JP2747551B2 - Surface-treated plastic film and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a surface-treated plastic film having excellent writing, printing and printability, and more particularly, to a prepaid card, a printout receiving paper, an OHP film and the like. The present invention relates to various printing plastic films.

[Prior Art] It is necessary to print, print or write directly on a plastic film in a prepaid card, a printout receiving paper, an OHP film and the like. However, if you print and write directly on the surface of a normal plastic film,
Neither printing ink nor the adhesiveness or setting property is present on the surface of the plastic film, so that good printed matter cannot be obtained, and satisfactory printing and writing cannot be performed.

Conventionally, a surface-treated plastic film in which a plastic surface is subjected to a corona treatment or a primer treatment in order to improve printability has been proposed.

[Problems to be Solved by the Invention] The following physical properties are usually required for a sheet excellent in printability / printing or writing suitability.

In other words, small surface electrical resistance that easily releases static electricity generated by rubbing between surfaces and good slippage of the surface. Good runnability with a low coefficient of friction. Setting property to accelerate solvent thickening by absorbing solvent, vegetable oil, etc. in offset ink. And hydrophilicity to dampening water in offset printing, and lipophilicity to ensure wetting to resin (oiliness) in offset printing.

In the above-mentioned conventional plastic film which has been subjected to an easy adhesion treatment, the printability is poor when set, and the drying time is long, so that it does not always show good printability and printability.

In addition, writing with an aqueous pen or printing with an ink jet printer cannot be practically used because the plastic film does not have sufficient hydrophilicity.

The present invention has been made based on the above background,
The purpose is to print and print, that is,
An object of the present invention is to provide a surface-treated plastic film having excellent running properties, setting properties, balanced hydrophilicity and lipophilicity, and suitable for writing with an aqueous pen and printing with an ink jet printer.

[Means for Solving the Problems] The above problems are solved by the surface-treated plastic film of the present invention.

That is, the surface-treated plastic film according to the present invention is formed by forming a hydrophilic inorganic-organic composite layer having inorganic colloidal particles on the substrate surface of the plastic film, and the inorganic-organic composite layer is formed with silicon on the surface of the colloidal silica particles. It is characterized by comprising a porous layer made of an inorganic-organic composite polymer having a siloxane-bonded carbon chain.

The method for producing a surface-treated plastic film according to the first aspect of the present invention comprises the steps of: adding an inorganic organic composite resin comprising a reaction product of inorganic colloidal particles, an ethylene-based monomer, and a silane-based monomer to a hydrophilic polymer; And preparing a hydrophilic resin composition, and using the hydrophilic resin composition to form a hydrophilic inorganic-organic composite layer on the substrate surface of a plastic film.

The method for producing a surface-treated plastic film according to the second aspect of the present invention is directed to an inorganic-organic composite resin comprising a reaction product of inorganic colloidal particles, an ethylene-based monomer, a silane-based monomer, and a hydrophilic monomer. A hydrophilic resin composition is prepared by adding a hydrophilic resin, and a hydrophilic inorganic-organic composite layer is formed on a substrate surface of a plastic film using the hydrophilic resin composition. is there.

 Hereinafter, the present invention will be described in more detail.

Surface-treated plastic film The film according to the present invention is a surface-treated plastic film excellent in writing, printing and printability, and has a hydrophilic inorganic organic material having a plastic film substrate and inorganic colloidal particles formed on the substrate surface. And a composite layer.

As the plastic film used in the present invention, polyethylene, polypropylene, polyvinyl chloride,
Polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, polycarbonate, nylon, polystyrene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, triacetate, polyethersulfone, cellophane, ethylene-acrylic acid copolymer, ethylene -Methacrylic acid copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer elastomer, acid-modified polyolefin, styrene-butadiene-acrylonitrile copolymer, polyamine, polysulfone, polyacetal, polymethylmethicry Rate, polyphenylene oxide, polyurethane, polybutadiene terephthalate, polyimide and other plastics.

The colloidal particles used in the present invention are particles (dispersoids) that can be dispersed in a colloid solution and have a particle size of 1 m.
μ to 100 μ.

The colloidal particles are substantially made of an inorganic material,
As such, for example, silica SiO ₂ , alumina Al
₂ O ₃ , lithium silicate SiO ₂ · LiO ₂ , antimony oxide Sb ₂
It is made of O ₅ , ferrite Fe ₂ O ₃ or the like. Specifically, there are colloidal silica, alumina sol, lithium silicate sol, antimony sol, ferrite sol,
Colloidal silica is preferred from the viewpoint of the transparency of the inorganic-organic composite layer.

Colloidal silica is prepared from a colloidal solution obtained by growing silica particles to about 1 to 100 mμ while neutralizing a water glass of Na ₂ O · nSiO ₂ with an acid in an aqueous solution. Colloidal silica includes acidic colloids and basic colloids.

The inorganic-organic composite layer formed on the substrate surface has hydrophilicity. It is desirable that the degree of hydrophilicity is determined so as to be suitable for writing with an aqueous pen or printing with an ink jet printer.

In a preferred embodiment, the surface-treated film according to the present invention has both porosity in addition to hydrophilicity to the inorganic-organic composite layer. As this porosity, the pore size is 5 to 500 mμ
m, and the number of holes is preferably in the range of 5 to 1000 holes / μm ² .

In the present invention, the structure of the inorganic-organic composite layer is not necessarily clear, but at least one of the raw material monomers of the inorganic-organic composite layer is cross-linked to form a functional group on the surface of the inorganic colloidal particles when the inorganic-organic composite layer is formed. It is obtained. For example, when colloidal silica is used as the colloidal particles, the inorganic-organic composite layer is made of an inorganic-organic composite polymer having a carbon chain siloxane-bonded to silicon on the surface of the colloidal particles.

Manufacturing Method Two embodiments of the method for manufacturing a surface-treated plastic film according to the present invention will be described below.

In the first embodiment, an inorganic-organic composite resin having inorganic colloidal particles, a hydrophilic polymer is blended to prepare a hydrophilic resin, using the obtained hydrophilic resin, one surface of the substrate surface of the plastic film, Alternatively, a hydrophilic inorganic-organic composite layer is formed on both surfaces, or on the entire or partial surface.

As the inorganic-organic composite resin having inorganic colloidal particles, the following raw materials, (a) an ethylenic monomer, (b) a silane-based monomer, and (c) colloidal silica are converted into solids in terms of (a) Anionic surfactant or nonionic surfactant in a ratio such that 0.20 parts by weight of (ii) silane monomer and 1 to 200 parts by weight of colloidal silica are used per 100 parts by weight of ethylenic monomer. There is a water-soluble resin dispersion obtained by emulsion polymerization in an aqueous medium in the presence of an activator.

(A) Ethylene monomer: As the ethylene monomer, there is at least one kind of monomer selected from α, β-ethylenically unsaturated carboxylic acid alkyl ester and alkenylbenzene. Here, as the α, β-ethylenically unsaturated carboxylic acid alkyl ester, typically, (meth) acrylic acid and C 1
To 18 alkanols, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, decyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate. Further, alkenylbenzene includes styrene, α
-Methylstyrene, o-, m-, p-vinyl ketone and the like.

In the present invention, a monomer copolymerizable with the above-mentioned α, β-ethylenically unsaturated carboxylic acid alkyl ester and alkenylbenzene can be blended. Such copolymerizable monomers include (meth) acrylic acid,
Maleic acid, maleic anhydride, fumaric acid, crotonic acid,
And itaconic acid.

(B) Silane-based monomer: As the silane-based monomer used herein, there is a monomer containing a polymerizable unsaturated double bond and an alkoxysilane group in a molecule. Here, as a monomer containing a polymerizable unsaturated double bond and an alkoxysilane group in the molecule,
Examples thereof include di- or trialkoxysilane compounds such as divinyldimethoxysilane, divinylbis-β-methoxy-ethoxysilane, vinyltriethoxysilane, vinyltris-β-methoxy-ethoxysilane, and γ-methacryloxypropyltrimethoxysilane. The amount of the silane-based monomer is 0.1 to 10 parts by weight based on 100 parts by weight of the ethylenic monomer. This is because if the amount is less than 0.1 part by weight, the reaction with the OH group on the surface of the colloidal silica becomes insufficient, while if it exceeds 10 parts by weight, the aqueous resin dispersion cannot be obtained due to excessive reaction and the stability is also low. Because it is bad.

Copolymerization conditions can be appropriately selected according to the type of raw materials, desired product characteristics, and the like. The description given above for the inorganic colloidal particles used in this embodiment applies mutatis mutandis. The content of the colloidal particles contained in the inorganic-organic composite layer is appropriately changed depending on the type of colloidal particles and organic components, but when using colloidal silica as the colloidal particles, for example, 100 parts by weight of the organic component 0.1 to 500 parts by weight, preferably 1 to 200 parts by weight.
This is because if the ratio exceeds the upper limit, the layer-forming property deteriorates, and if the ratio is less than the lower limit, improvement in hardness and heat resistance of the layer film due to an organic-inorganic composite action cannot be obtained. The surface-treated plastic film of the present invention is excellent in printing and printability,
Specifically, it has a small surface electric resistance to easily release static electricity generated by rubbing between surfaces, shows a running property (small friction coefficient) to make the surface slippery, a solvent in offset ink, vegetable water It has a setting property to accelerate thickening of the resin by absorbing the like, and has a balance between lipophilicity and hydrophilicity for ensuring wetting with a fountain solution and resin (oiliness) in offset printing.

Examples of the hydrophilic polymer compounded in the composite resin include polyvinyl alcohol, polyvinyl methyl ether, vinyl methyl ether, maleic anhydride copolymer, vinyl-based water-soluble polymer such as polyvinylpyrrolidone, polyacrylic acid-based resin, and polyacrylamide-based polymer. Acrylic water-soluble polymers such as resins, fibrous water-soluble polymers such as methylcellulose, ethylcellulose, carboxymethylcellulose and hydroxyethylcellulose, other synthetic water-soluble polymers such as polyethylene oxide and polyethyleneimine, soluble starch, cationic starch, etc. Processed or modified starch, corn starch, wheat starch,
One or two kinds selected from raw starch such as rice starch, potato starch, and sweet potato starch, plant gums such as gum arabic and tragacanth, and plant-based natural water-soluble polymers such as seaweeds such as sodium alginate, glue, and agar. More than one polymer may be used. Modified products of these water-soluble polymers can also be used. In the present invention, as the preferable hydrophilic polymer, a vinyl-based and a cellulose-based water-soluble polymer substance, particularly, polyvinyl alcohol and polyvinyl pyrrolidone can be suitably used.

The amount of the hydrophilic polymer added is 5 parts to 1000 parts, preferably 25 parts to 500 parts, per 100 parts by weight of the inorganic-organic composite resin.

In the production method of the second aspect according to the present invention, in preparing an inorganic-organic composite resin having inorganic colloidal particles, a hydrophilic monomer is added to prepare a hydrophilic resin, and the obtained hydrophilic resin is used. The present invention is characterized in that a hydrophilic inorganic-organic composite layer is formed on a substrate surface of a plastic film.

In this embodiment, the hydrophilic inorganic-organic composite resin having inorganic colloidal particles is obtained by reacting inorganic colloidal particles, an ethylene-based monomer, a silane-based monomer, and a hydrophilic monomer. The description of the inorganic colloidal particles in this embodiment, such as an inorganic-organic composite resin and a plastic film, applies mutatis mutandis to the above description. The hydrophilic monomer used in this embodiment has a hydrophilic group, for example, hexylethyl methacrylate, polyethylene glycol diacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, ethylene glycol methacrylate, diethylene glycol methacrylate, tetraethylene Ethylene glycol methacrylate, methoxydiethylene glycol methacrylate,
Methoxytetraethylene glycol methacrylate and the like.

The amount of the hydrophilic monomer is 1 to 1000 parts by weight, preferably 10 to 500 parts by weight, based on 100 parts by weight of the inorganic-organic composite resin.

[Operation] The present invention configured as described above operates as follows.

The surface-treated plastic film in the present invention is:
A hydrophilic inorganic-organic composite layer having inorganic colloidal particles is formed on the film substrate surface. The inorganic-organic composite resin forming this layer is obtained by cross-linking at least one kind of raw material organic monomer with a functional group on the surface of the inorganic colloidal particles at the time of forming the composite resin, and a hydrophilic polymer is blended with this resin. In an embodiment, the hydrophilic polymer forms part of the matrix of the composite layer to impart hydrophilicity to the composite layer. In addition, in a mode in which a hydrophilic monomer is added before synthesizing the inorganic-organic composite resin, another raw material organic monomer reacts with the hydrophilic monomer to impart hydrophilicity to the composite layer. In a preferred embodiment of the surface-treated plastic film of the present invention, the inorganic-organic composite resin layer has porosity in addition to hydrophilicity.
In the embodiment showing porosity, for example, when colloidal silica is used, the inorganic-organic composite layer is composed of an inorganic-organic composite polymer having a carbon chain siloxane-bonded to silicon on the surface of the colloidal particles.

When an emulsion containing emulsion particles made of such a polymer is coated on the surface of a plastic film, this polymer is a composite polymer with inorganic colloidal particles, and the molecular weight of the obtained polymer is usually tens of thousands to hundreds of thousands. Due to the high molecular weight of about several million in comparison with the degree, the dispersed emulsion particles do not completely fuse with each other and are fused with leaving holes. On the other hand, in normal emulsion particles, the emulsion particles are completely fused to each other. Thus, a porous film is formed on the surface of the film of the present invention.

[Effects of the Invention] According to the present invention, the following effects can be obtained.

Judging from the above constitutions and actions, as demonstrated by the following examples, (a) The present invention has excellent running properties, setting properties, balanced hydrophilicity and lipophilicity, and A surface-treated plastic film suitable for writing with a pen or printing with an inkjet printer is obtained.

(B) Further, in the film according to the present invention, since the hydrophilic inorganic-organic composite layer also has porosity, it absorbs the solvent, vegetable oil and the like in the offset ink to speed up the thickening of the resin, and furthermore, dampening water In addition, the film is provided with a setting property and a balance between hydrophilicity and lipophilicity by securing the wettability to oil, and the printing and printing characteristics are remarkably improved.

(C) In the surface-treated plastic film according to the present invention, the colloidal particles (inorganic substances) are cross-linked with an organic component to form a high-molecular weight composite, thereby improving the heat resistance of the coating. Various properties of the present invention can be obtained by the organic composite action. Further, since colloidal silica is used, there is an advantage that the transparency of the entire film is high.

(D) The method for producing a surface-treated plastic film according to the present invention makes it possible to economically produce a surface-treated plastic film such as an OHP film that has good running properties and toner adhesion of a PPC copier and can be used with an aqueous pen. can do.

[Examples] The present invention will be specifically described with reference to the following production examples.

Example 1 Based on 100 parts by weight of an inorganic-organic composite resin (Hoechst Gosei Co., Ltd., Movinyl 8030) obtained by reacting an acrylic monomer with an inorganic colloid (colloidal silica).
100 parts by weight of polyvinyl alcohol were added. The obtained resin mixture is used as a transparent plastic film (PET film,
100 μm) The surface was coated on both sides to a thickness of 5 μm.

The image was not blurred even when writing on the obtained surface-treated plastic sheet with an aqueous pen. Further, as a result of printing with a PPC copying machine (Fuji Xerox 5370), the running property and the toner fixing property were good. Further, as a result of printing with an ink jet printer (Seiko Epson Corp., HG-2000), good transfer was obtained.

Example 2 100 parts by weight of polyvinylpyrrolidone with respect to 100 parts by weight of an inorganic-organic composite resin (Hoechst Gosei Co., Ltd., Movinyl 8000) obtained by reacting an acrylic styrene monomer with inorganic colloidal (colloidal silica) Was added.
The obtained resin mixture is applied to a transparent plastic film (PET
(Film, 100 μm) was coated on both surfaces to a thickness of 5 μm.

Even when writing on the obtained surface-treated plastic sheet with an aqueous pen, the image was not blurred as in Example 1. In addition, as a result of printing with a PPC copier (Fuji Xerox 5370), the running property and toner fixing property are good. As a result of printing with an ink jet printer (Seiko Epson Corporation, HG-2000), good transfer is obtained. did.

Example 3 The inorganic-organic composite resin (Hoechst Synthetic Co., Ltd., Movinyl 8030) used in Example 1 and the inorganic-organic composite resin (Hoechst Synthetic Co., Ltd., Movinyl 8000) used in Example 2 were mixed at a ratio of 1: 1. And 100 parts by weight of gelatin was added to 100 parts by weight of the mixed resin. The obtained resin mixture was coated on both surfaces of a transparent plastic film (PET film, 100 μm) to a thickness of 5 μm.

Even when writing on the obtained surface-treated plastic sheet with an aqueous pen, the image was not blurred as in Example 1. In addition, as a result of printing with a PPC copier (Fuji Xerox 5370), the running property and toner fixing property are good. As a result of printing with an ink jet printer (Seiko Epson Corporation, HG-2000), good transfer is obtained. did.

Example 4 An inorganic-organic composite resin obtained by reacting an acrylic styrene-based monomer, inorganic colloidal silica, and hexylethyl methacrylate at a weight ratio of 1: 1: 0.1 was coated on a PET transparent film having a thickness of 5 μm on a 100 μm surface. Was coated on both sides. The obtained surface-treated plastic film had the same effect as in Example-1.

Claims (5)

(57) [Claims] A hydrophilic inorganic-organic composite layer having inorganic colloidal particles is formed on a substrate surface of a plastic film, and the inorganic-organic composite layer is formed of a carbon chain siloxane-bonded to silicon on the surface of colloidal silica particles. A surface-treated plastic film comprising a porous layer comprising an inorganic-organic composite polymer. 2. The surface-treated plastic film according to claim 1, wherein the inorganic-organic composite layer contains a hydrophilic polymer. 3. The surface-treated plastic film according to claim 1, wherein the inorganic colloidal particles are selected from colloidal silica, alumina sol, lithium silicate sol, antimony sol, and ferrite sol. 4. A hydrophilic resin composition is prepared by blending a hydrophilic polymer with an inorganic-organic composite resin comprising a reaction product of inorganic colloidal particles, an ethylene-based monomer and a silane-based monomer, A method for producing a surface-treated plastic film, comprising forming a hydrophilic inorganic-organic composite layer on a substrate surface of a plastic film using the hydrophilic resin composition. 5. A hydrophilic resin composition obtained by adding a hydrophilic resin to an inorganic-organic composite resin comprising a reaction product of inorganic colloidal particles, an ethylene monomer, a silane monomer and a hydrophilic monomer. A method for producing a surface-treated plastic film, comprising preparing an article and forming a hydrophilic inorganic-organic composite layer on a substrate surface of the plastic film using the hydrophilic resin composition.