JP5413298B2 - Manufacturing method of resin laminate - Google Patents

Description

  The present invention relates to a method for producing a resin laminate.

Mobile phones, digital cameras, digital video cameras, televisions, personal computers, portable game consoles, GPS (Global Positioning System), liquid crystal displays such as touch panels, goggles, CDs (compact discs) and DVDs (digital video) A resin laminate is used to protect the surface of a disk), and the surface of the resin laminate is usually subjected to a hard coat treatment for the purpose of preventing scratches and abrasion.
When using the above-mentioned members, the hard coat layer on the outermost surface comes into contact with the skin, so the surface of the hard coat layer becomes dirty due to the adhesion of sebum film formed by sebum or sweat, which is a secretory component from the skin. There was a problem that.
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 difficult to prevent dirt due to adhesion of the skin film. When dirt adheres, the contact angle of the dirt increases and the reflected light scatters. There was a problem of becoming more noticeable. In addition, when decoration is performed by printing characters and patterns, the printing ink is repelled, and screen printing or gravure printing cannot be used for printing, resulting in a limited use.

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

  The object of the present invention is a resin excellent in preventing dirt due to adhesion of sebum film without degrading hard coat properties such as scratch resistance and abrasion resistance and optical properties such as transmittance and haze. It is providing the manufacturing method of a laminated body.

Such a problem is solved by the present invention described in the following (1) to (4).
(1) An ultraviolet curable resin comprising an ultraviolet curable compound (A), a fatty acid, a fatty acid ester or a derivative thereof (B), and a polysiloxane compound (C) on the front and back surfaces or one side of the resin substrate. Applying the composition; and
The manufacturing method of the resin laminated body which has the process of hardening | curing the apply | coated ultraviolet curable resin composition.
(2) The modified polysiloxane compound (Cs) with respect to the cured product of the ultraviolet curable compound (As) in a portion from the surface of the hard coat layer to 100 nm of the hard coat layer made of the cured product of the ultraviolet curable resin composition The method for producing a resin laminate according to item (1), wherein the content ratio [(Cs) / (As)] is 0.0007 or more and 0.15.
(3) The hard coat layer made of a cured product of the ultraviolet curable resin composition is a fatty acid, a fatty acid ester or a fatty acid ester thereof with respect to a cured product of the ultraviolet curable compound (As) in a portion from the surface of the hard coat layer to 100 nm. The method for producing a resin laminate according to (1) or (2) above, wherein the content ratio [(Bs) / (As)] of the derivative (Bs) is 0.07 or more and 3.3 or less.
(4) The manufacturing method of the resin laminated body of any one of said (1)-(3) whose said resin base material is a resin base material containing an acrylic resin or a polycarbonate resin.

  According to the present invention, a resin laminate excellent in preventing soiling due to adhesion of a sebum film without degrading hard coat properties such as scratch resistance and abrasion resistance and optical properties such as transmittance and haze. A manufacturing method can be provided.

  The present invention provides an ultraviolet curable composition comprising an ultraviolet curable compound (A), a fatty acid, a fatty acid ester or a derivative thereof (B), and a polysiloxane compound (C) on the front and back surfaces or one side of the resin substrate. A method for producing a resin laminate comprising a step of applying a resin composition and a step of curing an applied ultraviolet curable resin composition. By using this method of producing a resin laminate, scratch resistance and resistance It is possible to provide a method for producing a resin laminate excellent in preventing soiling due to adhesion of a sebum film without degrading hard coat properties such as wear and optical properties such as transmittance and haze.

First, in the method for producing a resin laminate of the present invention, an ultraviolet curable compound (A), a fatty acid, a fatty acid ester or a derivative thereof (B), and polysiloxane are formed on a resin base material on both front and back surfaces or one surface of the resin base material. It has the process of apply | coating the ultraviolet curable resin composition containing a compound (C).
The method for applying the ultraviolet curable resin composition is not particularly limited, but for example, using a known method such as a roll coating method, a flow coating method, a spray coating method, a curtain coating method, a dip coating method, a die coating method, An ultraviolet curable resin composition is apply | coated to the front and back both surfaces or one side of the said resin base material.
Then, the hard coat layer which is the hardened | cured material of an ultraviolet curable resin composition is formed by having the process of hardening | curing the apply | coated ultraviolet curable resin composition.

  For example, when an ultraviolet curable resin composition is applied on a resin substrate and contains a dilution solvent, the temperature of the resin substrate and the atmosphere is increased and the dilution solvent is sufficiently dried to form a coating film. A hard coat layer can be formed by curing the coating film by irradiating with ultraviolet rays. For example, general electroded or electrodeless high-pressure mercury lamps or metal halide lamps 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 a curing means, a photopolymerization initiator described later is not necessary.

When the ultraviolet curable resin composition is applied to the resin substrate, the thickness of the coating film of the ultraviolet curable resin composition is not particularly limited, but in order to obtain practical performance as a hard coat layer, it is 1 μm or more and 50 μm. The following is preferable. By setting the thickness of the coating film of the ultraviolet curable resin composition within the above range, it becomes possible to uniformly cure to the inside by ultraviolet irradiation, and the adhesion between the hard coat layer and the resin laminate is improved. Cracks due to curing shrinkage of the coating film are less likely to occur.
The thickness of the resin laminate is not particularly limited, but is 0.02 mm in order to enable downsizing and thinning while maintaining the performance such as impact resistance and workability particularly required for the above applications. The preferred range is 2 mm or less. This is particularly effective for protective covers.

  The resin laminate of the present invention is composed of a resin base material and a hard coat layer formed on both surfaces of the resin base material or one of them.

The ultraviolet curable resin composition used in the method for producing a resin laminate of the present invention includes a resin composition containing an ultraviolet curable compound (A), a fatty acid, a fatty acid ester or a derivative thereof (B), and a polysiloxane compound (C). It is applied to both the front and back sides or one side of the resin substrate and cured.
The ultraviolet curable compound (A) is a compound that is cured by being irradiated with ultraviolet rays, and is an ultraviolet curable oligomer or an ultraviolet curable monomer. Among general ultraviolet curable oligomers and ultraviolet curable monomers, Or a combination of an ultraviolet curable oligomer and an ultraviolet curable monomer.
As the ultraviolet curable oligomer or the ultraviolet curable monomer, compounds generally used as an ultraviolet curable oligomer or an ultraviolet curable monomer to be cured by ultraviolet irradiation can be used.

The ultraviolet curable oligomer is used for improving the properties required for the hard coat layer, such as scratch resistance, abrasion resistance, impact resistance, workability, and flexibility.
Examples of the ultraviolet curable oligomer include a urethane acrylate oligomer, an epoxy acrylate oligomer, and a polyester acrylate oligomer.
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.
The UV curable oligomer is particularly preferably a urethane acrylate oligomer, and further, a combination of a UV curable oligomer having 6 or more functions for achieving high hardness and a UV curable oligomer having 3 or less functions for imparting flexibility, It is more preferable in achieving an excellent balance between hardness and impact resistance.
The molecular weight of the ultraviolet curable oligomer is preferably 300 to 30,000, particularly preferably 500 to 10,000. The molecular weight of the ultraviolet curable oligomer is a weight average molecular weight and is measured by GPC (gel permeation chromatography).

Examples of the ultraviolet curable compound (A) include pentafunctional or higher polyfunctional ultraviolet curable monomers or multimers thereof. Further, the ultraviolet curable compound (A) may be a combination of a polyfunctional ultraviolet curable monomer having 5 or more functional groups and a multimer thereof and an ultraviolet curable oligomer.
The ultraviolet curable compound (A) is a pentafunctional or higher polyfunctional ultraviolet curable monomer or a multimer thereof, or a pentafunctional or higher polyfunctional ultraviolet curable monomer or a multimer thereof and an ultraviolet curable oligomer. Is preferable in that the various physical properties (scratch resistance, abrasion resistance, impact resistance, workability, flexibility, etc.) required for the hard coat layer are increased.
In particular, as the ultraviolet curable compound (A), a combination of the above-mentioned pentafunctional or higher polyfunctional ultraviolet curable monomer and a trifunctional or lower urethane acrylate oligomer can achieve an excellent balance between hardness and impact resistance. This is preferable.
Examples of the pentafunctional or higher polyfunctional ultraviolet curable monomer or the dimer or higher compound include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, and tripentaerythritol octaacrylate. .
In the present invention, “pentafunctional” means that the number of functional groups that undergo a polymerization reaction by ultraviolet rays in one molecule, for example, an acrylic group, a methacrylic group, a vinyl group, and the like is five.

Use of the UV curable monomer makes it easy to adjust the crosslink density of the UV curable composition forming the hard coat layer and the viscosity of the UV curable composition, and to adhere the hard coat layer to the resin laminate. Can be improved.
Examples of the UV curable monomer include pentaerythritol tetraacrylate, ditrimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol triacrylate. Examples include acrylate, ethoxylated pentaerythritol tetraacrylate, polyethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated hydrogenated bisphenol A diacrylate, ethoxylated cyclohexanedimethanol diacrylate, and tricyclodecane dimethanol diacrylate.
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 resin laminate of the present invention contains a fatty acid, a fatty acid ester, or a derivative (B) thereof. 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 the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, arachidic acid, and lignoceric acid.
Examples of the fatty acid ester include glycerin fatty acid ester (monoglyceride), organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin condensed ricinoleic acid ester, ethoxylated glycerin fatty acid ester, propylene glycol fatty acid ester, and sucrose fatty acid ester. , Triolein, lecithin, and the like. Specifically, acetic acid monoglyceride, lactic acid monoglyceride, citric acid monoglyceride, diacetyltartaric acid monoglyceride, succinic acid monoglyceride, castor oil (ricinoleic acid triglyceride), polyoxyethylene hydrogenated castor oil, polyoxyethylene glyceryl isostearate, polyoxystearate Ethylene glyceryl, polyoxyethylene glyceryl diisostearate, polyoxyethylene hydrogenated castor oil laurate, polyoxyethylene hydrogenated castor oil isostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, polyoxyethylene tetraoleate Sorbit, tetrastearic acid polyoxyethylene sorbitol, hydrogenated castor oil (hydrogenated ricinoleic acid triglyceride), Polyoxyethylene castor oil, polyoxyethylene phytosterol, polyoxyethylene hydrogenated dimerdilinoleic acid esters, polyoxyethylene cholesteryl ether, polyoxyethylene decyl tetradecyl ether.

A fatty acid derivative is a compound having a structure in which part or all of the side chain of a fatty acid is replaced with another organic group from a methyl group. The fatty acid ester derivative is a compound having a structure in which part or all of the side chain of the fatty acid ester is replaced with another organic group from a methyl group. Examples of the organic group related to the fatty acid derivative and the fatty acid ester derivative include a polyether group, a polyalkyl group, an aralkyl group, and a polyester group. These may be used alone or in combination of two or more.
Among these, as fatty acid, fatty acid ester or derivatives thereof (B), polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl isostearate, polyoxyethylene glyceryl tristearate, polyoxyethylene glyceryl diisostearate, polylauric acid poly Oxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil isostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol tetraoleate, polyoxyethylene sorbitol tetrastearate, polyoxyethylene Castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytosterol, polyoxyethylene cholesteryl ether, One or more hydrocarbons (straight or cyclic) having 12 or more carbon atoms in the molecule among fatty acids, fatty acid esters and / or their derivatives such as dioxylinoleic acid hydrogenated dioxyethylene, and the like, and A structure having a polyether chain having a total of 10 or more repeating units in the same molecule is preferable, and further, two or more linear hydrocarbons having 16 to 18 carbon atoms in the molecule, and A structure having two or more polyether chains having a total of 20 to 80 repeating units in the same molecule is particularly preferred.

Content ratio [(Bs) / (As)] of fatty acid, fatty acid ester or derivative thereof (Bs) to the cured product of the ultraviolet curable compound (As) of the hard coat layer in the portion from the surface of the hard coat layer to 100 nm However, it is 0.07 or more and 3.3 or less, preferably 0.1 or more and 3 or less, more preferably 0.5 or more and 2 or less.
By setting the content ratio [(Bs) / (As)] within this range, the effect of preventing the contamination due to the adhesion of the sebum film is particularly enhanced.
Furthermore, the effect of making the contact angle of the sebum film adhering to the surface lower and making it less noticeable, the effect of remarkably improving the wiping property of the sebum film, or its sufficient durability can be obtained, The optical properties are not deteriorated due to a decrease or an increase in haze, the performance of the hard coat layer itself is maintained, the fatty acid, the fatty acid ester or their derivative (B) is not deposited on the surface, and the appearance is improved. There are no problems.
The content ratio [(Bs) / (As)] is a weight ratio. Further, the weight ratio [(Bs) / (As)] is calculated based on the content of one kind of fatty acid, fatty acid ester or derivative thereof (Bs) alone, When fatty acid esters or their derivatives (Bs) are a combination of two or more, it is calculated based on their total content.
Moreover, the part from the surface of a hard-coat layer to 100 nm refers to the part by the side of the surface from the position of 100 nm from the surface among hard-coat layers. The portion other than 100 nm from the surface of the hard coat layer refers to a portion of the hard coat layer on the resin substrate side from a position of 100 nm from the surface.
The content ratio [(Bs) / (As)] of fatty acid, fatty acid ester or derivative thereof (Bs) to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer is: Using a time-of-flight secondary ion mass spectrometer TOF-SIMS (Time Of Flight-Secondary Ion Mass Spectroscopy), a cured product of an ultraviolet curable compound (As) and a fatty acid, a fatty acid ester or a derivative thereof from the surface of the hard coat layer ( The content of Bs) is obtained, and is a value calculated from the obtained content value.
Examples of the method for setting the content ratio [(Bs) / (As)] in the above range include, for example, the ultraviolet curable compound (A) and the fatty acid, fatty acid ester or the like in the ultraviolet curable resin composition forming the hard coat layer. The content of the derivative (B) may be appropriately adjusted.
For example, it adjusts by mix | blending 0.01-5 weight part of fatty acid, fatty acid ester, or those derivatives (B) with respect to 100 weight part of ultraviolet curable compounds (A) in an ultraviolet curable resin composition. Is possible.

Content ratio [(Br) / (Ar)] of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer Is 0.08 or less, preferably 0.03 or less, particularly preferably more than 0 and 0.01 or less.
The content ratio [(Br) / (Ar)] can be calculated from the following formula (1), for example.

Ａｔ：ハードコート層全体の（Ａ）成分の含有量（重量）
Ｂｔ：ハードコート層全体の（Ｂ）成分の含有量（重量）
ｔ ：ハードコート層の厚さ（μｍ）
Ａｓ：ハードコート層の表面から１００ｎｍの（Ａ）成分の含有量（重量）
Ｂｓ：ハードコート層の表面から１００ｎｍの（Ｂ）成分の含有量（重量）
なお、ハードコート層全体の（Ａ）成分の含有量とは、前記ハードコート層の表面から１００ｎｍまでの部分に含まれる（Ａ）成分と前記ハードコート層の表面から１００ｎｍ以外の部分に含まれる（Ａ）成分との合計に含有量である。同様に、ハードコート層全体の（Ａ）成分の含有量とは、前記ハードコート層の表面から１００ｎｍまでの部分に含まれる（Ａ）成分と前記ハードコート層の表面から１００ｎｍ以外の部分に含まれる（Ａ）成分との合計に含有量である。

At: Content (weight) of component (A) in the entire hard coat layer
Bt: Content (weight) of component (B) in the entire hard coat layer
t: thickness of hard coat layer (μm)
As: Content (weight) of component (A) 100 nm from the surface of the hard coat layer
Bs: Content (weight) of component (B) 100 nm from the surface of the hard coat layer
The content of the component (A) in the entire hard coat layer is included in a portion other than 100 nm from the surface of the hard coat layer and the component (A) included in the portion from the surface of the hard coat layer to 100 nm. (A) It is content in the sum total with a component. Similarly, the content of the component (A) in the entire hard coat layer is included in a portion other than 100 nm from the surface of the hard coat layer and the component (A) included in the portion from the surface of the hard coat layer to 100 nm. It is content in the sum total with (A) component.

In the resin laminate of the present invention, in particular, at least one selected from fatty acids, fatty acid esters or derivatives thereof (B) is added to the ultraviolet curable compound (A) in a portion from the surface of the hard coat layer to a depth of 100 nm. The cured product is characterized by being contained at a higher concentration than the portion other than 100 nm from the surface of the hard coat layer.
When the fatty acid, fatty acid ester or derivative thereof (B) is contained in a high concentration up to a portion deeper than the surface of the hard coat layer, the contact angle of the sebum film adhering to the surface is lowered to make it inconspicuous, Although the effect of remarkably improving the wiping property of the film can be obtained, the optical properties are deteriorated due to a decrease in transmittance or an increase in haze, or the performance of the hard coat layer itself is deteriorated. It is not preferable for the use of the resin laminate.

The hard coat layer according to the resin laminate of the present invention preferably further contains a modified polysiloxane compound (C). The modified polysiloxane compound (C) is a compound having polydimethylsiloxane as a basic structure, and has a structure in which part or all of the side chain of polydimethylsiloxane is replaced with another organic group from a methyl group. Examples of the organic group related to the modified polysiloxane compound (C) 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.
Specifically, the modified polysiloxane compound (C) is particularly preferably polyether-modified polydimethylsiloxane or polyether-modified polymethylalkylsiloxane. The polyether group as the organic group related to the modified polysiloxane compound (C) is composed of a homopolymer of ethylene oxide or polyprene oxide, or a copolymer of ethylene oxide or polyprene oxide.

The content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) in the portion from the surface of the hard coat layer to a depth of 100 nm is 0.0007. As described above, it is 0.15 or less, preferably 0.001 or more and 0.1 or less, more preferably 0.005 or more and 0.05 or less.
When the content ratio [(Cs) / (As)] is within the above range, the contact angle of the sebum film adhering to the surface is lowered and made inconspicuous, and the wiping property of the sebum film is remarkably improved. Or the durability is increased. Furthermore, the smoothness of the hard coat layer is easily obtained, and the performance of the hard coat layer itself is enhanced.
In order to obtain the content ratio [(Cs) / (As)] of the portion from the surface of the hard coat layer to a depth of 100 nm, the content is appropriately adjusted. For example, it can be adjusted by blending 0.0001 to 0.3 parts by weight of the modified polysiloxane compound (C) with respect to 100 parts by weight of the ultraviolet curable compound (A).

  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 membrane are, for example, fatty acids 7.9 to 39.0%, triglycerides 9.5 to 49.4%, diglycerides / monoglycerides 2.3 to 4.3%, wax esters 22.6 to 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 or fatty acid ester derivatives. 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.

  Moreover, when the hardened | cured material of the ultraviolet curable compound (A) which forms a hard-coat layer contains a modified polysiloxane compound (C) and does not contain a fatty acid, fatty acid ester, or derivatives (B), modified polysiloxane compound ( Although a laminate having a smooth surface and sufficient optical properties such as transmittance and haze can be obtained by the single effect of C), the wiping property of the sebum film is slightly less than when the modified polysiloxane compound (C) is not included. However, the effect of reducing the contact angle of the sebum film adhering to the surface to make it less noticeable, or significantly improving the wiping property of the sebum film cannot be obtained.

  In this invention, the hardened | cured material of the ultraviolet curable compound (A) which forms a hard-coat layer is a compound with affinity with a sebum film, a fatty acid, fatty acid ester or those derivatives (B), and a modified polysiloxane compound (C ) At the same time, the effect of lowering the contact angle of the sebum film adhering to the surface of the hard coat layer and making it inconspicuous is increased, and the smooth surface has no deterioration in optical properties such as transmittance and haze The effect of improving the wiping property of the sebum film is enhanced. The cured product of the ultraviolet curable compound (A) that forms the hard coat layer contains a fatty acid, a fatty acid ester or a derivative thereof (B), and a modified polysiloxane compound (C) in a high concentration on the surface of the hard coat layer. These effects increase.

The thickness of the hard coat layer is preferably 1 μm or more and 50 μm or less. When the thickness of the hard coat layer is within the above range, it can be uniformly cured to the inside by ultraviolet irradiation, and the adhesion between the hard coat layer and the resin laminate is good, and due to the curing shrinkage of the coating film. Cracks do not occur.

  The hard coat layer according to the resin laminate of the present invention is obtained by applying an ultraviolet curable resin composition to the surface of a resin base material and then irradiating the ultraviolet curable resin composition with ultraviolet rays to cure the resin. It is formed on the surface of the substrate.

  The ultraviolet curable resin composition used for forming the hard coat layer according to the resin laminate of the present invention contains an ultraviolet curable compound (A) and a fatty acid, a fatty acid ester or a derivative thereof (B). The ultraviolet curable composition preferably further contains a modified polysiloxane compound (C) in addition to the ultraviolet curable compound (A) and the fatty acid, fatty acid ester or derivative thereof (B). The content of the ultraviolet curable compound (A), fatty acid, fatty acid ester or derivative thereof (B) and modified polysiloxane compound (C) in the ultraviolet curable composition is the content ratio [(Bs) / (As)]. Or it selects suitably by the installation value of content-ratio [(Cs) / (As)].

The ultraviolet curable resin composition can contain a photopolymerization initiator. A photoinitiator is added to an ultraviolet curable composition in order to start reaction (polymerization) of an 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, aromatic ketones such as benzophenone and benzoylbenzoic acid, alphagecarbonyls such as benzyl, benzyldimethyl ketal, benzyl Benzyl ketals such as diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-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 desirably used in combination of two or more.

  The ultraviolet curable resin composition can contain, in addition to the above components, a surface conditioner, a diluent solvent, an inorganic or organic filler, as necessary.

  The surface conditioner contained in the ultraviolet curable resin composition is added to the ultraviolet curable resin composition as necessary in order to obtain an excellent appearance by smoothing the coated film after coating, For example, a small amount of a fluorine compound or an acrylic copolymer can be mentioned.

The ultraviolet curable composition used for forming the hard coat layer of the 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 resin composition is added to the ultraviolet curable resin composition as necessary in order to easily apply the ultraviolet curable resin composition to the resin laminate.
Examples of such substances 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. Esters such as ketones, ethyl acetate, butyl acetate, and methoxypropyl acetate, cellosolve solvents such as ethyl cellosolve, and glycol solvents such as methoxypropanol, ethoxypropanol, and methoxybutanol can be used alone or in combination.

As a method for producing an ultraviolet curable resin composition for forming a hard coat layer, the above-mentioned (A), (B), (C), a photopolymerization initiator, and other surface conditioners to be added as necessary Each component such as a diluting solvent, inorganic or organic filler is weighed and mixed, and is prepared by stirring and mixing so as to obtain a uniform ultraviolet curable resin composition.
For example, each component is mixed, heated as necessary (desirably 60 ° C. or less), and until uniform using a stirrer such as a dissolver or a dispersing device such as a ball mill, for example, for about 1 to 30 minutes, It can be prepared by mixing and stirring.

As a resin base material which concerns on the resin laminated body of this invention, if it is common resin, it can be used without being restrict | limited especially.
Applications of the resin laminate of the present invention include mobile phones, digital cameras, digital video cameras, televisions, personal computers, portable game machines, GPS (Global Positioning System), liquid crystal displays such as touch panels, goggles, CDs, DVDs. From the viewpoints of transparency, workability, and impact resistance, the resin base material is preferably an acrylic resin or a polycarbonate resin. In addition, as the resin base material, for example, a general transparent resin such as polyethylene terephthalate resin, polyvinyl chloride resin, and polystyrene resin is also preferable.
The thickness of the resin base material is not particularly limited, but is 0.02 mm or more in order to reduce the size and thickness while maintaining the performance (impact resistance, workability, etc.) particularly required for the above applications. The range of 2 mm or less is preferable.

  The image display body of the present invention is an image display body having a display portion, and the above-mentioned resin laminate is used for the display portion of the image display body. Specifically, it is a mobile phone or a liquid crystal display body. Is preferred.

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 materials were used.
<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) Dipentaerythritol hexaacrylate (trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) << UV curable monomer >>
(A4) Pentaerythritol tetraacrylate (trade name: A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) << UV curable monomer >>
(A5) 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 glyceryl isostearate (trade name: GWIS-110, manufactured by Nippon Emulsion Co., Ltd.)
(B2) Polyoxyethylene glyceryl tristearate (trade name: GWS320, manufactured by Nippon Emulsion Co., Ltd.)
(B3) polyisoethylene glyceryl diisostearate (trade name: GWIS-260EX, manufactured by Nippon Emulsion Co., Ltd.)
(B4) Lauric acid polyoxyethylene hydrogenated castor oil (trade name: RWL-150, manufactured by Nippon Emulsion Co., Ltd.)
(B5) Isostearic acid polyoxyethylene hydrogenated castor oil (trade name: Emalex RWIS-10, manufactured by Nippon Emulsion Co., Ltd.)
(B6) Tetraoleic acid polyoxyethylene sorbit (trade name: Emanon 460V, manufactured by Kao Corporation)
(B7) tetrastearate polyoxyethylene sorbit (trade name: Nikkor GS460, manufactured by Nikko Chemicals)
(B8) Polyoxyethylene castor oil (trade name: C-40 manufactured by Nippon Emulsion Co., Ltd.)
(B9) Polyoxyethylene hydrogenated castor oil (trade name: Emanon CH-60, manufactured by Kao Corporation)
(B10) Polyoxyethylene phytosterol (trade name: Nikkor BPS-10, manufactured by Nikko Chemicals)
(B11) Polyoxyethylene hydrogenated dimer linoleic acid ester (trade name: EMALEX DICD-30, manufactured by Nippon Emulsion Co., Ltd.)
<Modified polysiloxane compound (C)>
(C1) Modified polysiloxane compound (trade name: SH28PA, manufactured by Toray Dow Corning) (C2) Modified polysiloxane compound (trade name: Granol 400, manufactured by Kyoeisha Chemical Co., Ltd.)
<Photopolymerization initiator>
1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Japan)

<Example 1>
(A) As an ultraviolet curable compound, 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, Irgacure 184 was added as a photopolymerization initiator in an amount of 5% by weight with respect to the ultraviolet curable compound. To this, (B) fatty acid, fatty acid ester or derivatives thereof, polyoxyethylene glyceryl isostearate (GWIS-110) was added at a blending ratio shown in Table 1, and the blended solution was sufficiently stirred to cure the UV curable resin composition. And then stored in a sealed container.
As the resin base material, an acrylic resin base material having a thickness of 1.5 mm ("SUMIPEX E" manufactured by PMMA Sumitomo Chemical Co., Ltd.) was prepared, and using the bar coater, the above-prepared ultraviolet ray was formed so that the wet film thickness was about 15 μm. The curable resin composition was applied on a resin substrate.
The resin base material coated with the ultraviolet curable resin composition is placed in a hot air circulation oven at 50 ° C. and dried for 10 minutes, and then the coating film is cured by irradiating with ultraviolet rays using a metal halide lamp (USHIO Inc.). A resin laminate having a hard coat layer with a thickness of 3 μm was obtained. When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 1.1. Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.

<Example 2>
(A) As an ultraviolet curable compound, EB1290 / EB8402 / A-TMMT / A-
Except that the ratio of BPE-4 was changed to 55/5/30/10 and (B) the fatty acid, fatty acid ester or derivative thereof was changed to polyoxyethylene glyceryl tristearate (GWS320), the same as in Example 1. Thus, a resin laminate having a hard coat layer with a thickness of 3 μm was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 0.9. Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less. <Example 3>
(B) Fatty acid, fatty acid ester or their derivatives are changed to polyoxyethylene glyceryl diisostearate (GWIS-260EX), and (B) fatty acid, fatty acid ester or their derivatives and (C) SH28PA as a modified polysiloxane compound at the same time A resin laminate having a hard coat layer with a film thickness of 5 μm was obtained in the same manner as in Example 1 except that it was added at a blending ratio shown in Table 1 and applied with a wet film thickness of about 25 μm.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 1.0, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.005. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.

<Example 4>
(A) Among the UV curable compounds, EB1290 is changed to A-DPH, (B) fatty acid, fatty acid ester or derivative thereof is changed to polyoxyethylene hydrogenated castor oil (RWL-150), (C ) A resin laminate having a 5 μm thick hard coat layer was obtained in the same manner as in Example 3 except that SH28PA was added as a modified polysiloxane compound and the wet film thickness was about 25 μm.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 2.1, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.05. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.
<Example 5>
(B) Fatty acid, fatty acid ester or derivative thereof is changed to polyoxyethylene hydrogenated castor oil (RWIS-10), and the dilution solvent is changed to 80/20 mixed dilution solvent of propylene glycol monomethyl ether / isobutyl alcohol, Example 3 except that the resin base material was changed to a polycarbonate resin base material having a thickness of 0.5 mm ("Polyca Ace" manufactured by PC Sumitomo Bakelite Co., Ltd.), the drying temperature was changed to 70 ° C, and the drying time was 5 minutes. Similarly, a resin laminate having a hard coat layer with a thickness of 5 μm was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] is 3. Similarly, the content ratio of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) [(Cs) / (
As)] was 0.1. Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.

<Example 6>
(B) Tetraoleic acid polyoxyethylene sorbite (460V) is changed as fatty acid, fatty acid ester or derivatives thereof, (C) the modified polysiloxane compound is changed to granol 400, and the resin base material is polyethylene having a thickness of 188 μm. A resin laminate having a hard coat layer with a thickness of 5 μm was obtained in the same manner as in Example 3 except that it was changed to a terephthalate resin base material (PET Toyobo “Cosmo Shine A4300”).
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 0.1, and the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.001. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.
<Example 7>
(A) The ratio of A-DCP / EB8402 / A-TMMT / A-BPE-4 of the ultraviolet curable compound was changed to 70/10/10/10, and (B) fatty acid, fatty acid ester or derivative thereof was changed. Resin laminate having a hard coat layer with a film thickness of 5 μm in the same manner as in Example 3 except that the polyoxyethylene sorbitol tetrastearate (GS460) was changed and (C) the modified polysiloxane compound was changed to granol 400. Got.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 0.5, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.005. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.

<Example 8>
(A) As a UV curable compound, the ratio of EB1290 / A-DCP / EB8402 / A-TMMT / A-BPE-4 was 30/30/20/10/10, and (B) fatty acid, fatty acid ester or their A resin laminate having a hard coat layer with a film thickness of 8 μm is obtained in the same manner as in Example 7 except that the derivative is changed to polyoxyethylene castor oil (C-40) and the wet film thickness is about 40 μm. It was.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 1.8, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.03. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.
<Example 9>
(A) As an ultraviolet curable compound, EB1290 / A-DCP / EB8402 / AB
Except that the ratio of PE-4 was 25/30/25/20 and (B) fatty acid, fatty acid ester or derivative thereof was changed to polyoxyethylene hydrogenated castor oil (CH-60), the same as in Example 7 Thus, a resin laminate having a hard coat layer with a thickness of 8 μm was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 0.8, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.015. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.

<Example 10>
(B) A hard coat having a film thickness of 3 μm in the same manner as in Example 7 except that the fatty acid, fatty acid ester or derivative thereof was changed to polyoxyethylene phytosterol (BPS-10) and the wet film thickness was about 15 μm. A resin laminate having a layer was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 1.5, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.02. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.
<Example 11>
(B) A hard coat layer having a film thickness of 3 μm is provided in the same manner as in Example 10 except that the fatty acid, fatty acid ester or derivative thereof is changed to polyoxyethylene hydrogenated dimer dilinoleate (DICD-30). A resin laminate was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) relative to the ultraviolet curable compound (hardened product of As) in the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 2.3, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.07. . Further, the content ratio of fatty acid, fatty acid ester or derivative thereof (Br) to the cured product of the ultraviolet curable compound (Ar) of the hard coat layer in a portion other than 100 nm from the surface of the hard coat layer [(Br) / (Ar )] Was calculated from the above formula (1) and was 0.08 or less.

<Comparative Example 1>
(B) Fatty acid, fatty acid ester or a derivative thereof, polyoxyethylene glyceryl isostearate (GWIS-110) was added in the mixing ratio shown in Table 1, and the film thickness was 3 μm in the same manner as in Example 1. A resin laminate having a hard coat layer was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 3.6.
<Comparative example 2>
(B) Fatty acid, fatty acid ester derivatives thereof, polyoxyethylene glyceryl diisostearate (GWIS-260EX) was added in the blending ratio shown in Table 1 in the same manner as in Example 3, and a film thickness of 5 μm. A resin laminate having a hard coat layer was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 0.05, and the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.005. .

<Comparative Example 3>
(B) A resin laminate having a hard coat layer with a thickness of 5 μm was obtained in the same manner as in Example 7 except that no fatty acid, fatty acid ester or derivative thereof was added.
When the content of the modified polysiloxane compound (Cs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Cs) / (As) ] Was 0.005.
<Comparative Example 4>
(B) Fatty acid, fatty acid ester or derivatives thereof were added at the blending ratios shown in Table 1, and a hard coat having a film thickness of 5 μm was obtained in the same manner as in Example 7 except that (C) component was added excessively. A resin laminate having a layer was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 0.5, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.3. <Comparative Example 5>
(B) Fatty acid, fatty acid ester or derivatives thereof, and (C) a modified polysiloxane compound in the same manner as in Example 7 except that a hard coating layer having a film thickness of 5 μm was added in the blending ratio shown in Table 1. A resin laminate having the following was obtained.
When the content of fatty acid, fatty acid ester or derivative thereof (Bs) with respect to the cured product of the ultraviolet curable compound (As) of the hard coat layer at a portion of 100 nm from the surface of the hard coat layer was measured, the content ratio [(Bs) / (As)] was 4.3, and similarly, the content ratio [(Cs) / (As)] of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) was 0.2.

The following evaluation was implemented about the produced said resin laminated body.
<Measurement Method of Content Ratio ([(Bs) / (As)] and [(Cs) / (As)]])
Measurement of a portion of 100 nm from the surface of the hard coat layer was performed using a time-of-flight secondary ion mass spectrometer TOF-SIMS (Time Of Flight-Secondary Ion Mass Spectroscopy). Using the prepared resin laminate, the content of each component from the surface of the hard coat layer to a depth of 100 nm was measured by measuring while performing ion sputtering from the sample surface of the resin laminate. A specific peak was specified in advance using each component and used as a measurement peak. The content of each component was the average value of the portion from the outermost surface to a depth of 100 nm. The ratio was a weight ratio.

<Appearance, cloudy surface>
Using the produced resin laminate, visual observation was performed at a distance of 10 cm directly below a 20 W 3-wavelength fluorescent lamp in a dark room, and the cloudiness of the hard coat surface, the presence or absence of precipitates, and the smoothness of the surface were confirmed.
<Optical characteristics>
Using the produced resin laminate, the total light transmittance (Tt) and haze (Hz) are measured in accordance with JIS K 7105 using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). did.

<Hard coat properties>
Using the prepared resin laminate, 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 sample surface was visually checked for scratches. And evaluated according to the following criteria.
A: No scratches / practical superior B: Several scratches / practical enough C: Overall scratches / practical poor

<Anti-fouling property of sebum film>
Sebum film adherence prevention I (Adhesion stains are not noticeable / invisible)
Triolein as a sebum component was attached to the index finger, and the finger was pressed against the surface of the hard coat layer of the resin laminate on which the finger was produced at a constant load (1 kg) for retransfer. The surface of the hard coat layer to which triolein was transferred was observed at a magnification of 200 times with a microscope (VK9700 manufactured by Keyence Corporation).
Evaluation was made according to the following criteria according to the triolein adhesion state.
A: Triolein adhering to a fingerprint is in a state where 70% or more of the area is wet and spread (not a droplet having a diameter of 100 μm or less) (the fingerprint is very difficult to see)
B: Triolein adhering to the fingerprint shape is wet and spread by 50% or more and less than 70% in area (a state where the droplet is not a droplet having a diameter of 100 μm or less) (the fingerprint is difficult to see)
C: Triolein adhering to the fingerprint is in the form of droplets with an area of more than 50% and a diameter of 100 μm or less, and is not wet and spread (the fingerprint is easy to see)

Sebum film adherence prevention II (Inconspicuousness / invisibleness after wiping off attached dirt)
After transferring triolein to the hard coat layer surface in the same manner as described above, a wiper (trade name: Handy Wiper, manufactured by Kuraray Co., Ltd.) is attached to a holder having a diameter of 30 mm, a constant load (1 kg), a constant speed (6000 m / min). ), And the surface of the test specimen was visually observed in a dark room at a distance of 10 cm immediately below a 20 W 3-wavelength fluorescent lamp to confirm the state of triolein adhesion. Moreover, the increase ((DELTA) H) of the haze compared with the test before was measured based on JISK7105 using the haze meter (brand name: NDH2000, Nippon Denshoku Kogyo Co., Ltd.).
A: Sebum membrane is almost completely wiped off, ΔH is less than 0.05% B: Sebum membrane is almost wiped off, ΔH is 0.05% or more and less than 0.2% C: Sebum membrane Is almost not wiped off and is white and cloudy, and ΔH is 0.2% or more

  Tables 1 and 2 show the results of evaluating the resin laminates produced in each Example and Comparative Example.

As is apparent from the results in Table 1, in Examples 1 to 11 using the resin laminate of the present invention, Example 1 in which fatty acids, fatty acid esters or derivatives thereof (component (B)) were contained in the appropriate range. In Example 2 and Example 2, excellent adhesion prevention property (I) of the sebum film is shown. In Examples 3 to 11, in addition to the component (B), the modified polysiloxane compound (component (C) ) Is contained within an appropriate range, and exhibits a good sebum film adhesion dirt prevention property (I) and a better sebum film adhesion dirt prevention adhesion dirt prevention property (II). It had the effect of preventing the adhesion dirt. Moreover, the hard coat property and appearance, total light transmittance, and haze also maintained practical performance.
Moreover, about Examples 1-11, printability evaluation was implemented and there was no problem in particular about printability, and it was favorable.
On the other hand, in Comparative Example 1 in which the component (B) is excessively contained and in Comparative Example 5 in which both the component (B) and the component (C) are excessively contained, there is a problem in hard coat properties and appearance, and the sebum film adheres The antifouling property was not evaluated. Moreover, although (C) component is contained in an appropriate amount, the content of (B) component is less than the appropriate range in Comparative Example 2, (B) component is not included, and (C) component is included in the appropriate range. In Comparative Example 3 and Comparative Example 4 in which the component (C) was excessively contained, there was no problem in hard coat properties and appearance, but sufficient seizure film antifouling property could not be obtained.

Claims (4)

An ultraviolet curable resin composition comprising an ultraviolet curable compound (A), a fatty acid, a fatty acid ester or a derivative thereof (B), and a polysiloxane compound (C) on a resin substrate on both front and back surfaces or one surface of the resin substrate. Applying step;
The manufacturing method of the resin laminated body which has the process of hardening | curing the apply | coated ultraviolet curable resin composition.   Content ratio of the modified polysiloxane compound (Cs) to the cured product of the ultraviolet curable compound (As) in a portion from the surface of the hard coat layer to 100 nm of the hard coat layer made of the cured product of the ultraviolet curable resin composition [(Cs) / (As)] is 0.0007 or more and 0.15, The manufacturing method of the resin laminated body of Claim 1.   A hard coat layer made of a cured product of the ultraviolet curable resin composition is a fatty acid, a fatty acid ester or a derivative thereof (Bs) for a cured product of the ultraviolet curable compound (As) in a portion from the surface of the hard coat layer to 100 nm. ) Content ratio [(Bs) / (As)] is 0.07 or more and 3.3 or less, The method for producing a resin laminate according to claim 1 or 2.   The method for producing a resin laminate according to any one of claims 1 to 3, wherein the resin substrate is a resin substrate containing an acrylic resin or a polycarbonate resin.