JP5835552B2 - Antistatic laminate, method for producing the same, and curable composition - Google Patents

Description

  The present invention relates to an antistatic laminate, a method for producing the same, and a curable composition.

  Conventionally, from the viewpoint of securing the performance of information communication equipment and safety measures, it has been carried out to form a scratch-resistant coating film (hard coat) or an antistatic coating film (antistatic film) on the surface of the equipment. ing. In recent years, in the field of optical components (for example, plastic lenses) and display panels, prevention of adhesion of dust due to static electricity is required, and the need for an antistatic film is very high.

  The antistatic film used in such a field is formed by applying a curable composition in which conductive particles are dispersed in a mixed solution containing a binder resin and an organic solvent, and then curing by heating and / or radiation. A cured film has been proposed (see, for example, Patent Document 1). In addition, a technique has been proposed in which conductive particles are unevenly distributed in the vicinity of the cured film interface by mixing a dispersant having a specific structure with the conductive particles to suppress the surface resistance value to be low (for example, Patent Document 2). reference).

JP 2001-131485 A JP 2008-247948 A

  However, the conventional antistatic film has a problem that the uneven distribution of the conductive particles is unstable, so that sufficient conductivity (antistatic property) cannot be exhibited. Therefore, in order to increase the conductivity of the antistatic film, the amount of conductive particles contained in the curable composition has to be increased. When the amount of the conductive particles in the curable composition is increased, the transparency may decrease due to an increase in visible light absorption by the cured film. Thus, the conventional antistatic film has room for improvement in terms of productivity.

  Therefore, some embodiments according to the present invention provide a curable composition that can improve productivity and can form a cured film excellent in transparency and antistatic property by solving the above-mentioned problems, or the cured film. An antistatic laminate having the above and a method for producing the same are provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the antistatic laminate according to the present invention is:
A cellulose resin substrate;
A cured film of a curable composition containing a polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) for dissolving a cellulose resin, and a conductivity-imparting component (B),
The cellulose resin substrate and the cured film are laminated in contact with each other, and the conductivity imparting component (B) is unevenly distributed on the opposite side of the cellulose resin substrate in the cured film. Here, the component that dissolves the cellulose resin is a cellulose resin film having a thickness of 18 μm cut into a size of 18 cm × 1 cm, soaked in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film at 80 ° C. The component whose mass reduction | decrease rate of the film when dried with a vacuum dryer for 24 hours is 1% or more is said.

[Application Example 2]
One aspect of the antistatic laminate according to the present invention is:
A cellulose resin substrate;
2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate And a cured film of a curable composition containing the conductivity-imparting component (B),
The cellulose resin substrate and the cured film are laminated in contact with each other, and the conductivity imparting component (B) is unevenly distributed on the opposite side of the cellulose resin substrate in the cured film.

  Here, “the conductivity imparting component (B) is unevenly distributed on the side opposite to the cellulose resin substrate in the cured film” means that the conductivity imparting component on the side opposite to the cellulose resin substrate in the cured film is used. It means that the density of (B) is higher than the density of the conductivity-imparting component (B) on the cellulose resin substrate side in the cured film. The relative magnitude of the density of the conductivity-imparting component (B) on the cellulose resin substrate side and the opposite side of the cellulose resin substrate in the cured film can be determined, for example, by observing the cross section of the antistatic laminate with an electron microscope. Can be determined. The larger the difference in density of the conductivity-imparting component (B) between the cellulose resin substrate side and the opposite side, the better. The conductivity imparting component (B) is present at a high density on the side opposite to the cellulose resin substrate in the cured film, and the conductivity imparting component (B) is substantially present on the cellulose resin substrate side in the cured film. It is particularly preferred that it is not present in

[Application Example 3]
In the antistatic laminate of Application Example 1 or Application Example 2,
The said cured film can contain the cellulose resin which forms the said cellulose resin base material.

[Application Example 4]
In the antistatic laminate of any one of Application Examples 1 to 3,
The conductivity-imparting component (B) may be conductive particles.

[Application Example 5]
In the antistatic laminate of Application Example 4,
The conductive particles may be at least one selected from antimony-containing tin oxide particles and phosphorus-containing tin oxide particles.

[Application Example 6]
In the antistatic laminate of Application Example 4 or Application Example 5,
Content of the said electroconductive particle can be 5 mass% or more and 20 mass% or less in the said curable composition except an organic solvent.

[Application Example 7]
In the antistatic laminate of any one of Application Examples 1 to 3,
The conductivity-imparting component (B) may be a conductive polymer.

[Application Example 8]
In the antistatic laminate of Application Example 7,
Content of the said conductive polymer can be 0.1 mass% or more and 5 mass% or less in the said curable composition except an organic solvent.

[Application Example 9]
One aspect of the method for producing an antistatic laminate according to the present invention is as follows.
A curable composition containing a polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) for dissolving the cellulose resin and a conductivity-imparting component (B) was applied to a cellulose resin substrate. Thereafter, a curing step is included. Here, the component that dissolves the cellulose resin is a cellulose resin film having a thickness of 18 μm cut into a size of 18 cm × 1 cm, soaked in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film at 80 ° C. The component whose mass reduction | decrease rate of the film when dried with a vacuum dryer for 24 hours is 1% or more is said.

[Application Example 10]
One aspect of the method for producing an antistatic laminate according to the present invention is as follows.
2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ) And a conductivity-imparting component (B) are applied to the cellulose resin substrate and then cured.

[Application Example 11]
In the production method of the antistatic laminate of Application Example 9 or Application Example 10,
The conductivity-imparting component (B) may be conductive particles.

[Application Example 12]
In the method for producing an antistatic laminate of Application Example 11,
The conductive particles may be at least one selected from antimony-containing tin oxide particles and phosphorus-containing tin oxide particles.

[Application Example 13]
In the manufacturing method of the antistatic laminate of Application Example 11 or Application Example 12,
Content of the said electroconductive particle can be 5 mass% or more and 20 mass% or less in the said curable composition except an organic solvent.

[Application Example 14]
In the production method of the antistatic laminate of Application Example 9 or Application Example 10,
The conductivity-imparting component (B) may be a conductive polymer.

[Application Example 15]
In the method for producing an antistatic laminate of Application Example 14,
Content of the said conductive polymer can be 0.1 mass% or more and 5 mass% or less in the said curable composition except an organic solvent.

[Application Example 16]
One aspect of the curable composition according to the present invention is:
A curable composition used for producing an antistatic laminate,
It contains a polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) that dissolves the cellulose resin, and a conductivity-imparting component (B). Here, the component that dissolves the cellulose resin is a cellulose resin film having a thickness of 18 μm cut into a size of 18 cm × 1 cm, soaked in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film at 80 ° C. The component whose mass reduction | decrease rate of the film when dried with a vacuum dryer for 24 hours is 1% or more is said.

[Application Example 17]
One aspect of the curable composition according to the present invention is:
A curable composition used for producing an antistatic laminate,
2-hydroxyethyl (meth) acrylate, acryloylmorpholine, γ-butyrolactone acrylate, hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4- A polymerizable compound (A) containing 5% by mass or more and 75% by mass or less of a polymerizable component (A1) which is at least one selected from hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, ethylene glycol diacrylate and diethylene glycol diacrylate ) And a conductivity-imparting component (B).

[Application Example 18]
In the curable composition of Application Example 16 or Application Example 17,
The conductivity-imparting component (B) may be conductive particles.

[Application Example 19]
In the curable composition of Application Example 18,
The conductive particles may be at least one selected from antimony-containing tin oxide particles and phosphorus-containing tin oxide particles.

[Application Example 20]
In the curable composition of Application Example 18 or Application Example 19,
Content of the said electroconductive particle can be 5 mass% or more and 20 mass% or less in the said curable composition except an organic solvent.

[Application Example 21]
In the curable composition of Application Example 16 or Application Example 17,
The conductivity-imparting component (B) may be a conductive polymer.

[Application Example 22]
In the curable composition of Application Example 21,
Content of the said conductive polymer can be 0.1 mass% or more and 5 mass% or less in the said curable composition except an organic solvent.

  According to the antistatic laminate of the present invention, a layer in which the conductivity-imparting component (B) is present at a high density is formed on the surface of the cured film opposite to the surface in contact with the cellulose resin substrate. Thus, excellent conductivity (antistatic property) is imparted when the layer becomes a conductive path.

  According to the method for producing an antistatic laminate according to the present invention, by applying and curing the curable composition on a cellulose resin as a base material, on the surface side opposite to the surface in contact with the cellulose resin. A layer in which the conductivity imparting component (B) is present at a high density can be formed. Since such a layer serves as a conductive path, a laminate having excellent conductivity (antistatic property) can be produced. Moreover, since the layer in which electroconductivity provision component (B) exists in high density is formed in the surface side opposite to the surface which contacts a cellulose resin, the electroconductivity provision component (B) contained in a curable composition The amount of can be reduced. As a result, the transparency of the laminate can be ensured and the productivity can be improved.

It is sectional drawing which showed typically the laminated body for antistatic which concerns on this Embodiment.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included.

1. Curable composition The curable composition which concerns on this Embodiment contains (A) polymeric compound and (B) electroconductivity provision component. Hereinafter, each component of the curable composition which concerns on this Embodiment is demonstrated in detail. In the present specification, the materials (A) to (D) may be abbreviated as components (A) to (D), respectively.

1.1. (A) Polymerizable compound The polymerizable compound (A) used in the present embodiment is not particularly limited as long as it is a polymerizable compound, but a compound having an ethylenically unsaturated group is preferred. (A) The polymerizable compound is a polymerizable compound that dissolves the cellulose resin (hereinafter also referred to as “(A1) component”), and a polymerizable compound other than the (A1) component (hereinafter also referred to as (A2) component). , Can be classified.

  In addition, the content of the component (A) in the curable composition according to the present embodiment is preferably 80 to 99% by mass when the total of the components excluding the solvent (D) is 100% by mass, 90 -98 mass% is more preferable. When the content of the component (A) is in the above range, a cured film having high hardness can be formed.

1.1.1. (A1) Component The curable composition which concerns on this Embodiment contains the polymeric compound which melt | dissolves (A1) cellulose resin. In the present invention, the “polymerizable compound that dissolves the cellulose resin” means that the mass of the cellulose resin film of the substrate having a thickness of 80 μm cut into a size of 18 cm × 1 cm is a ₀ (g), and this film is a room temperature environment. When the mass of the film after dipping in 6 g of the polymerizable compound for 2 hours and drying the taken-out film with a vacuum dryer at 80 ° C. for 24 hours is defined as a ₁ (g), ((a ₀ -a ₁ ) / A ₀ ) A polymerizable compound having a mass reduction rate of 1% or more represented by x100.

  When the curable composition according to the present embodiment contains the component (A1), the (B) conductivity imparting component is unevenly distributed at the time of film formation, resulting in excellent conductivity (antistatic properties). ) Can be formed.

  (B) Although the mechanism by which the uneven distribution of the conductivity imparting component appears is not clear, in the present embodiment, for example, it is considered as follows. When the curable composition concerning this Embodiment is apply | coated on a cellulose resin base material, since (A1) component melt | dissolves a cellulose resin, it elutes in the curable composition with which the cellulose resin was apply | coated. Here, (B) the conductivity-imparting component is inferior in affinity with the eluted cellulose resin, so it is presumed that the cellulose resin concentration is unevenly distributed in the curable composition, that is, on the side opposite to the substrate. The

  On the other hand, in the curable composition containing only the resin that does not dissolve the cellulose resin of the base material, the cellulose resin does not dissolve in the curable composition. I don't get up. As a result, conductivity cannot be imparted to the cured film surface.

  (A1) Examples of the polymerizable compound that dissolves the cellulose resin include compounds having one polymerizable group such as an ethylenically unsaturated group (hereinafter referred to as “monofunctional compound”), Examples thereof include compounds having two or more polymerizable groups such as saturated groups (hereinafter referred to as “polyfunctional compounds”). As the monofunctional compound as the component (A1), for example, polymerization in which the mass reduction rate of a film such as 2-hydroxyethyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, N-vinylformamide is 10% or more Polymerizable compounds; polymerizable compounds having a film mass reduction rate of 5% or more and less than 10% such as γ-butyrolactone acrylate, N-vinylcaprolactam; and the like; And polymerizable compounds that are less than%. Other examples include glycidyl methacrylate, tetrahydrofurfuryl acrylate, 4-hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin monomethacrylate, and the like. Examples of the polyfunctional compound (A1) include ethylene glycol diacrylate and diethylene glycol diacrylate. These components may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The content of the component (A1) in the polymerizable compound (A) is 5% by mass to 75% by mass, preferably 10% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass. % Or less. In this specification, “component (A)” refers to the sum of components (A1) and (A2). By blending the component (A1) in the above range, not only can a cured film having high hardness be obtained, but also (B) the conductivity imparting component is unevenly distributed on the side opposite to the cellulose resin substrate in the cured film. It becomes easy.

1.1.2. (A2) Component The polymerizable compound other than the component (A1) which is the component (A2) is used for the purpose of improving the film-forming property of the curable composition and the hardness and scratch resistance of the cured film. Examples of the component (A2) include monofunctional compounds and polyfunctional compounds other than the component (A1). Among these, a polyfunctional compound is preferable in that a cured film having excellent hardness and scratch resistance can be formed by forming a crosslinked structure. As the polyfunctional compound as the component (A2), for example, a polyfunctional (meth) acrylic ester compound, a polyfunctional vinyl compound, a polyfunctional epoxy compound, or a polyfunctional alkoxymethylamine compound is preferable. More preferred are (meth) acrylic ester compounds and polyfunctional vinyl compounds. Multifunctional (meth) acrylic ester compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol Examples include diacrylate, tetraethylene glycol diacrylate, fluorinated adamantyl diacrylate, 1,4-butanediol diacrylate, isobornyl acrylate, and butyl acrylate. Examples of the polyfunctional vinyl compound include divinylbenzene. Polyfunctional epoxy compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglyceride. A glycidyl ether etc. are mentioned. Examples of the polyfunctional alkoxymethylamine compound include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like.

  Further, the component (A2) may contain a monofunctional (meth) acrylic ester compound, a monofunctional vinyl compound, a monofunctional epoxy compound and the like to the extent that the effects of the present invention are not impaired.

  The ratio of the polyfunctional compound contained in the component (A2) is preferably 50 to 100% by mass and 80 to 100% by mass when the total amount of the component (A2) is 100% by mass. More preferred is 100% by mass.

1.2. (B) Conductivity imparting component The curable composition according to the present embodiment contains (B) a conductivity imparting component. (B) A conductivity imparting component is a component for imparting conductivity (antistatic property) to a cured film formed by curing the curable composition according to the present embodiment. Conductivity can be imparted to the surface of the cured film by forming a layer in which (B) the conductivity imparting component exists at a high density on the surface of the cured film. In addition, the presence of (B) the conductivity imparting component at a high density on the surface of the cured film is expected to increase the hardness of the cured film and improve the scratch resistance or reduce the curl.

  Examples of the (B) conductivity-imparting component include conductive particles and conductive polymers. In the curable composition concerning this Embodiment, electroconductive particle and electroconductive polymer may each be used independently, and they can also be used in combination. Hereinafter, the conductive particles and the conductive polymer will be described in this order.

1.2.1. Conductive particles The conductive particles are not particularly limited as long as they have conductivity, but metal oxide particles are preferable. Examples of the metal oxide constituting the metal oxide particles include antimony-containing tin oxide (ATO), tin-containing indium oxide (ITO), phosphorus-containing tin oxide (PTO), fluorine-containing tin oxide, aluminum-containing zinc oxide, and gallium. Examples thereof include zinc oxide. Among these, antimony-containing tin oxide (ATO) and phosphorus-containing tin oxide (PTO) are preferable. These electroconductive particles may be used individually by 1 type, and may be used in combination of 2 or more type.

  The median diameter of the conductive particles is preferably in the range of 20 to 90 nm, and more preferably in the range of 35 to 70 nm. If the median diameter is less than the above range, the electrical conductivity may be insufficient. If the median diameter is exceeded, sedimentation may occur in the curable composition, the transparency of the coating film may decrease, (Haze value) may increase. Here, the median diameter means a diameter in which the large side and the small side are equivalent when the powder is divided into two from a certain particle diameter. This median diameter can be measured by a particle size distribution measuring apparatus based on the dynamic light scattering method.

  The conductive particles are preferably in the form of powder. Examples of commercially available products of antimony-containing tin oxide (ATO) that can be used in this embodiment include SN-100P (manufactured by Ishihara Sangyo Co., Ltd., primary particle size: 10 to 30 nm), SN-102P (Ishihara Sangyo Co., Ltd.) (Manufactured by company, primary particle size: 10 to 30 nm). Examples of commercially available phosphorus-containing tin oxide (PTO) include ELCOM TL-30S (manufactured by JGC Catalysts & Chemicals Co., Ltd.), EP SP2 (manufactured by Mitsubishi Materials Corporation), and the like.

  In the curable composition according to the present embodiment, when conductive particles are used as the conductivity imparting component (B), the content of the conductive particles is when the total of the components excluding the solvent is 100% by mass. , Preferably it is 5-20 mass%, More preferably, it exists in the range of 10-20 mass%. If the content of the conductive particles is less than the above range, conductivity may not be expressed on the surface of the cured film. If the content exceeds the above range, the improvement in conductivity is limited and productivity may decrease. is there.

In addition, in the cured film formed by apply | coating the curable composition containing electroconductive particle as (B) electroconductivity imparting component to a cellulose resin base material and making it harden | cure, what is a surface which contacts a cellulose resin base material? A layer having high density of conductive particles is formed on the opposite surface side. Therefore, sufficient conductivity (antistatic property) is imparted to the surface of the cured film even when the content of the conductive particles in the curable composition is 5 to 20% by mass, which is less than usual (about 20 to 40% by mass). can do. Thereby, the transparency of the laminate can be ensured and the productivity can be improved. The surface resistance value of the antistatic laminate is, for example, 10 ¹³ Ω / □ or less, preferably 10 ¹¹ Ω / □ or less, and more preferably 10 ⁹ Ω / □ or less.

1.2.2. Conductive polymer "Conductive polymer" refers to a polymer compound having electrical conductivity composed of a conjugated polymer and a dopant.

  Examples of the conjugated polymer constituting the conductive polymer include a polymer of 3,4-dioxythiophene generally indicated as “PEDOT”.

  Examples of the dopant constituting the conductive polymer include (co) polymers having sulfonic acid and / or sulfonate. Examples of the (co) polymer having sulfonic acid and / or sulfonate include polystyrene sulfonate (PSS) and isoprene sulfonic acid (co) polymer.

  In addition, the weight average molecular weight (Mw) of a dopant is not specifically limited, What is necessary is just to be the range of 1,000-500,000.

  The isoprene sulfonic acid (co) polymer may be composed only of an isoprene polymer having a sulfonic acid group, or may be a copolymer having another structure. Examples of the copolymer include a copolymer with styrene. A copolymer containing an isoprene polymer having a sulfonic acid group can take various configurations such as a ternary block copolymer, a ternary random copolymer, a binary block copolymer, and a binary random copolymer. .

  The proportion of structural units derived from isoprenesulfonic acid and isoprene in the isoprenesulfonic acid (co) polymer is 40 mol% or more when the total amount of structural units derived from monomers in the copolymer is 100 mol%. It is preferable that it is 60 mol% or more. There exists a possibility that electroconductivity may fall that the ratio of the structural unit derived from isoprenesulfonic acid and isoprene is less than 40 mol%.

  The sulfonation rate of the isoprenesulfonic acid (co) polymer is preferably 15 mol% or more, and more preferably 50 mol% or more. There exists a possibility that electroconductivity may fall that a sulfonation rate is less than 15 mol%. The sulfonation rate of the isoprene sulfonic acid (co) polymer is the ratio (mol%) of the sulfonated structural unit derived from isoprene to the total amount of structural units derived from isoprene contained in the copolymer. ).

  Specific examples of the isoprene sulfonic acid (co) polymer include a ternary block copolymer of isoprene sulfonic acid-styrene-isoprene sulfonic acid, a random block copolymer of isoprene sulfonic acid-styrene, and the like.

  Examples of commercially available isoprenesulfonic acid (co) polymers include DK201, DK202A, DK106, DK114, and TED manufactured by JSR Corporation.

Next, an example of a method for producing a conductive polymer will be described.
To the aqueous solution of the isoprene sulfonic acid (co) polymer, an oxidant that is a polymerization catalyst and 3,4-ethylenedioxythiophene monomer are added and stirred at 20 to 80 ° C. for 4 to 24 hours. A conductive polymer is obtained by producing 3,4-ethylenedioxythiophene) (AI; PEDOT).

  The conductive polymer is often used in the form of a solution containing a complex composed of a conjugated polymer and a dopant, an oxidant, and a solvent in the manufacturing process. There is no restriction | limiting in particular as this oxidizing agent, The thing conventionally used as a polymerization catalyst of 3, 4- ethylenedioxythiophene can be used. For example, hydrogen peroxide solution, p-toluenesulfonate, ammonium persulfate, sodium persulfate, potassium persulfate, iron (III) chloride, iron (III) sulfide and the like can be mentioned.

  In addition, when manufacturing the curable composition which concerns on this Embodiment, although the method of adding the solution in which the conjugated polymer and dopant which were mentioned above were mixed beforehand to a curable composition is employ | adopted normally, it is conjugate. You may employ | adopt the method of mixing, after adding a system polymer and a dopant separately to a curable composition.

  (B) When a conductive polymer is used as the conductivity-imparting component, the content of the conductive polymer is preferably 0.1 to 5% by mass when the total of the components excluding the solvent is 100% by mass, More preferably, it is 0.2-4 mass%, Most preferably, it exists in the range of 0.3-3 mass%. If the content of the conductive polymer is less than the above range, conductivity may not be exhibited on the surface of the cured film, and if it exceeds the above range, the hardness of the cured film may be reduced.

  In the present invention, the term “conductive polymer” means a complex composed of a conjugated polymer and a dopant, and the content of the conductive polymer does not include an oxidizing agent.

  Moreover, in the cured film formed by apply | coating the curable composition containing electroconductive particle as a electroconductivity imparting component to a cellulose resin base material and making it harden | cure, what is a surface which contacts a cellulose resin base material? A layer having a high density of conductive polymer is formed on the opposite surface side. Therefore, even when the content of the conductive polymer in the curable composition is less than usual, sufficient conductivity (antistatic property) can be imparted to the cured film surface. As a result, it becomes easy to ensure the transparency of the cured film.

1.3. (C) Polymerization initiator The curable composition according to the present embodiment may contain (C) a polymerization initiator. As such a (C) polymerization initiator, for example, when it contains a (meth) acrylic ester compound and / or a vinyl compound as the component (A), a compound that thermally generates active radical species (thermal polymerization initiator) And general-purpose products such as compounds (radiation (light) radical polymerization initiators) that generate active radical species upon irradiation with radiation (light). In addition, when an epoxy compound and / or an alkoxymethylamine compound is contained as the component (A), general-purpose products such as an acidic compound and a compound (radiation (light) acid generator) that generates an acid by radiation (light) irradiation are used. Can be mentioned. Among these, a radiation (photo) polymerization initiator is preferable.

  The radiation (photo) radical polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxy Benzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

  Commercially available products of radiation (photo) radical polymerization initiators include, for example, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur, manufactured by BASF Japan Ltd. 1116, 1173, Lucirin TPO, 8893; Ubekril P36 manufactured by UCB; Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B manufactured by Lamberti.

  The thermal radical polymerization initiator is not particularly limited as long as it is decomposed by heating to generate radicals to initiate polymerization, and examples thereof include peroxides and azo compounds. Specific examples include: Examples include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile.

  As the radiation (photo) acid generator, compounds of triarylsulfonium salts and diaryliodonium salts can be used. Examples of commercially available radiation (light) acid generators include CPI-100P and 101A manufactured by San Apro.

  In the curable composition according to the present embodiment, the content of the (C) polymerization initiator used as necessary is preferably 0.01 when the total of the components excluding the solvent is 100% by mass. It is in the range of ˜15% by mass, more preferably 0.1˜8% by mass. By blending in the above range, a cured film with higher hardness and scratch resistance can be obtained. In addition, (C) a polymerization initiator can also use multiple types of compounds together.

1.4. (D) Solvent The curable composition according to the present embodiment adjusts the thickness of the coating film (hereinafter referred to as “curable composition layer”) and the viscosity of the curable composition when applied to the cellulose resin substrate. In order to achieve this, (D) it can be diluted with a solvent. For example, when the curable composition according to this embodiment is used as an antistatic film or a coating material, the viscosity at 25 ° C. is usually 0.1 to 50,000 mPa · sec, preferably 0.5 to 10 1,000 mPa · s.

  (D) Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N -Amides such as methylpyrrolidone.

  In the curable composition which concerns on this Embodiment, content of (D) solvent used as needed is 50-10,000 when the sum total of the component except (D) solvent is 100 mass parts. It is preferably within the range of parts by mass. (D) The content of the solvent can be appropriately determined in consideration of the coating film thickness, the viscosity of the curable composition, and the like.

  In addition, you may select the solvent which melt | dissolves a cellulose resin as a part or all of the (D) solvent used as needed in the curable composition which concerns on this Embodiment. Here, the solvent for dissolving the cellulose resin means that an 80 μm-thick cellulose resin film cut into a size of 18 cm × 1 cm is immersed in 6 g of the component at 25 ° C. for 2 hours, and the taken-out film is 24 A component whose mass reduction rate of the film is 1% or more when dried in a vacuum drier for a period of time and is not included in the component (A1). Specific examples include cyclohexanone, acetone, methyl ethyl ketone, acetylacetone, diacetone alcohol, and the like. (D) By using a part or all of the solvent as a solvent that dissolves the cellulose resin, the cellulose resin can be eluted more efficiently, and the adhesion between the cured film and the substrate can be further improved. The uneven distribution of components can be further increased. (D) The proportion of the solvent used as the solvent for dissolving the cellulose resin can be appropriately determined according to the amount of (D) the solvent used, the type of component (A1), and the amount used.

1.5. Other Additives The curable composition according to the present embodiment includes, as necessary, a particle dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, an antiaging agent, and a thermal polymerization inhibitor. , Colorants, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like.

1.6. Manufacturing method of curable composition The curable composition which concerns on this Embodiment is (A) polymeric compound, (B) electroconductivity provision component, (C) polymerization initiator, (D) solvent, as needed, It can be prepared by adding other additives and mixing at room temperature or under heating conditions. Specifically, it can prepare using mixers, such as a mixer, a kneader, a ball mill, and a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition temperature of the thermal polymerization initiator.

2. 2. Antistatic laminate and production method thereof 2.1. Method for Producing Laminate for Antistatic A method for producing a laminate for antistatic according to the present embodiment includes (a) a polymerizable component containing 5% by mass to 75% by mass of a polymerizable component (A1) that dissolves a cellulose resin. A step of preparing a curable composition containing the compound (A) and the conductivity-imparting component (B) (hereinafter also referred to as “step (a)”), and (b) the curable composition as a cellulose resin substrate. And a step of curing after application (hereinafter also referred to as “step (b)”).

  According to such a method for producing an antistatic laminate, by applying and curing the curable composition on a cellulose resin substrate as a substrate, the surface opposite to the surface in contact with the cellulose resin substrate ( B) A cured film having a layer in which the conductivity-imparting component is present at high density can be formed. Since such a layer serves as a conductive path, a laminate having excellent conductivity (antistatic property) can be produced. In addition, according to the method for producing an antistatic laminate, a layer in which the (B) conductivity-imparting component is present at a high density is formed on the surface opposite to the surface in contact with the cellulose resin. The amount of (B) conductive particles contained in the composition can be reduced. As a result, the transparency and productivity of the cured film can be improved. Hereinafter, it demonstrates for every process.

2.1.1. Step (a)
Step (a) is a step of preparing the curable composition described above. Since the structure and manufacturing method of the curable composition are as described above, detailed description thereof is omitted.

2.1.2. Step (b)
Step (b) is a step in which the curable composition prepared in step (a) is applied to a cellulose resin substrate and then dried and cured.

  The method for applying the curable composition prepared in step (a) to the cellulose resin substrate is not particularly limited. For example, bar coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating. Well-known methods such as lip coating, die coating, dip coating, offset printing, flexographic printing, and screen printing can be used.

  After coating by the above method, volatile components such as a solvent are dried. Specifically, the said curable composition is apply | coated on a cellulose resin base material, and a volatile component is dried at 0-200 degreeC, Preferably it is 20-150 degreeC, More preferably, it is 20-120 degreeC. If the temperature exceeds 200 ° C., the cellulose resin substrate may be deformed, or the binder component that contributes to the curing of the curable composition layer may volatilize to lower the strength. Examples of the drying method include a hot air type, a drum type, an infrared type, an induction heating type, and the like, and are appropriately determined depending on the size and thickness of the substrate. When heating with the hot air method, if the wind speed is too fast, the uneven distribution of the conductivity-imparting component and the appearance of the coating film may be impaired, so the wind speed of the hot air is preferably 20 m / second or less, More preferably, it is 5 m / sec or less.

  When the curable composition prepared in step (a) is applied on a cellulose resin substrate, the component (A1) contained in the curable composition interacts with the cellulose resin contained in the cellulose resin substrate. And a cellulose resin may mix in a curable composition layer, or a (A1) component may osmose | permeate a cellulose resin base material. Whether or not the cellulose resin is mixed in the curable composition layer is determined by, for example, measuring the obtained cured film with a Raman spectrometer and observing a peak of a specific functional group of the cellulose resin. Can be determined.

The curing conditions for the curable composition are not particularly limited. Specifically, the curable composition is applied on a cellulose resin substrate, preferably after drying a volatile component at 0 to 200 ° C., and then subjected to a curing treatment with radiation and / or heat for antistatic use. A laminate can be formed. A preferable condition for curing with heat is 20 to 150 ° C., and is performed in a range of 10 seconds to 24 hours. When curing with radiation, it is preferable to use ultraviolet rays or electron beams. Irradiation light amount of the ultraviolet rays is preferably 0.01 to 10 J / cm ^2, more preferably 0.1~2J / cm ^2. Moreover, the irradiation conditions of an electron beam are a pressurization voltage of 10-300 kV, an electron density of 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount of 1-10 Mrad.

2.2. FIG. 1 is a cross-sectional view schematically showing an antistatic laminate according to the present embodiment. As shown in FIG. 1, in the antistatic laminate 100 according to the present embodiment, a cured film 20 obtained by curing the above-described curable composition is formed on a cellulose resin substrate 10 as a substrate. The density of the conductivity imparting component 22 on the side opposite to the cellulose resin substrate in the cured film 20 is higher than the density of the conductivity imparting component 22 on the cellulose resin substrate side in the cured film 20. That is, a region 26 (hereinafter, also referred to as “conductive layer 26”) in which the conductivity imparting component 22 exists at a relatively high density is formed on the opposite side of the cured resin film 20 from the cellulose resin base material. A region 24 (hereinafter also referred to as “hard coat layer 24”) in which the conductivity-imparting component 22 does not substantially exist is formed on the cellulose resin substrate side in the film 20. The boundary between the region 24 and the region 26 is not necessarily clear, but most of the conductivity imparting component 22 in the cured film 20 gathers in the region 26 and the region 24 does not substantially contain the conductivity imparting component 22. It is preferable that the boundary is clear. When the conductivity imparting component 22 is unevenly distributed in the region 26, the conductivity of the region 26 is higher than that of the region 24. Thereby, the laminated body excellent in antistatic property can be obtained. Further, when the region 24 contains a polyfunctional compound as the component (A), a cured film having a crosslinked structure is formed, so that an antistatic laminate having excellent hardness and scratch resistance can be obtained.

  The antistatic laminate 100 is provided with a high refractive index layer and a low refractive index layer on the surface opposite to the surface in contact with the cellulose resin substrate 10 of the cured film 20 within a range that does not affect the antistatic performance. You may provide in this order. Further, an intermediate refractive index layer may be provided between the high refractive index layer and the low refractive index layer. In addition, in this invention, a cured film means the film | membrane obtained by apply | coating and hardening a curable composition, and there may be adjustment of a component in the process of application | coating and hardening.

  The reason why the conductivity imparting component 22 is unevenly distributed is not necessarily clear, but since the (A1) component dissolves the cellulose resin and the cellulose resin is eluted into the curable composition layer, the affinity with the cellulose resin is low. It is presumed that the conductivity imparting component 22 is unevenly distributed on the side where the cellulose resin concentration in the curable composition layer is low (that is, the side opposite to the cellulose resin substrate in the curable composition layer). By curing the curable composition in such a state, the cured film 20 in which the conductivity imparting component 22 is unevenly distributed on the side opposite to the cellulose resin substrate in the cured film can be formed.

  On the other hand, in the curable composition containing only the polymerizable compound that does not dissolve the cellulose resin of the substrate, since there is no interaction with the cellulose resin, the (B) conductivity imparting component may be unevenly distributed on the surface of the cured film. This is not possible, and the conductivity (antistatic function) on the surface of the cured film is impaired.

In addition, the surface resistance of the obtained cured film is preferably 1 × 10 ¹³ Ω / □ or less, more preferably 1 × 10 ¹¹ Ω / □ or less, and 1 × 10 ⁹ Ω / □ or less. It is particularly preferred. When the surface resistance exceeds 1 × 10 ¹³ Ω / □, the antistatic performance is not sufficient, and dust may be easily attached or the attached dust may not be easily removed.

  Hereinafter, each layer of the antistatic laminate according to the present embodiment will be described.

2.2.1. Cellulose resin substrate The substrate used in the antistatic laminate according to the present embodiment is a cellulose resin substrate. By using a cellulose resin as a substrate, the (A1) component contained in the curable composition described above dissolves or swells the cellulose resin, so that the conductivity imparting component 22 is present at a relatively high density. 26 can be formed. On the other hand, when a resin other than the cellulose resin is used as the base material, the above-described effects are not achieved. In the present embodiment, the cellulose resin base material may be a base material itself formed of a cellulose resin, or a base material having a cellulose resin layer on the surface of a base material such as polyethylene terephthalate or polycarbonate. . Here, examples of the cellulose resin that can be used as the substrate include triacetyl cellulose (TAC), diacetyl cellulose, and cellulose acetate butyrate.

  In addition, the antistatic laminate having a cellulose resin as a base material is widely used in a hard coat and / or reflection such as a lens part of a camera, a screen display part of a television (CRT), or a protective film for a polarizer in a liquid crystal display device. An excellent antistatic effect can be obtained in the field of application of the antistatic film.

2.2.2. Hard Coat Layer The hard coat layer 24 is composed of a region that is formed on the cellulose resin substrate 10 side of the cured film 20 obtained by curing the curable composition described above and that is substantially free of the conductivity-imparting component 22. Is done.

  Although the thickness of the hard-coat layer 24 is not specifically limited, Preferably it is 1-50 micrometers, More preferably, it is 1-10 micrometers. If the thickness of the hard coat layer 24 is less than 1 μm, the hardness may be insufficient. On the other hand, if the thickness exceeds 50 μm, it is difficult to form a homogeneous film or the curling of the laminate is increased. It may be difficult. When the hard coat layer is formed, the component (A1) dissolves the cellulose resin as described above. Therefore, the obtained hard coat layer 24 is a layer containing the cellulose resin in addition to the component (A).

2.2.3. Conductive layer The conductive layer 26 is formed on the side opposite to the cellulose resin substrate 10 of the cured film 20 obtained by curing the curable composition described above, and the conductivity imparting component 22 is present at a relatively high density. Consists of regions.

  The thickness of the conductive layer 26 is not particularly limited, but is preferably 50 to 200 nm, more preferably 60 to 150 nm, and particularly preferably 80 to 120 nm. By setting the thickness of the conductive layer 26 within the above range, a laminate having sufficient conductivity (antistatic property) can be obtained within a range not impairing transparency.

3. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

3.1. Production example of conductive particles 3.1.1. Production of ATO (antimony-doped tin oxide) particle sol (Production Example 1)
In a plastic container, ATO particles (manufactured by Ishihara Sangyo Co., Ltd., trade name “SN-100P”, primary particle size 10 to 30 nm), Adeka Pluronic TR-701 (manufactured by ADEKA Corporation), and methanol were added to 72.75 / They were mixed at a blending amount of 2.25 / 175 (mass ratio) (total solid content 30%, total inorganic content 29.1%). Subsequently, the container was stirred for 2.5 hours using a paint shaker to obtain 250 g of a dispersion sol having a median diameter of 75 nm (solid content concentration: 30%).

3.1.2. Production of PTO (phosphorus-doped tin oxide) particle sol (Production Example 2)
In a plastic container, 28.5 PTO particles (manufactured by JGC Catalysts & Chemicals, Inc., ELCOM TL-30S, primary particle size 20 nm), Adeka Pluronic TR-701 (manufactured by ADEKA), and propylene glycol monomethyl ether (PGME). /1.5/70.0 (mass ratio) in a blending amount (total solid content 30%, total inorganic content 28.5%). Subsequently, the container was stirred for 2.5 hours using a paint shaker to obtain 100 g of a dispersion sol having a median diameter of 72 nm (solid content concentration: 30%).

3.2. Production example of conductive polymer 3.2.1. Conductive polymer (B-1)
Sepulzida (registered trademark) SAS-PE-J01 (manufactured by Shin-Etsu Polymer Co., Ltd., PEDOT / PSS, dopant molecular weight: 100,000 to 200,000) was used as the conductive polymer (B-1).

3.2.2. Production of conductive polymer (B-2) (Production Example 3)
Isoprenesulfonic acid-styrene random copolymer (trade name “DK106”, manufactured by JSR Corporation, molar ratio = 80/20, sulfonation rate of isoprene unit: 90%, molecular weight: 20,000) 0.320 parts by mass In an aqueous solution containing 18.57 parts by mass containing 0.481 parts by mass of ammonium persulfate as an oxidizing agent and 0.300 parts by mass of 3,4-ethylenedioxythiophene as a monomer, the mixture is stirred at 60 ° C. for 6 hours. Reacted. In this way, a conductive polymer (B-2) was obtained.

3.2.3. Production of conductive polymer (B-3) (Production Example 4)
0.278 parts by mass of isoprenesulfonic acid-styrene random copolymer (trade name “TED”, manufactured by JSR Corporation, molar ratio = 50/50, sulfonation rate of isoprene unit: 100%, molecular weight: 10,000) In an aqueous solution containing 16.13 parts by mass containing 0.507 parts by mass of ammonium persulfate as an oxidizing agent and 0.316 parts by mass of 3,4-ethylenedioxythiophene as a monomer, the mixture is stirred at 60 ° C. for 6 hours. Reacted. In this way, a conductive polymer (B-3) was obtained.

3.2.4. Conductive polymer (B-4)
Oligotron (registered trademark) NM (manufactured by SIGMA-ALDRICH, PEDOT / PSS, dopant molecular weight: 1,700) was used as the conductive composite (B-4).

3.3. Production Example of Curable Composition In a container shielded from ultraviolet rays, 15 parts by mass of PTO (phosphorus-doped tin oxide) particle sol obtained in Production Example 2 (5 parts by mass as a solid content), 2-hydroxyethyl acrylate (product) Name “light ester HOA”, manufactured by Kyoeisha Chemical Co., Ltd.) 26 parts by mass, dipentaerythritol pentaacrylate (trade name “SR399E”, manufactured by Sartomer) 66 parts by mass, 2-methyl-1 [4- (methylthio) phenyl] Uniform curing by adding 3 parts by mass of 2-morpholinopropan-1-one (trade name “Irgacure (registered trademark) 907”, manufactured by BASF Japan Ltd.) and an appropriate amount of methyl isobutyl ketone and stirring at room temperature for 2 hours. Sex composition was obtained. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 30 minutes, weighed, and the solid content was determined to be 50% by mass.

3.4. Example 1 (Preparation of antistatic laminate)
The curable composition obtained in “3.3. Production Example of Curable Composition” was applied on a triacetyl cellulose film using a bar coater so that the total cured film thickness was about 7 μm. After drying at ° C. for 2 minutes, it was cured using a high-pressure mercury lamp (300 mJ / cm ² ) under a nitrogen flow to obtain an antistatic laminate.

3.5. Examples 2-49, Comparative Examples 1-7
An antistatic laminate was obtained in the same manner as in Example 1 except that a curable composition containing the components shown in Tables 2 to 8 in the compositions shown in Tables 2 to 8 was used.

3.5. Evaluation test 3.5.1. (A) Solubility of polymerizable compounds in triacetyl cellulose First, the solubility of (A) polymerizable compounds described in Tables 2 to 8 in triacetyl cellulose was evaluated. The mass of an 80 μm-thick triacetyl cellulose film (trade name “TDY-80UL”, manufactured by FUJIFILM Corporation) cut to a size of 18 cm × 1 cm is a ₀ (g), and this film is 6 g at 25 ° C. When the mass of the film after dipping in a polymerizable compound for 2 hours and drying the taken-out film in a vacuum dryer at 80 ° C. for 24 hours is a ₁ (g), ((a ₀ −a ₁ ) / a ₀ ) The mass reduction rate of the film represented by x100 was measured. When the mass reduction rate is 1% or more, it is determined that the polymerizable compound dissolves triacetyl cellulose. When the mass reduction rate is less than 1%, the polymerizable compound does not dissolve triacetyl cellulose. It was judged. The results are shown in Table 1.

  Next, the following items of the antistatic laminates obtained in Examples and Comparative Examples were evaluated. The results are also shown in Tables 2 to 8.

3.5.2. Measurement of surface resistance value The surface resistance (Ω / □) of the cured film was measured using a high resistance meter (manufactured by Agilent Technologies, product name “Agilent 4339B”), and a resiliency cell 16008B (manufactured by Agilent Technologies, Inc.). ) And applied voltage 100V.

3.5.3. Measurement of haze value The haze value (%) of the antistatic laminate produced as described above was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).

3.5.4. Measurement of total light transmittance The total light transmittance (%) of the antistatic laminate produced as described above was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). It was measured.

3.6. Evaluation results From the results of Tables 2 to 8, it was found that the laminates of Examples 1 to 49 were significantly lower in surface resistance than the laminates of Comparative Examples 1 to 7 and excellent in antistatic properties. did. (B) The laminated body of Examples 1-26 produced from the curable composition containing electroconductive particle as an electroconductivity provision component is the range of 5-20 mass% in which content of electroconductive particle is less than usual. However, it has been found that sufficient conductivity can be obtained. By reducing the content of conductive particles, it becomes easy to ensure transparency. Furthermore, the laminates of Examples 27 to 49 prepared from the curable composition containing the conductive polymer as the conductivity imparting component (B) are excellent in transparency from the results of the haze value and the total light transmittance. Turned out to be.

Moreover, about the laminated body of Examples 1-49 and Comparative Examples 1-7, the cross section was sliced and the Raman spectroscopic measurement of the hard-coat layer (The JEOL Co., Ltd. make and the format "JRS-SYSTEM2000" was used) was performed. As a result, a peak at 1740 cm ⁻¹ derived from the carbonyl group of triacetylcellulose was detected from the hard coat layers of Examples 1 to 49, but from the hard coat layers of Comparative Examples 1 to 7 to triacetyl cellulose. No derived peak was detected. That is, it was shown that the triacetyl cellulose of the base material was mixed in the hard coat layers of Examples 1 to 49.

  Furthermore, when the cross section of the laminated body of Examples 1-49 was observed with the scanning electron microscope, the density of (B) electroconductivity provision component in the opposite side to the cellulose resin base material in a cured film is cellulose in a cured film. It became clear that it was higher than the density of the (B) electroconductivity provision component in the resin base material side. In addition, (B) electroconductivity provision component did not exist substantially in the cellulose resin base material side in a cured film. On the other hand, in the laminated body of Comparative Examples 1-7, the density of (B) electroconductivity provision component was substantially uniform in the cured film.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 10 ... Cellulose resin base material, 20 ... Cured film, 22 ... Conductivity provision component, 24 ... Area | region (hard-coat layer) in which electroconductivity provision component does not exist substantially, 26 ... Conductivity provision component has a relatively high density (Existing layer), 100 ... antistatic laminate

Claims (10)

A cellulose resin substrate;
A cured film of a curable composition containing a polymerizable compound (A) containing 5% by mass to 75% by mass of 2-hydroxyethyl (meth) acrylate as a polymerizable component (A1) and a conductivity-imparting component (B); With
The cellulose resin substrate and the cured film are laminated in contact with each other, and the conductivity imparting component (B) is unevenly distributed on the opposite side of the cellulose resin substrate in the cured film,
The conductivity imparting component (B) is conductive particles,
The antistatic laminate, wherein the content of the conductive particles is 5% by mass or more and 20% by mass or less in the curable composition excluding the organic solvent. A cellulose resin substrate;
A cured film of a curable composition containing a polymerizable compound (A) containing 5% by mass to 75% by mass of 2-hydroxyethyl (meth) acrylate as a polymerizable component (A1) and a conductivity-imparting component (B); With
The cellulose resin substrate and the cured film are laminated in contact with each other, and the conductivity imparting component (B) is unevenly distributed on the opposite side of the cellulose resin substrate in the cured film,
The conductivity imparting component (B) is a conductive polymer,
The antistatic laminate, wherein the content of the conductive polymer is 0.1% by mass or more and 5% by mass or less in the curable composition excluding the organic solvent. In claim 1 or claim 2,
The laminated body for antistatics in which the said cured film contains the cellulose resin which forms the said cellulose resin base material. In claim 1,
The antistatic laminate, wherein the conductive particles are at least one selected from antimony-containing tin oxide particles and phosphorus-containing tin oxide particles.   A curable composition containing a polymerizable compound (A) containing 5% by mass to 75% by mass of 2-hydroxyethyl (meth) acrylate as a polymerizable component (A1) and a conductivity-imparting component (B) is used as a cellulose resin group. Including a step of curing after applying to the material, the conductivity imparting component (B) is conductive particles, and the content of the conductive particles is 5% by mass or more in the curable composition excluding the organic solvent. The manufacturing method of the laminated body for antistatic which is 20 mass% or less.   A curable composition containing a polymerizable compound (A) containing 5% by mass to 75% by mass of 2-hydroxyethyl (meth) acrylate as a polymerizable component (A1) and a conductivity-imparting component (B) is used as a cellulose resin group. Including a step of curing after applying to the material, the conductivity-imparting component (B) is a conductive polymer, and the content of the conductive polymer is 0.00 in the curable composition excluding the organic solvent. The manufacturing method of the laminated body for antistatic which is 1 to 5 mass%. In claim 5,
A method for producing an antistatic laminate, wherein the conductive particles are at least one selected from antimony-containing tin oxide particles and phosphorus-containing tin oxide particles. The polymerizable component (A1) contains a polymerizable compound (A) containing 2-hydroxyethyl (meth) acrylate in an amount of 5% by mass to 75% by mass and a conductivity imparting component (B), and the conductivity imparting component (B ) Are conductive particles, and the content of the conductive particles is 5% by mass or more and 20% by mass or less in the curable composition excluding the organic solvent, and the antistatic laminate using a cellulose resin as a substrate. A curable composition used to produce a body. The polymerizable component (A1) contains a polymerizable compound (A) containing 2-hydroxyethyl (meth) acrylate in an amount of 5% by mass to 75% by mass and a conductivity imparting component (B), and the conductivity imparting component (B ) Is a conductive polymer, and the content of the conductive polymer is 0.1% by mass or more and 5% by mass or less in the curable composition excluding an organic solvent, and a cellulose resin is used as a base material. A curable composition used for producing an antistatic laminate. In claim 8,
A curable composition, wherein the conductive particles are at least one selected from antimony-containing tin oxide particles and phosphorus-containing tin oxide particles.

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