JP2005231089A - Antistatic transfer sheet and antistatic treated article - Google Patents

Abstract

【Task】
An antistatic transfer sheet that is less dependent on humidity and can maintain antistatic properties over a long period of time, and that can also effectively impart antistatic properties to molded products. The member provides an antistatically treated article having high transparency, low haze, and high hard coat properties.
Second antistatic layer 22 (if necessary), releasable substrate 11, release layer 13 (if necessary), antistatic layer 21, transparent cross-linked cured resin layer 23, primer layer 25 (if necessary) And an adhesive layer 27 (if necessary), wherein the antistatic layer is a conductive organic polymer, preferably a polythiophene polymer.
[Selection] Figure 1

Description

  The present invention relates to an antistatic transfer sheet. More specifically, the present invention relates to an antistatic transfer sheet that can easily impart antistatic treatment properties to articles that cannot be directly imparted with antistatic properties efficiently by using a transfer method. And an antistatic treated article.

  In the present specification, “/” marks indicate that they are laminated together. “PET” is an abbreviation, functional expression, common name, or industry term for “polyethylene terephthalate”.

(Technical Background) Many packages of food, home appliances, daily necessities, etc. are antistatic treated so that dust does not adhere during distribution and storage. Also, electronic and electrical products such as TVs (television receivers), personal computers and mobile phones are not only bad in appearance due to the adhesion of dust, but also there is a risk of fire due to the discharge of accumulated electric charges and failure of electronic components due to the discharge current. Yes, antistatic treatment is applied to prevent this.
For example, liquid crystal display devices such as personal computers, word processors, and liquid crystal televisions (TVs) are illuminated from the back by a surface light source device (also referred to as a backlight) because the liquid crystal itself does not emit light. The surface light source device emits light from an incident light source from a light exit surface, and further scatters, diffuses, and collects light, and makes the luminance of the irradiated surface uniform, so that a reflector, a light guide plate, a lens It is composed of many optical members such as a film, a light diffusing film, a polarizing film, a viewing angle adjusting film, an antireflection film, an antiglare film, a touch panel and a display window material. When these members are assembled into a display device, cutting waste and environmental dust adhere to the optical member during the processing, assembly, and use as the display device, which adversely affects the display. However, it is difficult to efficiently impart antistatic properties to molded products such as light guide plates and display windows, and for optical members, in addition to antistatic properties, high transparency, low haze, High hard coat properties (represented by pencil hardness, scratch resistance against steel wool, etc.) are required.
Also, conventional antistatic layers such as surfactants are required to have antistatic properties that are easy to deteriorate in long-term use and high-temperature and high-humidity environments, and are less dependent on humidity and can be maintained for a long period of time. ing.
As described above, the antistatic treatment to various articles is required to maintain antistatic properties for a long period of time with little transparency and humidity dependency, and to efficiently impart antistatic properties to molded products. Yes. Furthermore, high transparency, low haze, and high hard coat properties are also required for articles subjected to antistatic treatment.

(Prior Art) Conventionally, as a method for imparting antistatic properties to articles, a method in which an antistatic agent is directly applied to the surface of an article or an antistatic agent is directly added to an article has been mainstream. However, if direct coating is difficult because the surface of the component is uneven, or if it is difficult to add an antistatic agent to the article, an antistatic agent (including a layer) is added to the surface of the article. Transcription was also performed.
As such antistatic agents, conductive materials such as metals such as nickel, copper and silver and conductive carbon such as graphite, or anionic, cationic or nonionic surfactants are known. . However, the conductive material has good antistatic performance and stability over time, but has a problem that it is colored and the transparency is deteriorated. In addition, the surfactant has good transparency, but it moves to the surface over time, is wiped off with a cloth or washed away with water, etc., and the effect is reduced and stability over time (sustainability) is lacking. There was a defect, and there was no perfect one that achieved both transparency and antistatic properties over time.
Also, as an attempt to maintain antistatic properties for a long time while maintaining transparency, it is known to polymerize a resin material having a relatively low molecular weight with good antistatic properties into a resin (for example, Patent Documents). 1-2.) However, there are limitations on the types of resins that can be contained, and it is necessary to use a compatibilizing agent in combination, or a considerably large amount is required, which is also expensive.
Furthermore, it is known to contain an alkali metal salt of a halogen-containing acid such as lithium trifluoromethanesulfonate as an attempt to maintain antistatic properties for a long time while maintaining transparency (for example, Patent Documents). 3). However, when the content of lithium trifluoromethanesulfonate is large, the amount of migration to the surface is large and the appearance is lowered, resulting in a reduction in commercial value. In addition, there is a drawback in that the appearance becomes poor due to whitening even under high temperature and high humidity. In addition, none of the publications describes or suggests improvement of hard coat properties.

JP-A-2-233743 JP-A-3-26756 Japanese Patent Laid-Open No. 7-82411

  Accordingly, the present invention has been made to solve such problems. The purpose is to apply an antistatic layer containing a conductive organic polymer by a transfer method to provide antistatic properties to articles of various materials and shapes. It is an object to provide an antistatic transfer sheet that can maintain anti-static properties, can provide antistatic properties with good antistatic properties with time and excellent transparency. Furthermore, the article to which the antistatic layer is transferred is to provide an antistatic-treated article having both high anti-static properties, high transparency and low haze, and also high hard coat properties. .

In order to solve the above problems, an antistatic transfer sheet according to the invention of claim 1 has at least an antistatic layer and a transparent cross-linked cured resin layer as a transfer layer on one surface of a releasable substrate. In the antistatic transfer sheet, the antistatic layer contains at least a conductive organic polymer.
The antistatic transfer sheet according to the invention of claim 2 is such that the conductive organic polymer is a polythiophene polymer.
An antistatic transfer sheet according to a third aspect of the invention comprises a second antistatic layer on the other surface of the releasable substrate, a release layer between the releasable substrate and the antistatic layer, and / Or an adhesive layer on the opposite side of the transparent cross-linked cured resin layer to the antistatic layer.
According to a fourth aspect of the present invention, there is provided an antistatic transfer sheet having a primer layer between the transparent crosslinked cured resin layer and the adhesive layer.
The antistatic treated article according to the invention of claim 5 is formed by transferring the antistatic layer and the transparent crosslinked cured resin layer using the antistatic transfer sheet according to any one of claims 1 to 4. , That is.

  (Function and effect) The inventors of the present invention have intensively studied and adopted a method of transferring the antistatic layer provided in the transfer layer of the transfer sheet to the article, and including the conductive organic polymer in the antistatic layer. As a result, it has been found that an antistatic treatment can be applied to an article of any material and shape, and both antistatic properties and transparency can be achieved, and in addition, a specific hard coat property can be expressed. Thus, the present invention has been achieved.

According to the first aspect of the present invention, it is possible to efficiently impart antistatic properties to articles of any material and shape. In addition, it is less dependent on humidity and can maintain antistatic properties over a long period of time, has good anti-static stability over time (sustainability), high transparency, low haze, and high An antistatic transfer sheet having a hard coat antistatic layer is provided.
According to the second aspect of the present invention, there is provided an antistatic transfer sheet having an antistatic layer that is less dependent on humidity and can maintain antistatic properties over a long period of time.
If an antistatic layer is also formed on the other surface of the releasable substrate of the present invention of claim 3, the antistatic transfer sheet exhibits good antistatic properties during the production and transfer of the antistatic transfer sheet. If a release layer is further provided between the base material and the antistatic layer, the peeling force during transfer is stable and can be easily transferred, and the transparent cross-linked cured resin layer If there is an adhesive layer on the opposite side of the antistatic layer, the antistatic transfer can be transferred without providing an adhesive layer on the transfer target or providing the transparent crosslinked cured resin layer itself with no adhesiveness. A sheet is provided.
According to the present invention of claim 4, since the transparent cross-linked cured resin layer and the adhesive layer have good adhesion, an antistatic transfer sheet that does not easily fall off from the transfer body is provided.
According to the fifth aspect of the present invention, there is provided an antistatic treated article having both antistatic properties excellent in stability over time, high transparency and low haze, and high hard coat properties.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of an antistatic layer transfer sheet showing one embodiment of the present invention.

  (Invention of product) The antistatic layer transfer sheet of the present invention comprises a releasable substrate 11 having a second antistatic layer 22 if necessary / a release layer 13 / an antistatic layer 21 / a transparent crosslink if necessary. It consists of a cured resin layer 23 / a primer layer 25 if necessary and an adhesive layer 27 if necessary. Among these layers, the antistatic layer 21 / transparent cross-linked cured resin layer 23 / primer layer 25 / adhesive layer 27 are transfer layers, which are transferred to the article to be transferred and transferred to the second charge by the transfer process. It peels from the prevention layer 22 / release part 11 / release layer 13. In the following description, the entire layer configuration including the layers provided as necessary will be described. However, the items provided as necessary are not essential in the implementation.

The material used for the antistatic transfer sheet of the present invention and the forming method thereof will be described.
(Substrate) The releasable substrate 11 may be appropriately selected from those used in ordinary transfer sheets, and is not particularly limited, but is a flexible film (or sheet) substrate. A material is preferred. Examples of the material of the releasable substrate 11 include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, ethylene glycol-1,4 cyclohexadimethanol-terephthalic acid copolymer. Polymers, polyester resins such as polyester thermoplastic elastomers, polyethylene resins, polypropylene, polymethylpentene, polybutene, ethylene-propylene-butene copolymers, olefin thermoplastic elastomers, polyolefin resins such as cyclic olefin resins, poly Ether ether ketone, polyether sulfone resin, polyamide resin, fluorine resin, polyvinyl chloride and the like can be used.

  Among these, a uniaxial or biaxially stretched polyester resin film is more preferable because of its excellent heat resistance. The thickness of the releasable substrate is usually preferably about 6 μm to 188 μm. The releasable substrate 11 may be colored as long as it has flexibility, and may be provided with a pattern, characters, or the like by printing or the like.

  (Second antistatic layer) A second antistatic layer 22 is provided on the side of the releasable substrate 11 opposite to the antistatic layer 21 as necessary. The second antistatic layer is for preventing dust from adhering due to the generation of static electricity during the production, storage and transfer of the antistatic transfer sheet. It is not limited and various antistatic agents can be applied.

  Examples of the antistatic agent used for the second antistatic agent 22 include higher glycol ethylene oxide (EO) adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polyethylene glycols such as polypropylene glycol ethylene oxide adducts, Alkylphenol EO adducts, alkylene oxides such as polyethylene oxide, fatty acid esters of glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbit and sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines, etc. Nonionic surfactants such as polyhydric alcohols and polyhydric alcohol esters, carboxylates such as alkali metal salts of higher fatty acids, higher alcohol sulfates, higher alkyls Sulfate esters such as ether sulfates, sulfonates such as alkylbenzene sulfonates and paraffin sulfonates, phosphate esters such as higher alcohol phosphates, phosphates, phosphonates, phosphonates, etc. Anionic surfactants, higher alkyl amines, cyclic amines, hydantoin derivatives, amide amines, ester amides, quaternary ammonium salts such as alkyltrimethylammonium salts, pyridine and other heterocyclic rings, cation surface activity such as phosphonium or sulfoniums Agents, amino acids such as higher alkylaminopropionates, aminosulfonic acids, sulfuric or phosphoric acid esters of aminoalcohols, higher alkyldimethylbetaines, higher alkyldihydroxyethylbetaines and other alkyls Surfactants such as amphoteric surfactants such as betaines, natural surfactants such as saponins, carbon black, graphite, modified graphite, carbon black graft polymer, tin oxide-indium oxide, tin oxide-antimony oxide, oxidation Conductive powders such as tin and titanium oxide-tin oxide-antimony oxide can also be applied.

  In addition, a high molecular weight antistatic agent in which a conductivity-providing functional group of a low molecular weight antistatic agent such as a surfactant is bonded to a polymer can also be applied. Polymer type antistatic agents are also classified into nonionic, anionic, cationic and amphoteric types, and polyether type (polyethylene oxide, polyethylene oxide cross-linked product, copolymer of polyethylene oxide and other resin, polyethylene glycol, Nonionic and quaternary ammonium salt type (quaternary ammonium base-containing copolymer (quaternary ammonium base-containing (meth) acrylate copolymer, quaternary) such as polyethylene glycol and other resin copolymer) Cationic systems such as ammonium base-containing maleimide copolymers and quaternary ammonium base-containing methacrylimide copolymers), sulfonic acid systems (polystyrene sulfonate soda), amphoteric betaines (carbobetaine graft copolymers), etc. There is an anionic system.

  Furthermore, polyacetylene, polyaniline, polythiophene, polypyrrole, polyphenylene sulfide, poly (1,6-heptadiyne), polybiphenylene (polyparaphenylene), polyparafinylene sulfide, polyphenylacetylene, polo (2,5-thienylene), or Conductive polymers such as these derivatives can be used.

  These antistatic agents may be used alone or in combination, and may be applied alone or mixed in another binder. These surfactant contents are about 0.01-10 mass%. Moreover, you may add additives, such as a plasticizer, a stabilizer, a hardening | curing agent, a dispersing agent chelating agent, a pH adjuster, antiseptic | preservative, and an antifoamer, as needed.

  (Release layer) A release layer 13 is provided on the surface of the antistatic layer 21 of the releasable substrate 11 as necessary. The release layer 13 is provided for the purpose of causing peeling at the interface between the antistatic layer 21 and the release layer 13. Basically, the release layer 13 is a layer that is peeled and removed from the transfer layer such as the antistatic layer 21 together with the releasable substrate 11 during transfer. In some cases, a part of the release layer 13 may be transferred to the transfer target, but the function is not substantially affected, and this is within the scope of the present invention. As a material of the release layer 13, a release resin having release properties with respect to the transfer layer (the antistatic layer 21 on the outermost surface thereof), a resin containing a release agent, or the like can be applied. For example, depending on the selected antistatic layer, the release resin is usually acrylic resin, vinyl acetate resin, melamine resin, polyester resin, urethane resin, fluorine resin, silicone resin, epoxy. Resins, fiber-based resins, ionizing radiation curable resins that crosslink with ionizing radiation, and the like. Resins containing a release agent include, for example, fluorine resins, silicone resins, or acrylic resins, vinyl resins, polyester resins, and fiber resins obtained by adding or copolymerizing release agents such as various waxes. Etc. Examples of the ionizing radiation curable resin include (meth) acrylate-based and epoxy-based monomers and oligomers having a functional group that is polymerized (cured) by ionizing radiation such as ultraviolet (UV) and electron beam (EB). It is a resin containing.

  (Formation of Release Layer) The release layer 13 is formed by dispersing or dissolving the resin in a solvent (solvent) to obtain a low route, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod coat, kiss coat. It is formed by applying and drying by a known coating method such as knife coating, die coating, comma coating, flow coating, spray coating, etc., and removing the solvent. If necessary, heat drying at a temperature of 30 ° C. to 200 ° C., or aging, or in the case of an ionizing radiation curable resin, irradiation is performed with ionizing radiation for crosslinking.

  The thickness of the release layer 13 is usually about 0.01 μm to 5.0 μm, preferably about 0.1 μm to 3.0 μm. The thinner the thickness is, the better. However, when the thickness is 0.1 μm or more, better film formation is obtained and the peeling force is stabilized.

  (Antistatic layer) An antistatic layer 21 is provided on one surface of the substrate 11 or the release layer 13. The above-mentioned second antistatic layer 22 is not particularly limited as long as it is sufficient to obtain antistatic properties, and various antistatic agents can be applied. However, the antistatic layer 21 is less dependent on humidity and can maintain antistatic properties over a long period of time. Moreover, the antistatic layer 21 has high transparency, low haze, and high hard coat properties. Apply the agent.

Antistatic agents used for the antistatic layer 21 are polyacetylene, polyaniline, polythiophene, polypyrrole, polyphenylene sulfide, poly (1,6-heptadiyne), polybiphenylene (polyparaphenylene), polyparafinylene sulfide, polyphenylacetylene, polo ( 2,5-thienylene) or a derivative thereof, preferably a polythiophene-based conductive organic polymer.
By using the conductive organic polymer, it is less dependent on humidity and can maintain antistatic properties over a long period of time, and has high transparency and low haze. Pencil hardness and scratch resistance against steel wool can be remarkably improved. Specifically, it will be described later in Examples.

  The reason why the scratch resistance against pencil hardness, steel wool, etc. is improved is not clear, but the improvement in scratch resistance due to the low film strength and the slipperiness of the surface at a low coating amount is due to the lower transparent crosslinked cured resin layer 23. This is presumably because the anti-scratch property is exhibited beyond the antistatic layer 21.

One or a plurality of these conductive organic polymers may be used, and they may be applied alone or mixed with other binders. When it is applied alone, it may be appropriately dissolved or dispersed in a solvent, applied by a known coating method such as roll coating, gravure coating, bar coating, spray coating, etc., and dried to form the antistatic layer 21. . In this case, the thickness of the antistatic layer 21 is greater than 0 and not more than about 5 μm, and preferably about 0.01 to 1 μm.
In addition, when mixed into the binder, the antistatic layer 21 may be formed by adding about 0.01 to 10% by mass to the binder and applying it in the same manner as in the individual. In this case, the thickness of the antistatic layer 21 is about 0.1 to 10 μm, preferably about 0.1 to 5 μm.
In addition, even when mixed alone or in other binders, for example, additives such as plasticizers, stabilizers, curing agents, dispersant chelating agents, pH adjusters, preservatives, antifoaming agents are added as necessary. May be.

The surface specific resistance of the antistatic layer 21 according to JIS-K-6911 is about 1 × 10 ¹² Ω / □ or less, preferably 1 × 10 ¹⁰ Ω / □ or less, more preferably 1 × 10 ⁸ Ω / □. It is as follows.
At about 1 × 10 ¹² Ω / □, there is only an antistatic function to prevent dust adhesion, and when it becomes 1 × 10 ¹⁰ Ω / □ or less, the antistatic function is improved, and at 1 × 10 ⁸ Ω / □ or less, the optical function is improved. It can be used for optical members that are severely affected. Further, at 1 × 10 ¹² Ω / □ or more, the antistatic property is poor, and dust cannot easily be used due to adhesion.

  (Transparent cross-linked cured resin layer) As the transparent cross-linked cured resin layer 23, a layer obtained by curing a resin composition that is cross-linked and cured by a chemical reaction at room temperature, heat, ionizing radiation, or the like can be applied. It is. The thickness of the transparent crosslinked cured resin layer 23 is usually about 1 to 10 μm. Examples of the thermosetting resin composition include thermosetting resins such as polyurethane resins, phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins.

  The polyurethane resin is a resin obtained by a reaction between a polyhydric alcohol (polyol) and a polyvalent isocyanate (polyisocyanate). Examples of the polyhydric alcohol include polyhydric alcohols such as ethylene glycol, trimethylolpropane, pentaerythritol, glycerin, α-methylglucoside, sorbitol, dipentaerythritol, EO, PO, 1,2-, 2,3- or 1 , 3-butylene oxide, styrene oxide, α-olefin oxide having 6 to 18 carbon atoms, alkylene oxide such as epichlorohydrin (2 to 18 carbon atoms of alkylene group), polyoxyalkylene polyol, acrylic polyol, polyester polyol, A polyether polyol or the like is used. Polyvalent isocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate aromatic polyisocyanate, tetra Aliphatic polyisocyanates such as methylene diisocyanate and hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) And alicyclic polyisocyanates.

  Examples of the ionizing radiation curable resin composition that is cured by ionizing radiation include (meth) acrylates of polyfunctional compounds such as polyhydric alcohols (hereinafter, acrylate and methacrylate are referred to as (meth) acrylates) and the like. A compound having a radically polymerizable unsaturated group in the molecule, a compound having a cationically polymerizable functional group in the molecule such as an epoxy compound, or a monomer (monomer) or oligomer (or A known material comprising a prepolymer) can be applied. These monomers and oligomers (or prepolymers) may be used singly, or different monomers, different oligomers (or prepolymers), or monomers and oligomers (or May be used by mixing with (prepolymerized with ionizing radiation).

As the monomer of (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Examples include (meth) acrylates.
Examples of the (meth) acrylate oligomer (or prepolymer) include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. .
Examples of the epoxy compound include bisphenol type epoxy resins and novolak type epoxy resins.
Further, these monomers and oligomers (or prepolymers) usually used are in a liquid state at room temperature (normal temperature) in an uncrosslinked state and become solid only after crosslinking.

However, in the case of use in which a transfer sheet is transferred while being formed on a concavo-convex surface, it is preferable to use a form that forms a solid even in an uncrosslinked stage and becomes a solid in a crosslinked state upon irradiation with ionizing radiation.
The form of the ionizing radiation curable resin composition of this form is as follows. First, the ionizing radiation curable resin composition is dissolved (or dispersed) in a solvent to form a liquid, and then applied to the surface of the antistatic layer on the releasable substrate. After that, the solvent is evaporated and dried. Then, it is made non-adhesive solid with an uncrosslinked wrinkle to form an uncrosslinked transparent crosslinked cured resin layer, and a transfer sheet is prepared. In that case, if necessary, the ionizing radiation is irradiated in an appropriate amount, incompletely (partially) in a crosslinked state, within a range that does not impair molding followability to the uneven surface, or more completely dry, or The flow of the transparent cross-linked cured resin layer due to heat and stress during transfer may be prevented. Next, the transfer sheet is transferred onto the article while following the uneven surface with the transfer sheet. At this time, since the transparent cross-linked cured resin layer is not completely cross-linked, the thermoplastic additive composition is maintained, and sufficiently follows the uneven surface. Thereafter, the transparent crosslinked cured resin layer is crosslinked and cured by irradiating with ionizing radiation. At this time, the transparent crosslinked cured resin layer exhibits sufficient scratch resistance (hard coat property).

As an example of the ionizing radiation curable resin plastic that is in a solid state even in such an uncrosslinked stage,
(1) Oligomers (or prepolymers) such as (meth) acrylates, epoxy resins, or unsaturated polyesters having a high molecular weight and a melting point or melting temperature of room temperature or higher (usually 80 ° C. or higher),
(2) Monomers and oligomers (or prepolymers) such as liquid (meth) acrylates, epoxy resins, or unsaturated polyesters in an uncrosslinked state at room temperature, acrylic resins, urethane resins, etc. that are solid at room temperature Of non-adhesive solid at room temperature by adding a thermoplastic resin of
Etc.
Furthermore, the various ionizing radiation curable resin compositions listed above are used by adding additives such as a reactive diluent, a photopolymerization initiator, a photosensitizer, and a filler as necessary.

Examples of the reactive diluent include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, N-vinylpyrrolidone, and polyfunctional monomers such as tripropylene glycol diacrylate, trimethylolpropane tri ( Examples include meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and neopentyl glycol di (meth) acrylate.
The photopolymerization initiator is required to be added when using light such as ultraviolet rays and visible rays as ionizing radiation. Examples of photopolymerization initiators include acetophenones, benzophenones, and thioxanthones in the case of compounds having radically polymerizable unsaturated groups in the molecule, and in the case of compounds having a cationically polymerizable functional group in the molecule. Includes aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and the like. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and the like.

(Filler) The transparent cross-linked cured resin layer 23 may contain a filler, and organic fine particles and / or inorganic fine particles can be applied as the filler. Examples of the inorganic fine particles include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, glass, diatomaceous earth, mica powder, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, Although molybdenum disulfide can be used, silica is preferable.
As the organic fine particles, a thermoplastic resin having a glass transition temperature of 50 ° C. or higher is preferable. For example, WAX, polyethylene, fluorine resin, acrylic resin, methacrylic resin, phenol resin, urea resin, melamine resin, epoxy resin, Copolymerization of thermosetting resins such as unsaturated polyester resins, polystyrene, styrene and / or α-methylstyrene with other monomers (eg maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) Fine particles such as coalescence (for example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.) can be applied.

The particle diameter of the filler is in the range of about 0.001 to 30 μm, preferably about 0.01 to 20 μm in terms of average particle diameter. More preferably, it is about 0.1-5 micrometers silica. If it is less than this range, there is little improvement in hard coat properties, and if it exceeds this, haze will increase.
Furthermore, as content of a filler, it is about 1-100 mass parts with respect to 100 mass parts of transparent crosslinked hardening resin parts, Preferably it is 2-20 mass parts range. If it is less than this range, the improvement in hard coat properties is small, and if it exceeds this, haze increases, which hinders the optical member. The shape of the fine particles is not particularly limited, and may be spherical, rectangular, plate-like, flake-like, needle-like, or hollow.
Thus, when a filler is contained in the transparent crosslinked cured resin layer 23, the hard coat property can be remarkably improved because the filler functions as an anti-wear material.

  (Primer layer) Since the transparent cross-linked cured resin layer 23 may lack adhesion with other layers, a primer layer 25 is provided as necessary. The primer layer 25 improves the adhesiveness with the adhesive layer 27 formed on this surface, and the transparent cross-linked cured resin layer and the adhesive layer are sufficiently in close contact with each other, so that the transfer layer is removed from the transferred body after transfer. Can be difficult.

  Examples of the primer layer 25 include polyurethane resin, polyester resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, ethylene and acetic acid. A copolymer with vinyl or acrylic acid, an epoxy resin, or the like can be used. Preferred is a polyurethane resin composed of isocyanate or isocyanate and a polyhydric alcohol.

  These resins are appropriately dissolved or dispersed in a solvent to form a coating solution, which is applied to the transparent crosslinked cured resin layer 23 by a known coating method and dried to form a primer layer 25. In addition, when a resin, a monomer, an oligomer, a prepolymer, etc., and a reaction initiator, a curing agent, a crosslinking agent, etc. are combined as appropriate, or when a main agent and a curing agent are combined, they are applied and dried, dried or dried. It may be formed by reacting by an aging treatment after that. The primer layer 23 has a thickness of about 0.05 to 10 μm, preferably 0.1 to 5 μm.

  (Adhesive layer) An adhesive layer 27 is provided on the transparent cross-linked cured resin layer 23 or on the surface of the primer layer 25 provided as necessary. By providing the adhesive layer 27, the transfer can be performed even when the adhesive layer is not provided on the transfer target body and the transparent crosslinked cured resin layer is in a completely crosslinked state. In addition, a transfer sheet having no adhesive layer 27, for example, [(second antistatic layer 22) / releasing substrate 11 / (releasing layer 13) / antistatic layer 21 / transparent crosslinked cured resin layer 23 / (Primer layer 25)]; In addition, a structure including the layers provided in parentheses as needed is also included in one form of the antistatic transfer sheet 1 of the present invention. In this case, an adhesive layer is provided on the transferred material side, or a transparent cross-linked cured resin layer is formed using an ionizing radiation curable resin plastic that is solid even at the uncrosslinked stage as described above, and the transparent By transferring the crosslinked cured resin layer in an uncrosslinked state and having thermoplasticity (thermoadhesiveness), it can be transferred to the transfer material (article) side.

  The adhesive layer 27 will be described. In a preferred embodiment of the present invention, the adhesive layer 27 is configured as one of the transfer layers on the antistatic transfer sheet 1 as shown in FIG. The adhesive layer is used for adhering [antistatic layer 21 / transparent cross-linked cured resin layer 23 / primer layer 25 (if necessary)] to the transfer material side, and has adhesive strength at room temperature. And those that develop adhesiveness or adhesive force by treatment such as heating, and are collectively referred to as an adhesive layer in the present specification.

  The material of the adhesive layer 27 may be adhesive and / or tacky, and includes what is called an adhesive, a pressure-sensitive adhesive, and a hot melt, and is not particularly defined. For example, acrylic, epoxy, vinyl acetate, vinyl chloride, isocyanate, silicone, styrene-butadiene, vinyl chloride-vinyl acetate, ethylene-vinyl acetate, polyester, rubber chloride, chlorinated polypropylene, Examples include polyurethane resins and the like, or emulsion resins, organic solvent resins, water-soluble resins, and the like mainly composed of a mixture thereof.

  (Formation of Adhesive Layer) As a method of forming the adhesive layer 27, a coating liquid obtained by diluting the above resin with water or an organic solvent is usually used as a printing method such as gravure printing, offset printing, or screen printing, or It may be formed by coating by a coating method such as roll coating, bar coating, comma coating, spray coating, or extrusion coating, followed by drying or cooling. Although there is no restriction | limiting in particular in the thickness of the contact bonding layer 27, Usually, it is about 1-10 micrometers.

  (Transfer method) As the transfer method, transfer is performed by heating and pressurization of a heating roller, a method called a so-called hot stamp method by those skilled in the art, a transfer sheet is inserted into an injection mold, and the heat and pressure of the injection resin A known method such as a so-called injection molding simultaneous transfer method, in which transfer is performed using, is not particularly limited.

(Transfer to be transferred) Articles to which the transfer layer including the antistatic layer is transferred using the transfer sheet of the present invention, that is, the transfer target include packaging containers for foods, home appliances, daily necessities, etc., TV, personal There are no particular restrictions on the housing, window material, instrument panel, etc. of electronic and electrical products such as computers and mobile phones.
Preferably, it is difficult to directly form an antistatic layer, and high transparency and low haze are required, and the antistatic property is required to have little change with time and humidity dependency. It is public as a body. For example, molded products such as edge light type surface light source light guide plates and display windows used in liquid crystal display devices such as personal computers, word processors, and liquid crystal TVs, or reflectors, lens films, light diffusion films, polarization films used in these, A viewing angle adjusting film, an antireflection film, an antiglare film, a touch panel, and the like.
There are various surface materials to be transferred by the transfer object, but this can be dealt with by appropriately selecting the material of the adhesive layer. For example, acrylic resins, polycarbonate resins, resins such as polystyrene, ceramics such as glass, and the like can be given.

  (Antistatic Transfer Body) An antistatic transfer sheet having a transfer layer transferred using an antistatic transfer sheet has high transparency, low haze, high hard coat properties, and antistatic properties are Because it is less dependent on humidity, it is maintained for a long time.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

(Example of substrate / release layer / antistatic layer / cured resin layer) A biaxially stretched PET film having a thickness of 38 μm is used as a release substrate, and one surface on the release substrate is exposed to EX- 114 (trade name of a release agent manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied by a gravure printing method so that the thickness becomes 1.0 μm (after drying), and dried to form a release layer. On the release layer, Denatron (manufactured by Nagase Sangyo Co., Ltd., trade name of polythiophene-based conductive organic polymer) is applied by gravure printing so that the thickness is 0.5 μm (after drying) and dried. Thus, an antistatic layer was formed.
As a resin liquid (composition) for forming a transparent cross-linked cured resin layer on the antistatic layer, EXF-151 (trade name of ionizing radiation curable resin manufactured by Dainichi Seika Kogyo Co., Ltd.) has a thickness of 5.0 μm. (After curing) Apply by slit coating method, and irradiate ultraviolet rays at a traveling speed of 20 m / min using two lamps of 120 W / cm of high-pressure mercury lamp (made by USHIO INC., Product name of curing device). Crosslinking and curing were performed to form a transparent crosslinked cured resin layer.
TM-AC (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name of primer layer composition) as a primer is applied to the surface of the transparent crosslinked cured resin layer by a slit coating method so that the thickness becomes 2.5 μm (after drying). The primer layer was formed by applying and drying.
TM-HS (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name of adhesive layer composition) is applied to the primer layer surface by a gravure printing method so that the thickness is 1.5 μm (after drying). The antistatic transfer sheet of Example 1 was obtained.

  Example 1 except that 5 parts by mass of silica particles having an average particle diameter of 3 μm are contained in 100 parts by mass of the transparent crosslinked cured resin in the resin liquid (composition) for forming the transparent crosslinked cured resin layer. Similarly, an antistatic transfer sheet of Example 2 was obtained.

  (Example of substrate / release layer / second antistatic layer / cured resin layer / primer layer / adhesive layer) An antistatic agent is provided on the surface of the releasable substrate opposite to the transparent crosslinked cured resin layer side. As in Example 1, an antistatic transfer sheet of Example 3 was obtained in the same manner as in Example 1 except that Sunstat 2012 (manufactured by Sanyo Chemical Industries, trade name of conductive surfactant) was used.

  (Example of article) The adhesive layer surface of the antistatic transfer sheet of Example 1 and the acrylic resin plate having a thickness of 1 mm, which is the transfer object, are stacked, and the surface is silicon rubber using a heating roll pressurizing type transfer machine. When the surface of the roll made of 200 ° C., the pressure of 300 kPa, and the line speed of 50 mm / second are pressed and the transfer sheet and the transfer target are once bonded and laminated, the release substrate is peeled off. Only the layers (antistatic layer /, transparent cross-linked cured resin layer / adhesive layer) were transferred and transferred onto the acrylic resin plate to obtain an article treated with the antistatic layer of Example 4.

  An antistatic treated article of Example 5 was obtained in the same manner as Example 4 except that the antistatic transfer sheet of Example 2 was used.

  An antistatic treated article of Example 6 was obtained in the same manner as in Example 4 except that the antistatic transfer sheet of Example 3 was used.

(Comparative Example 1) Sunstat 2012 (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name of surfactant) as an antistatic material to a resin liquid (composition) for forming a transparent crosslinked cured resin layer without providing an antistatic layer An antistatic transfer sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that 0.3% by mass was contained.

(Comparative Example 2)
An antistatic treated article of Comparative Example 2 was obtained in the same manner as Example 4 except that the antistatic transfer sheet of Comparative Example 1 was used.

(Evaluation) Evaluation is performed on the transferred article. Surface resistivity, haze, total light transmittance, change in color tone, pencil hardness as a measure representative of hard coat properties, and steel wool test. Surface resistivity was measured by the method specified in JIS-K-6911. Measurement. Immediately after the transfer, and after the transfer, the measurement was performed after 3 days in an atmosphere with a relative humidity of 80% and an air temperature of 30 ° C.
The haze and total light transmittance (hereinafter referred to as Tt) were measured using a haze meter HM150 (trade name, manufactured by Murakami Color Co., Ltd.) in accordance with JIS-K7105.
The pencil hardness test was measured according to JIS-K-5400.
The steel wool test uses a tribogear HEIDON reciprocating wear tester (manufactured by Shinto Kagaku Co., Ltd.), steel wool is mounted on the holder, and the transfer layer surface of the transferred article is reciprocated 200 times at a speed of 300 mm / min with a load of 3N. After the abrasion, the damaged state of the article surface after the test was visually observed.
The change in color tone was visually observed for a difference from that before the transfer layer including the antistatic layer was transferred.

(Results of Evaluation) As shown in Table 1, the results of evaluation are as follows. In Examples 4, 5, and 6, the surfaces are all 10 ⁷ units, which is sufficient as antistatic performance and has antistatic properties. The stability over time was also good. The pencil hardness was 3H and the hard coat property was good. Further, in terms of optical characteristics, the haze was low, the total light transmittance was high, the coloring was small, and the optical characteristics were excellent. In Example 5, in addition to the above, the steel wool test was less damaged and the hard coat property was even better. Furthermore, in Example 6, when the transfer sheet was unwound from the roll at the time of transfer, no dust was visually observed on the transfer sheet, and the antistatic property of the transfer sheet before the transfer process was good. On the other hand, in Examples 4 and 5, when the transfer sheet was unwound from the roll during transfer, the adhesion of dust onto the transfer sheet was visually observed. However, the transfer article was not so defective as to cause the transfer layer to come off.
In Comparative Example 2, the surface resistance was as high as 10 ¹⁰ units, and the temporal stability was also lower than those in each Example. In the steel wool test, many fine scratches were recognized, and the performance was poor compared to Examples 4, 5, and 6 as a whole.

It is sectional drawing of the antistatic layer transfer sheet which shows one Example of this invention.

Explanation of symbols

1: Antistatic transfer sheet 22: Second antistatic layer 11: Release base 13: Release layer 21: Antistatic layer 23: Transparent cross-linked cured resin layer 25: Primer layer 27: Adhesive layer 31: Transfer layer

Claims (5)

In the antistatic transfer sheet having at least an antistatic layer and a transparent cross-linked cured resin layer as a transfer layer on one surface of the releasable substrate, the antistatic layer contains at least a conductive organic polymer. A feature of an antistatic transfer sheet. The antistatic transfer sheet according to claim 1, wherein the conductive organic polymer is a polythiophene polymer. A second antistatic layer on the other surface of the releasable substrate, a release layer between the releasable substrate and the antistatic layer, and / or an antistatic layer of the transparent cross-linked cured resin layer; The antistatic transfer sheet according to claim 1, further comprising an adhesive layer on the opposite side. The antistatic transfer sheet according to claim 4, further comprising a primer layer between the transparent cross-linked cured resin layer and the adhesive layer. An antistatic treated article obtained by transferring an antistatic layer and a transparent cross-linked cured resin layer using the antistatic transfer sheet according to claim 1.

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