JPS6136997Y2 - - Google Patents

Description

[Detailed explanation of the idea]

This invention has scratch resistance, abrasion resistance, transparency,
The object of the present invention is to provide a recording material laminate having a surface protective layer with improved flexibility. In order to improve the abrasion resistance of base materials or products that have traditionally been prone to scratches, glass, metal, or resin with high surface hardness is vapor-deposited or coated on the surface to improve mechanical and chemical properties of the surface. has been done. However, in order to apply it to recording materials, the range of use is limited due to processability or processing conditions, such as the effects of heat and radiation during vapor deposition, drying, and curing, and in the case of microfilms, etc., the protective layer is not transparent. In addition, in the case of flexible base materials, the flatness may be impaired, making it difficult to obtain fully satisfactory results in terms of performance and workability. was desired. This invention solves these problems,
A laminated material with a protective layer made of a specific silicon compound that has excellent productivity and processability, and also satisfies scratch resistance, abrasion resistance, weather resistance, water resistance, chemical resistance, flexibility, and stain resistance. The purpose is to provide. The present inventors have previously proposed a laminate in which a silicon compound layer is provided directly on the recording layer, but when the recording layer is easily affected by heat, or when the recording layer swells due to the silicon compound or solvent, When melting, the recording layer may be disturbed, causing problems in use. The present invention not only solves the above problems, but also facilitates handling and significantly improves workability. The present invention has good flatness and is also excellent thermally and optically, so it is particularly effective for protecting recording layers made of flexible substrates. That is, the present invention provides a base film layer made of a flexible organic polymer solid containing a compound containing an epoxy group and a silanol and/or siloxane group in the molecule, or the above-mentioned compound, silanol and/or siloxane group. This is a laminated material in which a silicon compound layer consisting of a compound, a mixture of two or more selected from epoxy compounds, and a hardening agent is laminated, and the laminated film is provided on a recorded recording layer. The silicon compound can be laminated on one or both sides of the base film. In the case of single-sided recording, it is common to use them in combination so that the surface of the base film opposite to that on which the silicon compound is laminated faces the recording layer. This base film is applied to the recorded recording layer. To explain with drawings, the cross-sectional configuration is as shown in FIGS. 1 to 4. Figures 1 and 2 are intended for single-sided protection, and Figures 3 and 4 are intended for double-sided protection. The recording layer is often one-sided, but in this case, the effect of protecting both sides also serves to protect the recording medium base material. In the figure, A is a recorded recording layer, B is a flexible organic polymer film layer, C is a silicon compound layer, and D is an adhesive layer. The B, C, and D layers in FIG. 3 or 4 are the same as above. The method for protecting the recorded recording layer using the B/C laminated film is appropriately selected from the following various methods or a combination thereof. Since the laminated film has excellent flexibility and transparency, it makes full use of the characteristics of flexible polymer films and improves abrasion resistance, which is a drawback of polymer films. By using it as a protective film for the recording layer, it is possible to produce a laminated material with high workability and practicality without adversely affecting the recording layer compared to when the protective layer is directly provided on the recording layer. It is more preferable that the recording layer has flexibility, and continuous processing and continuous use are possible. ○B Overlap them as shown in Figure 1. In this case, the peripheral portions may be glued together, or they may be used simply by being fastened with clips or the like, or in some cases, they may be used as is by simply overlapping them. ○B As shown in FIGS. 2 and 3, the entire recording layer is laminated and combined via a highly transparent adhesive layer. ○C Make a bag as shown in Figure 4 and put the recording layer inside it. At this time, it goes without saying that the adhesive layer D may not be used and it may be fixed with a suitable holder. In addition to the above-mentioned advantages, the above ○C has the following features and is a preferred embodiment. * Because the bag has good transparency, it can be used while in the bag, and the recording layer can be copied and reproduced. * The bag has excellent flexibility and is easy to handle. * The recording layer can be changed freely as necessary (the bag can be used repeatedly). *There is no change in the recording layer because no heat is applied to the recording layer, and the recording layer does not come into contact with or adhere to the adhesive. The agent used in ○C above can be effectively applied as a variety of protective cases, such as microfilm jackets for automatic retrieval, and can be stored and reused in the bag, so important records can be saved when making copies, etc. There is no need to take items out of the bag one by one, and the recording layer has the great advantage of being able to be used repeatedly without being damaged. Furthermore, since the bag itself is covered with the silicon compound layer C, it will not be scratched, making it extremely useful for optical applications such as microfilm. The recorded recording layer A of the present invention refers to a material in which a layer on which characters, images, or signals are recorded is provided on at least one surface of a base material such as glass, metal, plastic plate, plastic film, or paper. Specific examples are as follows. Magnetic cards, magnetic tapes, magnetic disks, video disks, manuscripts for overhead projectors, pre-imaged films such as various silver salts, diazonium, and electrophotographs, optical letters masks, labels, decorations, etc.
Displays for packaging, printed matter, plate making, etc. Flexible organic polymer films include, for example, polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6 naphthalene dicarboxylate, polyolefins such as polypropylene and polyethylene, and polyamides such as so-called nylon-6 and nylon-12. , polyimide having a five-membered ring imide bond in the polymer main chain, cellulose derivatives such as cellulose ester, polycarbonate, (meth)acrylic acid ester copolymer, polyvinyl chloride, copolymer with maleic acid or itaconic acid and metal It is an organometallic polymer crosslinked by ions, and includes copolymers or blends thereof, but is not necessarily limited thereto. Although these polymer films can be used in an unstretched state, stretching, particularly biaxial stretching, improves mechanical properties and chemical properties, which is preferable. Among them, polyethylene terephthalate film is particularly preferably used. Furthermore, these polymer films can be subjected to known surface treatments or provided with a surface modification layer such as a primer to improve adhesion, if necessary. Although the thickness of the film layer is not particularly specified, it can be used in a range of, for example, 2 to 500 microns, more preferably 6 to 250 microns. Among the silicon compound layers used in the present invention, the compound containing an epoxy group and a silanol and/or siloxane group in the molecule has the general formula (However, X ¹ is

A group containing [Formula], R ¹ is C ₁ to ₆ alkyl or aryl, n is 2 or 3, a
is a compound represented by 0 to 2, and b is 1 to 6).

For example, a group containing [Formula]

[Formula] (R ² is hydrogen or methyl),

[Formula] etc. Specific representative examples include γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β(3,
A hydrolyzate of 4-epoxycyclohexyl)ethyltrialkoxysilane can be mentioned. Among the components of the present invention, compounds containing silanol and/or siloxane groups include hydrolysates of 4-alkoxy silicon and general formula

[expression] or

[Formula] (X ² is C ₁ to ₆ alkyl, halogen, vinyl, aryl, methacryloxy, mercapto, amino, H ₂ N-(CH ₂ ) _b -NH- group, R ¹ is C ₁ to ₆ alkyl or aryl, n is 2 or 3, b is 1
It is a compound represented by ~6). Specific examples include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, sec-butyl silicate, tert-butyl silicate, methyltrialkoxysilane, vinyltrialkoxysilane, vinyltriacetoxysilane, vinyl Trialkoxysilane, phenyltrialkoxysilane, methacryloxypropyltrialkoxysilane, chloropropyltrialkoxysilane, alkyltriacyloxysilane, γ-aminopropyltrialkoxysilane, N-β (aminoethyl)
γ-aminopropyltrialkoxysilane, γ-
Examples include mercaptopropyltrialkoxysilane, dialkyldialkoxysilane, alkylphenyldialkoxysilane, diphenyldialkoxysilane, N-β (aminoethyl)γ-aminopropylmethyldialkoxysilane, hydrolyzate of alkyltrichlorosilane, etc. be able to. Hydrolysis of these silicon compounds is produced by adding and stirring water or an acidic aqueous solution such as hydrochloric acid or sulfuric acid. This is usually carried out by adding acidic water to the silicon compound all at once or gradually. During hydrolysis, alcohol, alkoxy alcohol, organic carboxylic acids such as acetic acid, etc. are produced, so hydrolysis can be carried out without a solvent. Alternatively, the silicon compound can be mixed with a suitable solvent and then hydrolyzed. Usually, the obtained hydrolyzate solution is used as it is, but depending on the purpose, after hydrolysis is performed without a solvent, an appropriate amount of the generated alcohol, etc. is removed by heating and/or under reduced pressure before use. It is also possible to substantially replace the solvent by subsequently adding a suitable solvent. Alcohol, ester,
Various solvents such as ethers, ketones, halogenated hydrocarbons, and aromatic solvents such as toluene can be used depending on the purpose, and mixed solvents can also be used if necessary. In the case of two or more types, they may be hydrolyzed individually and then mixed, or two or more types may be mixed and then hydrolyzed. Epoxy compounds among the components are widely used in paints, casting, etc., such as polyolefin-based epoxy resins synthesized by peroxidation methods, cyclopentadiene oxide, or those obtained from hexahydrophthalic acid and epichlorohydrin. polyglycidyl esters, polyhydric phenols such as bisphenol A, catechol, and resorcinol, or (poly)ethylene glycol,
Polyglycidyl ethers obtained from epichlorohydrin and polyhydric alcohols such as (poly)propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, and sorbitol, cyclic epoxy resins, epoxidized vegetable oils, novolac type phenolic resins Examples include epoxy novolak resins obtained from phenolphthalein and epichlorohydrin, epoxy resins obtained from phenolphthalein and epichlorohydrin, and copolymers of glycidyl methacrylate and acrylate monomers such as methyl methacrylate or styrene. Although various epoxy curing agents can be used as the curing agent in the present invention, an aluminum compound having the structure shown below is particularly effective in achieving the object of the present invention. The compound has the general formula A1・Y _n・Z _(3-n) [However, Y is OL (L is C _1-6 alkyl), Z
is the general formula M ¹ COCH ₂ COM ² or
At least one ligand derived from a compound represented by M ³ COCH ₂ COOM ⁴ (M ¹ , M ² , M ³ , M ⁴ are all C _1-6 alkyl), and m
is an integer from 0 to 3]. Specific examples of this compound include various compounds, but from the viewpoint of solubility in the composition, stability, and effect as a curing catalyst, aluminum isopropoxide, aluminum ethoxide, aluminum tert. -butoxide, aluminum acetylacetonate, aluminum bis-ethylacetoacetate-mono-acetylacetonate, aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-
These include di-iso-propoxide-mono-methylacetoacetate, aluminum-di-sec-butoxide-mono-ethylacetoacetate, aluminum-di-methoxide-mono-methylacetoacetate, and the like. It is also possible to use a mixture of two or more of these. The appropriate amount of the curing agent added is 0.0001 to 0.5 parts by weight, particularly preferably 0.0005 to 0.2 parts by weight, per 1 part by weight of the above-mentioned compound or mixture. This results in defects such as decreased transparency and water resistance of the coating film or resin. Further, colloidal silica can be blended within a range that can maintain the properties of the silicon compound. An effective colloidal silica is a colloidal solution in which silicic anhydride is dispersed in water or an alcoholic solvent, which is produced by a well-known method and is commercially available. For purposes of this invention, particles with an average particle size of 5 to 100 millimeters are useful. In the composition of the present invention, it is also possible to use a surfactant to improve the flow during application and the smoothness of the coating film, and in particular, surfactants such as block or graft copolymers of dimethylsiloxane and alkylene oxide can be used. is valid. Furthermore, curing catalysts and additives (e.g., adhesion promoters, PH regulators, plasticizers, stabilizers, antioxidants, ultraviolet absorbers, lubricants, thickeners, antifoaming agents, colorants, etc.) are added as necessary. It is also permissible to use them in combination. Although the thickness of the silicon compound layer is not particularly specified, it is preferably in the range of 0.5 to 30 μm, for example. If it is too thin, it will not have sufficient wear resistance, and if it exceeds 30μ, it will take longer to harden, and there is a risk of reduced flatness and cracks. As a means of applying such a silicon compound layer, commonly used coating methods such as brush coating, dip coating, knife coating, roll coating, spray coating, flow coating, and rotation coating (spinner, whaler, etc.) can be easily used. It is. As the adhesive layer D, for example, saturated polyester resin, unsaturated polyester resin, alkyd resin,
Phenol resin, urea resin, melamine resin, epoxy resin, urethane resin, vinyl resin, acrylic resin, polyolefin resin, natural resin (e.g. pine resin, dammar, terpene resin, coumaron indene resin, natural rubber), water-soluble resin ( Examples include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, polyacrylamide, polyvinylpyrrolidone, polyethyleneimine), synthetic rubber, and copolymers or blends thereof. Furthermore, well-known additives can be added as appropriate. When the recording layer is easily affected by heat, pressure sensitive adhesives are preferably used. The laminated material obtained in the above manner has a transparent protective coating, has excellent hardness, particularly abrasion resistance, and scratch resistance, and hardly gets scratched even when rubbed strongly with hard materials such as steel wool. Since there is no deterioration in appearance or peeling of the recording layer due to scratches during use, which were problems with recorded recording layers, the product value is not only significantly improved, but also a protective laminated film is provided. Since there is no chemical change in the recording layer at all, the practical characteristics are not substantially affected. Examples will be described below, but the invention should not be limited to these. Note that parts and percentages in the examples are by weight unless otherwise specified. Example 1 A primer layer made of an acrylic acid ester copolymer was provided on one side of a biaxially stretched polyethylene terephthalate film (“Lumirror” manufactured by Toray Industries, Inc.) with a thickness of 25μ, and then γ-glycidoxypropyl 100 parts of a hydrolyzate (containing 58% solids) obtained by hydrolyzing trimethoxysilane with a 0.01N aqueous hydrochloric acid solution was added to "Dinacol" EX314 (Nagase Sangyo Co., Ltd.)
Co., Ltd. epoxy compound) 25 parts, aluminum acetylacetonate 6 parts, silicone surfactant
0.14 parts of isopropyl alcohol/n-butyl alcohol = 145 parts of a 2/1 mixture was added and blended by roll coating so that the solid content coating thickness was 3μ, dried at 140℃ for 1 minute, cured, and then continued. I rolled it up. An adhesive layer made of acrylic resin was provided on the non-coated surface of the laminated film, and then laminated onto the silver salt surface of an imaged silver salt optical mask having a polyester film having a thickness of 100 μm as a base. The obtained laminated material had good abrasion resistance, no scratches occurred even when rubbed with #0000 steel wool, and no deterioration in appearance was observed at all. There were no practical problems with respect to flexibility, transparency, optical uniformity, and durability. When the optical mask was brought into close contact with a copper-clad printed circuit board and a printed circuit pattern was printed on it, there were no scratches even after 300 printings, and the appearance was good. In the case of using only the imaged silver salt optical mask, the abrasion resistance was poor, and scratches occurred even when lightly rubbed with steel wool #0000. When the printed circuit pattern was printed in close contact with the copper-clad printed circuit board,
The number of uncensored uses was less than 10. Example 2 In Example 1, as the silicon compound layer, γ
- 100 parts of a hydrolyzate (containing 61% solids) obtained by hydrolyzing glycidoxypropylmethyldiethoxysilane with a 0.01N aqueous hydrochloric acid solution, and 45 parts of "Epicote" 828 (an epoxy compound manufactured by Ciel Chemical Co., Ltd.) ,
Methanol-dispersed colloidal silica (“Methanol Silica Sol” manufactured by Nissan Chemical Co., Ltd., solid content concentration 30%) 150
9 parts of aluminum acetylacetonate, 0.32 parts of a silicone surfactant, and 200 parts of a 2/1/1 mixture of isopropyl alcohol/n-butyl alcohol/toluene as a solvent. The same results as in Example 1 were obtained when the thickness was set to 3μ. Example 3 A primer layer made of an acrylic ester copolymer was provided on one side of a biaxially stretched polyethylene terephthalate film (“Lumirror” manufactured by Toray Industries, Inc.) with a thickness of 125μ, and then γ-glycidoxypropyl was applied on the primer layer. “Dinacol” EX320 (an epoxy compound manufactured by Nagase Sangyo Co., Ltd.) was added to 100 parts of the hydrolyzate obtained by hydrolyzing trimethoxysilane with a 0.01N aqueous hydrochloric acid solution.
45 parts, methanol-dispersed colloidal silica (“Methanol Sol” manufactured by Nissan Chemical Co., Ltd., solid content concentration 30%) 130
parts, aluminum acetylacetonate 10 parts, silicone surfactant 0.32 parts, isopropyl alcohol/n-butyl alcohol/toluene = 2/
A paint containing 200 parts of a 1/1 mixture was applied so that the solid content was 3 μm thick, dried at 150° C. for 1 minute, cured, and then rolled up continuously. The layer had good transparency, and a laminated film with good workability, flatness, and flexibility was obtained. A bag was made with the silicon compound layer of the laminated film on the outside, and the imaged silver salt microfilm was placed in the bag to be used as a jacket for the microfilm. While it was in the bag, it was searched mechanically, and then it was enlarged and projected and played back while it was still in the bag. It had good abrasion resistance and durability, and no deterioration in appearance was observed at all. Even after repeated use, there was no damage to the internal silver halide film, and high-quality images could be maintained for a long period of time.

[Brief explanation of drawings]

1 to 4 schematically show the cross-sectional structure of the laminated material of the present invention. A... Recorded recording layer, B... Flexible organic polymer film layer, C... Silicon compound layer, D...
Adhesive layer.

Claims (1)

[Claims for Utility Model Registration] A compound containing an epoxy group and a silanol and/or siloxane group in the molecule, or the above compound, silanol and/or siloxane group in the base film layer made of a plastic organic polymer solid. 1. A laminated material comprising a silicon compound layer comprising a compound, a mixture of two or more selected from epoxy compounds, and a curing agent, and the laminated film is provided on a recorded recording layer.