclosed in which a fluorine-based compound or a silicon-based compound is contained in a hard coat layer to improve water repellency and oil repellency and make it difficult to attach dirt (for example, Patent Documents). 1 and 2).
However, it is very difficult to completely prevent the adhesion of dirt, and in particular, it is very difficult to prevent dirt due to adhesion of the skin film. There was a problem that light was scattered and became more conspicuous.
In addition, when printing is applied to the hard coat layer, the conventional method of adding a fluorine compound or silicon compound to the hard coat layer makes the surface of the hard coat layer water and oil repellant. If you try to decorate with a pattern, etc., printing ink will be repelled, and printing using general-purpose printing methods such as screen printing and gravure printing will not be possible, limiting the usage. It was.

Japanese Patent No. 3344199 Japanese Patent Laid-Open No. 2007-160764

  The object of the present invention is to enable printing and application without causing deterioration of hard coat properties such as scratch resistance and abrasion resistance and optical properties such as transmittance and haze, and to prevent contamination due to adhesion of sebum film. An object of the present invention is to provide a surface protective resin laminate excellent in prevention.

Such a problem is solved by the present invention described in the following (1) to (8).
(1) A resin laminate for surface protection composed of a resin plate and a hard coat layer coated on both sides or one side of the resin plate,
The hard coat layer is made of a cured product of the ultraviolet curable compound (A), and the content of at least one compound selected from fatty acids, fatty acid esters or derivatives thereof (B) is the ultraviolet curable compound (A). The resin layered product for surface protection which is 0.01 weight part or more and 8 weight part or less with respect to 100 weight part of cured | curing material of this, and has a dent with a diameter of 1.3 micrometers or less on the surface of the said hard-coat layer.
(2) The content of the fatty acid, fatty acid ester or derivative thereof (B) in the hard coat layer is 0.1 parts by weight or more with respect to 100 parts by weight of the cured product of the ultraviolet curable compound (A). The resin laminate for surface protection according to (1), which is not more than parts by weight.
(3) The resin plate for surface protection according to (1) or (2), wherein the resin plate is formed of an acrylic resin or a polycarbonate resin.
(4) The resin laminate for surface protection according to any one of (1) to (3), wherein the resin plate has a thickness of 0.3 mm or more and 2 mm or less.
(5) The depth of the recess having a diameter of 1.3 μm or less on the surface of the hard coat layer is 0.008 μm or more and 0.15 μm or less, wherein any one of (1) to (4) The resin laminate for surface protection as described.
(6) The number of indentations or less in diameter 1.3μm on the surface of the hard coat layer, characterized in that the 1 mm ² at 800 or more 250,000 or less (1) any one of - (5) A resin laminate for surface protection as described in 1.
(7) The resin laminate for surface protection according to any one of (1) to (6), which is used for a liquid crystal display unit.
(8) A liquid crystal display produced by using the surface protective resin laminate according to any one of (1) to (7).

  According to the present invention, it is possible to add printing without degrading hard coat properties such as scratch resistance and abrasion resistance and optical properties such as transmittance and haze, and to prevent contamination due to sebum film adhesion. It is possible to provide an excellent surface protective resin laminate.

The present invention is a laminate for surface protection comprising a resin plate and a hard coat layer coated on both the front and back sides or one side of the resin plate, the hard coat layer comprising an ultraviolet curable compound (A). The content of at least one compound selected from fatty acids, fatty acid esters or derivatives thereof (B) is 0.01 parts by weight with respect to 100 parts by weight of the cured product of the ultraviolet curable compound (A). As mentioned above, it is a resin laminate for surface protection which is 8 parts by weight or less and has a dent having a diameter of 1.3 μm or less on the surface of the hard coat layer.
In the surface protective resin laminate of the present invention, a fatty acid, a fatty acid ester or a derivative thereof (B) is added to the hard coat layer as a compound having an affinity for the sebum film, and the surface of the hard coat layer has a diameter of 1. By having a dent of 3 μm or less, the contact angle of the sebum film adhering to the surface of the hard coat layer can be lowered to make it less noticeable. The diameter of the recess on the surface of the hard coat layer is more preferably 1.2 μm or less, and further preferably 1 μm or less.

The hard coat layer is a cured product of the ultraviolet curable compound (A), and is formed of a cured product of the ultraviolet curable compound (A).
The ultraviolet curable compound (A) is a compound that is cured by being irradiated with ultraviolet rays, and is an ultraviolet curable monomer or an ultraviolet curable oligomer, and any one of general ultraviolet curable monomers and ultraviolet curable oligomers. Or a combination of an ultraviolet curable monomer and an ultraviolet curable oligomer.
The content of the ultraviolet curable compound (A) is preferably 90% by weight or more and 99% by weight or less, and more preferably 93% by weight or more and 96% by weight or less with respect to the entire hard coat layer. By setting the content of the ultraviolet curable compound (A) within the above range, particularly good hard coat characteristics and optical characteristics can be obtained.
Examples of the UV curable monomer include dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate. , Ethoxylated pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate, polyethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated hydrogenated bisphenol A diacrylate, ethoxylated cyclohexanedimethanol diacrylate, tricyclodecanedi Examples include methanol diacrylate.
In addition, the ultraviolet curable oligomer includes an isocyanate compound obtained by reacting a polyol and diisocyanate, a compound obtained by reacting an acrylate monomer having a hydroxyl group, an oxirane ring and an acrylic resin of a low molecular weight bisphenol type epoxy resin or novolac epoxy resin. A compound obtained by esterification reaction with an acid, a polyester oligomer having hydroxyl groups at both ends by condensation of polycarboxylic acid and polyhydric alcohol, and then obtained by esterifying the hydroxyl groups at both ends with acrylic acid And the like. Specific examples include polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, alkyd acrylate, and polyol acrylate.
Here, the oligomer refers to a polymer having a number of repeating structural units (degree of polymerization) of about 2 to 20, and since the degree of polymerization is still small, it is not a polymer, that is, a polymer. It is the previous polymer.

  The ultraviolet curable oligomer is used to provide various physical properties (scratch resistance, abrasion resistance, impact resistance, workability, flexibility, etc.) necessary for the hard coat layer. For example, urethane acrylate Examples include oligomers, epoxy acrylate oligomers, and polyester acrylate oligomers.

The urethane acrylate oligomer is obtained, for example, by a reaction between an isocyanate compound obtained by reacting a polyol and diisocyanate and an acrylate monomer having a hydroxyl group.
The epoxy acrylate oligomer can be obtained, for example, by an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin and acrylic acid.
The polyester acrylate oligomer is obtained, for example, by obtaining a polyester oligomer having hydroxyl groups at both ends by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, and then esterifying the hydroxyl groups at both ends with acrylic acid.
As the ultraviolet curable oligomer, it is particularly preferable to use a urethane acrylate oligomer. Furthermore, an ultraviolet curable oligomer having at least 6 functionals for achieving high hardness, and an ultraviolet curable oligomer having no more than 3 functionals for imparting flexibility. Is more preferable for achieving a balance between excellent hardness and impact resistance.
In the present invention, “hexafunctional” means that the number of functional groups that undergo a polymerization reaction by ultraviolet rays in one molecule, for example, an acrylic group, a methacryl group, a vinyl group, and the like is six.

When the ultraviolet curable monomer is used, the crosslink density of the hard coat layer and the viscosity of the ultraviolet curable resin composition can be easily adjusted, and the adhesion between the hard coat layer and the resin plate can be improved.
Among these, a bifunctional acrylate having a cyclic structure is particularly preferable in that the hardness and heat resistance of the hard coat layer can be increased.

The hard coat layer according to the surface protective resin laminate of the present invention contains a fatty acid, a fatty acid ester, or a derivative thereof (B). That is, in this invention, the hardened | cured material of the ultraviolet curable compound (A) which forms the hard-coat layer contains a fatty acid, fatty acid ester, or those derivatives (B).
Examples of the fatty acid, fatty acid ester or derivative thereof (B) include the following, and these may be used alone or in combination of two or more.
Examples of fatty acids include myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, and lignoceric acid.
Examples of the fatty acid ester include polyoxyethylene fatty acid ester, propylene glycol fatty acid ester, glycerin fatty acid ester (triolein), polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxy Ethylene sorbit fatty acid ester, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene sorbit beeswax, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene sterol, polyoxyethylene hydrogenated sterol, polyoxyethylene Alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxye Alkylether phosphates, polyoxyethylene alkylene ether phosphate, and polyethylene glycol fatty acid ester.
Fatty acid derivatives and fatty acid ester derivatives have structures in which some or all of the methyl groups in the side chain in the fatty acid or fatty acid ester are replaced with other organic groups. Examples of the organic group include a polyether group, a polyalkyl group, an aralkyl group, and a polyester group, and these may be used alone or in combination of two or more.
Of these, fatty acids, fatty acid esters or derivatives thereof (B) include polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl isostearate, polyoxyethylene glyceryl tristearate, polyoxyethylene glyceryl diisostearate, polyoxylaurate Ethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil isostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol tetraoleate, polyoxyethylene sorbite tetrastearate, polyoxyethylene castor Oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytosterol, polyoxyethylene cholesteryl ether, polyethylene Of fatty acids, fatty acid esters and / or derivatives thereof such as oxyethylene hydrogenated dimer dilinoleate, etc., one or more hydrocarbons (straight or cyclic) having 12 or more carbon atoms in the molecule, and repeated A structure having a polyether chain having a total of 10 or more units in the same molecule is preferred, and further, two or more straight-chain hydrocarbons having 16 to 18 carbon atoms in the molecule and a repeating unit Are particularly preferred having a structure having two or more polyether chains having a total of 20 to 80 in the same molecule.

  The content of the fatty acid, fatty acid ester or derivative thereof (B) in the hard coat layer is 0.01 parts by weight or more and 8 parts by weight or less with respect to 100 parts by weight of the cured product of the ultraviolet curable compound (A). It is preferably 0.1 parts by weight or more and 5 parts by weight or less, and more preferably 0.3 parts by weight or more and 4 parts by weight or less. When the value is less than the above lower limit value, it is not possible to obtain a stain prevention property due to adhesion of sebum film, and when the value exceeds the upper limit value, hard coat characteristics and optical characteristics may be deteriorated.

  Here, the sebum film is a film formed on the surface of the skin by mixing lipid secreted from the sebaceous gland and sweat secreted from the sweat gland. The components of the sebum film are, for example, fatty acid 7.9-39.0%, triglyceride 9.5-49.4%, diglyceride monoglyceride 2.3-4.3%, wax ester 22.6-29.5%, Cholesterol ester is composed of 1.5 to 2.6%, cholesterol 1.2 to 2.3%, and squalene 10.1-13.9%, but 85% or more (other than squalene and cholesterol All) are composed of fatty acids, fatty acid esters or derivatives (B) thereof. Triglyceride is an ester bond between glycerin and three fatty acids, diglyceride is an ester bond between glycerin and two fatty acids, and monoglyceride is a bond between glycerin and one fatty acid. The wax ester is an ester bond of a fatty acid and a higher alcohol. Cholesterol ester is an ester bond of cholesterol and fatty acid.

From the above, it is possible to make the contact angle of the dirt adhered to the sebum film less noticeable by including the fatty acid, fatty acid ester or derivative thereof (B) in the hard coat layer.

A recess having a diameter of 1.3 μm or less is formed on the surface of the hard coat layer according to the surface protective resin laminate of the present invention. And it is estimated that the fatty-acid, fatty-acid ester, or those derivatives (B) exist in the dent part.
In the present invention, the diameter of the dent refers to the maximum diameter, and having a dent having a diameter of 1.3 μm or less means that the maximum diameter of the dent formed on the surface of the hard coat layer is 1.3 μm. When the diameter of all the dents formed on the surface of the hard coat layer is measured, the maximum diameter of them is 1.3 μm or less.

In order to reduce the contact angle of the adhered dirt on the sebum film, fatty acid, fatty acid ester or derivatives thereof (B) must be present on the outermost surface of the hard coat layer.
However, even if fatty acid, fatty acid ester or derivative thereof (B) is contained in the hard coat layer, the effect of lowering the contact angle cannot be obtained if there is no dent on the outermost surface of the hard coat layer.
The depression is formed when the hard coat layer of the surface protective resin laminate of the present invention is formed because the fatty acid, fatty acid ester or derivative thereof (B) has a hydrophobic portion in its molecule, It is presumed that adsorption occurs at the interface with the air layer (hydrophobic) during the formation of the coat layer, which is caused by partially inhibiting the leveling of the hard coat layer. By having a dent, the effect of preventing dirt is obtained, and when the maximum diameter of the dent exceeds 1.3 μm, optical characteristics such as transmittance and haze may be deteriorated.

  The depth of the recess having a diameter of 1.3 μm or less formed on the surface of the hard coat layer is preferably 0.008 μm or more and 0.15 μm or less, more preferably 0.01 μm or more and 0.1 μm or less. preferable. By setting it as the above range, optical properties such as transmittance and haze can be maintained, and there is an effect of preventing contamination due to adhesion of the sebum film. Here, the depth of the dent is the maximum depth of the dent.

The number of recesses having a diameter of 1.3 μm or less formed on the surface of the hard coat layer is preferably 800 or more and 250,000 or less per 1 mm ² , and more preferably 1000 or more and 200,000 or less. preferable. By setting it as the above range, optical properties such as transmittance and haze can be maintained, and there is an effect of preventing contamination due to adhesion of the sebum film.
The diameter (maximum diameter) of the recesses on the surface of the hard coat layer and the number of the recesses can be measured using a laser microscope (VK-9700 manufactured by Keyence Corporation). Moreover, the depth of the dent can be measured using an atomic force microscope (VN-8000 manufactured by Keyence Corporation), and is defined as the maximum depth.

The hard coat layer according to the surface protective resin laminate of the present invention is formed by applying an ultraviolet curable composition to a resin plate and then curing the ultraviolet curable composition by irradiation with ultraviolet rays.
The ultraviolet curable composition used for formation of a hard-coat layer contains the said ultraviolet curable compound (A) and 1 or more types of a fatty acid, fatty-acid ester, and those derivatives (B).

Moreover, the ultraviolet curable composition can contain a photoinitiator. The photopolymerization initiator is added to the ultraviolet curable composition in order to initiate the reaction (polymerization) of the ultraviolet curable compound by ultraviolet irradiation.
Photopolymerization initiators include, for example, benzoin or benzoin alkyl ethers such as benzoin, benzoin methyl ether benzoin isopropyl ether, benzophenone,
Aromatic ketones such as benzoylbenzoic acid, alphagecarbonyls such as benzyl, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane -1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propane -1-one, 2-methyl-1- [4- (methylthio) phenyl]-
Acetophenones such as 2-morpholinopropanone-1, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone,
Thioxanthones such as 4-dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1-phenyl-1, 2
Alpha-acyl oximes such as propanedione-2- [o-ethoxycarbonyl] oxime, amines such as ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and the like can be used. As the photopolymerization initiator, those having excellent surface curability and those having excellent internal curability are preferably used in combination of two or more.

  Further, the ultraviolet curable composition may contain a surface conditioner, a diluting solvent, an inorganic or organic filler, etc., if necessary, in addition to the above components.

  The surface conditioner contained in the ultraviolet curable composition is added to the ultraviolet curable composition as necessary in order to smoothen the coated film and obtain an excellent appearance. Examples of such materials include fluorine-based, modified silicon-based, and acrylic copolymers. It is preferable to use a small amount of a fluorine-based or silicon-based surface conditioner having excellent surface tension reducing ability.

The ultraviolet curable composition used for forming the hard coat layer according to the surface protective resin laminate of the present invention may be a dispersion or solution in which the above components are dispersed or dissolved in a solvent.
The solvent used for the preparation of the ultraviolet curable composition is added to the ultraviolet curable composition as necessary in order to facilitate the application of the ultraviolet curable composition to the resin plate.
Examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, and butanol, methyl ethyl ketone, 2-pentanone, and isophorone. Examples include ketones, ethyl acetate, butyl acetate, esters such as methoxypropyl acetate, cellosolve solvents such as ethyl cellosolve, and glycol solvents such as methoxypropanol, ethoxypropanol, and methoxybutanol. These may be used alone or in combination of two or more. It may be mixed.

The resin plate according to the surface protective resin laminate of the present invention is not particularly limited as long as it is a general transparent resin, but is assumed to be used for the present invention, such as a mobile phone, a digital camera, a digital video camera, and a liquid crystal television. Protective covers for LCDs such as personal computers, portable game machines, touch panels, goggles, CDs (compact discs) and DVDs (digital video discs) are acrylic from the viewpoint of transparency, workability, and impact resistance. What is formed with resin or polycarbonate resin is preferable.
As the resin plate, for example, a general transparent resin such as polyethylene terephthalate resin, polyvinyl chloride resin, and polystyrene resin is also suitable.

The thickness of the resin plate is preferably 0.3 mm or more and 2 mm or less. More preferably, it is 0.5 mm or more and 1.5 mm or less. By setting the thickness of the resin plate within the above range, it is possible to reduce the size or the thickness while maintaining the performance (impact resistance, workability, etc.) particularly required for the protective cover for the above-mentioned use.

The method for forming the hard coat layer formed on the surface protective resin laminate of the present invention is not particularly limited. For example, a roll coating method, a flow coating method, a spray coating method, a curtain coating method, a dip coating method, a die coating method, etc. The method of apply | coating an ultraviolet curable composition to the front and back both surfaces or single side | surface of a resin plate using these well-known methods is mentioned.
When the UV curable composition is coated on a transparent resin plate and contains a diluting solvent, the temperature of the resin plate and the atmosphere is raised to sufficiently dry the diluting solvent to form a coating film, which is then irradiated with UV rays. The hard coat layer can be formed by curing the coating film. For example, a general electroded or electrodeless high-pressure mercury lamp or metal halide lamp can be used for ultraviolet irradiation. Also, a low voltage electron beam irradiation apparatus of about 100 KeV can be used. When an electron beam is used as the curing means, the above-described photopolymerization initiator is not necessary.

  The thickness of the hard coat layer is not particularly limited, but is preferably 1 μm or more and less than 50 μm in order to obtain practical performance as the hard coat layer. When the thickness of the hard coat layer is 50 μm or more, it is difficult to uniformly cure to the inside by ultraviolet irradiation, and the adhesion between the hard coat layer and the resin plate may be defective, or cracks due to the curing shrinkage of the coating film May occur.

  The liquid crystal display body of the present invention is a liquid crystal display body produced using the surface protective resin laminate of the present invention, which is a liquid crystal display body having a display portion, and the surface protective resin laminate of the present invention is image-displayed. It is used for the display part of the body. Specifically, the liquid crystal display of the present invention is preferably a digital camera, a digital video camera, a liquid crystal television, a personal computer, a portable game machine, GPS, a liquid crystal display part of a touch panel, goggles, CD or DVD.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this. The following were prepared from commercially available raw materials.
<Ultraviolet curable compound (A)>
(A1) Hexafunctional urethane acrylate oligomer (trade name: EB1290, manufactured by Daicel Cytec Co., Ltd.) << UV curable oligomer >>
(A2) Bifunctional urethane acrylate oligomer (trade name: EB8402, manufactured by Daicel Cytec Co., Ltd.) << UV curable oligomer >>
(A3) Pentaerythritol tetraacrylate (trade name: A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) << UV curable monomer >>
(A4) Ethoxylated bisphenol A diacrylate (trade name: A-BPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.) << UV curable monomer >>
<Fatty acid, fatty acid ester or derivative thereof (B)>
(B1) Polyoxyethylene hydrogenated castor oil (trade name: Emanon CH-60, manufactured by Kao Corporation) (B2) Polyoxyethylene castor oil (trade name: C-40, manufactured by Nippon Emulsion Co., Ltd.)
(B3) Tetraoleic acid polyoxyethylene sorbit (trade name: 460V, manufactured by Kao Corporation)
(B4) Lauric acid polyoxyethylene hydrogenated castor oil (trade name: RWL-150, manufactured by Nippon Emulsion Co., Ltd.)
<Photopolymerization initiator>
1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Japan)
<Surface conditioner>
Silicon-based surface conditioner (trade name: Granol 450, manufactured by Kyoeisha Chemical Co., Ltd.)

[Example 1]
As the ultraviolet curable compound (A), EB1290 / EB8402 / A-TMMT / A-BPE-4 is blended at a ratio of 40/10/40/10 so that the concentration of the ultraviolet curable compound is 20% by weight. The mixture was diluted with a 50/50 mixed dilution solvent of propylene glycol monomethyl ether / isobutyl alcohol.
Here, 5 parts by weight of Irgacure 184 was added to 100 parts by weight of the ultraviolet curable compound, and Granol 450 was added to 0.05 part by weight of 100 parts by weight of the ultraviolet curable compound.
Furthermore, 1 part by weight of Emanon CH-60 was added to 100 parts by weight of the ultraviolet curable compound. The blended solution was sufficiently stirred to obtain an ultraviolet curable composition, and then stored in a sealed container.
Prepare a polycarbonate resin plate ("Polyca Ace" manufactured by Sumitomo Bakelite Co., Ltd.) with a thickness of 0.5 mm, and apply the UV curable composition on the resin plate using a metal bar coater so that the wet film thickness is 25 μm. Applied.
The coated plate is placed in a 50 ° C. hot air circulation oven, dried for 10 minutes, and then irradiated with ultraviolet rays using an 80 W / cm metal halide lamp (USHIO INC.) At an irradiation distance of 50 mm and a conveyor conveyance speed of 5 m / min. Then, the coating film was cured to obtain a resin laminate for surface protection having a hard coat layer with a dry film thickness of 5 μm.

[Example 2]
A surface protective resin laminate was obtained in the same manner as in Example 1 except that 0.5 parts by weight of Emanon CH-60 was added to 100 parts by weight of the ultraviolet curable compound.
[Example 3]
A resin laminate for surface protection was obtained in the same manner as in Example 1 except that 3 parts by weight of Emanon CH-60 was added to 100 parts by weight of the ultraviolet curable compound.

[Example 4]
Example 1 except that 1 part by weight of Emanon CH-60 was added to 100 parts by weight of the UV curable compound, and 3 parts by weight of C-40 was added to 100 parts by weight of the UV curable compound. In the same manner as in Example 1, a surface protective resin laminate was obtained.
[Example 5]
Example 1 except that 1 part by weight of Emanon CH-60 was added to 100 parts by weight of the UV curable compound, except that 4 parts by weight of 460 V was added to 100 parts by weight of the UV curable compound. Similarly, a resin laminate for surface protection was obtained.
[Example 6]
Example except that 5 parts by weight of RWL-150 was added to 100 parts by weight of UV curable compound instead of adding 1 part by weight of Emanon CH-60 to 100 parts by weight of UV curable compound In the same manner as in Example 1, a surface protective resin laminate was obtained.

[Comparative Example 1]
EB1290 / EB8402 / A-TMMT / A-BPE-4 was blended at a ratio of 40/10/40/10, and propylene glycol monomethyl ether / isobutyl alcohol was mixed so that the concentration of the UV-curable compound was 20% by weight. Diluted with 50/50 mixed dilution solvent.
Here, 5 parts by weight of Irgacure 184 was added to 100 parts by weight of the ultraviolet curable compound, and Granol 450 was added to 0.05 part by weight of 100 parts by weight of the ultraviolet curable compound. In addition, Emanon CH-60 was not added. The blended solution was sufficiently stirred to obtain an ultraviolet curable composition, and then stored in a sealed container.
Prepare a polycarbonate resin plate ("Polyca Ace" manufactured by Sumitomo Bakelite Co., Ltd.) with a thickness of 0.5 mm, and apply the UV curable composition on the resin plate using a metal bar coater so that the wet film thickness is 25 μm. Applied.
The coated plate is put in a hot air circulation oven at 50 ° C., dried for 10 minutes, and then 80 W
/ Cm metal halide lamp (manufactured by USHIO ELECTRIC CO., LTD.), A surface protecting resin having a hard coat layer with a dry film thickness of 5 μm by irradiating ultraviolet rays under conditions of an irradiation distance of 50 mm and a conveyor conveyance speed of 5 m / min. A laminate was obtained.

[Comparative Example 2]
A resin laminate for surface protection was obtained in the same manner as in Example 1 except that 10 parts by weight of Emanon CH-60 was added to 100 parts by weight of the ultraviolet curable compound.

The following evaluation was performed about the resin laminate for surface protection obtained as mentioned above.
<Dimple on hard coat layer surface>
The diameter of the dent (maximum diameter) and the number of dents on the surface of the hard coat layer were measured using a laser microscope (VK-9700, manufactured by Keyence Corporation). Moreover, the depth of the dent was measured using an atomic force microscope (VN-8000 manufactured by Keyence Corporation), and was defined as the maximum depth. The measurement was performed at three arbitrary positions in each sample size 10 cm × 5 cm.
Indentation diameter: All indentations in the field of view were measured and taken as the maximum diameter of those indentations.
The number of indentations: the number of dents per 1 mm ^2, from the field area of the laser microscope was calculated per 1 mm ^2.
Indentation depth: All indentations in the field of view were measured and taken as the maximum depth of those indentations. <Hard coat properties>
Steel wool # 0000 was attached to a holder having a diameter of 10 mm, and after 100 reciprocations at a constant load (500 g) and a constant speed (6000 mm / min), the presence or absence of scratches on the sample surface was visually observed and evaluated according to the following criteria. .
A: No scratch / practical superior B: Several scratches / practical enough but practical use limited C: Overall scratch / practical inferior

<Optical characteristics>
JIS K using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.)
In accordance with 7105, the total light transmittance (Tt) and haze (Hz) were measured.

<Anti-fouling property of sebum film>
(1) Dirt resistance I (Adhesive dirt is not noticeable / invisible)
The index finger is pressed against the nose, which is one of the parts with the largest amount of sebum film, to transfer the sebum film, and the finger is placed on the surface of the hard coat layer of the surface protective resin laminate prepared by the above method (1 kg). ) And re-transferred. The surface of the hard coat layer to which the sebum film was transferred was observed visually and with a microscope to confirm the state of adhesion of the sebum film, and evaluated according to the following criteria.
A: The sebum film adheres and adheres (the contact angle is low), and the adhered dirt of the sebum film is not noticeable. (Difficult to see)
B: The sebum film is repelled and adhered (the contact angle is high), and the adhered dirt of the sebum film is conspicuous. (Easy to see)
(2) Dirt resistance II (Inconspicuousness / invisibleness after wiping test for adhered dirt)
After the sebum film was transferred to the hard coat layer surface in the same manner as described above, a wiper (trade name: Handy Wiper, manufactured by Kuraray Co., Ltd.) was attached to a holder having a diameter of 30 mm, a constant load (1 kg), a constant speed (6000 m / min). ) 50 round trips. While observing the surface of the test body with a microscope, haze (Hz) was measured using the haze meter and evaluated according to the following criteria.
A: The sebum film is almost completely wiped off (some are completely familiar and attached at a contact angle of 0 °), and the haze is the same as before the dirt is adhered, and the sebum film is not noticeable.
(Difficult to see)
B: The sebum film was hardly wiped off (mostly repelled and adhered at a high contact angle), the haze was higher than before the dirt adhered, and the adhered dirt on the sebum film was conspicuous.
(Easy to see)

<Printability>
Using a commercially available two-component curable ink (trade name; HAC, manufactured by Seiko Advance), a 50 × 150 mm solid print was performed on the surface of the hard coat layer by a screen printing method using a T-270 screen mesh. After drying in a hot air circulating oven for 20 minutes and then allowing to stand at room temperature for 1 hour, a 25 square grid pattern was performed in accordance with JIS K 5400, and the following criteria were evaluated.
A: Printing can be performed without repelling ink at the time of printing, and ink peeling is not seen even in the first square after tape peeling.
B: Printing can be performed without repelling the ink, but after the tape is peeled, the ink at the first square is peeled off. C: The ink is repelled during printing, and printing cannot be performed.
The evaluation results are shown in Table 1.

As is clear from the results in Table 1, Examples 1 to 6 using the surface protective resin laminate of the present invention have a recess having a maximum diameter of 1.3 μm or less on the surface of the hard coat layer. It had the effect of preventing sebum film adhesion. Further, the hard coat property, the total light transmittance, and the haze maintained the practical performance, and the ink repelling at the time of printing was not observed, and the ink had good ink adhesion.
On the other hand, in Comparative Example 1 in which the fatty acid ester derivative is not added, there is no problem with hard coat properties, total light transmittance, and haze, but no dent is seen on the surface of the hard coat layer, and the seizure film adherence prevention property is poor. It was a thing.
Further, in Comparative Example 2 in which the fatty acid ester derivative (Emanon CH-60) was added excessively, the hard coat layer had a dent on the surface, and although the effect of preventing the sebum film from being adhered was obtained, the dent maximum The diameter was 1.3 μm or more, and a decrease in total light transmittance and an increase in haze were observed. In addition, the depth and number of dents on the surface of the hard coat layer were not measured because the maximum diameter of the dents was 2 μm.

Claims (8)

A resin laminate for surface protection composed of a resin plate and a hard coat layer coated on both the front and back sides or one side of the resin plate,
The hard coat layer is made of a cured product of the ultraviolet curable compound (A), and the content of at least one compound selected from fatty acids, fatty acid esters or derivatives thereof (B) is the ultraviolet curable compound (A). The resin layered product for surface protection which is 0.01 weight part or more and 8 weight part or less with respect to 100 weight part of cured | curing material of this, and has a dent with a diameter of 1.3 micrometers or less on the surface of the said hard-coat layer.   The content of the fatty acid, fatty acid ester or derivative thereof (B) in the hard coat layer is 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the cured product of the ultraviolet curable compound (A). The resin laminate for surface protection according to claim 1.   The resin laminate for surface protection according to claim 1 or 2, wherein the resin plate is formed of an acrylic resin or a polycarbonate resin.   The thickness of the said resin plate is 0.3 mm or more and 2 mm or less, The resin laminated body for surface protection of any one of Claims 1-3.   5. The surface protection according to claim 1, wherein a depth of a recess having a diameter of 1.3 μm or less on the surface of the hard coat layer is 0.008 μm or more and 0.15 μm or less. Resin laminate. 6. The surface protection according to claim 1, wherein the number of recesses having a diameter of 1.3 μm or less on the surface of the hard coat layer is 800 or more and 250,000 or less per 1 mm ^2. Resin laminate.   The resin laminate for surface protection according to any one of claims 1 to 6, which is used for a liquid crystal display unit. The liquid crystal display body produced using the resin laminated body for surface protection of any one of Claims 1-7.