JPH031152B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a flame-retardant transfer material. (Prior art) Various transfer materials have been known for transferring metal vapor deposited layers and colored resin layers containing dyes and pigments. A variety of resins are used, many of which are flammable. Therefore, traditionally, as necessary,
Methods such as adding a heat retardant to the resin constituting the transfer material to make it a flame-retardant resin, or coating the surface of the transfer material with a substantially transparent flame-retardant resin after transferring it to the transfer surface. This makes the transfer material or body flame retardant. However, the development of flame-retardant resins that are substantially transparent, do not impair the functions of the transfer material, and effectively impart flame retardancy has not been sufficient, so this method using conventional flame-retardant resins has not been fully developed. However, it has been difficult to impart good flame retardancy to transfer materials or transfer bodies using conventional flame retardant methods. (Purpose of the Invention) In view of the above, the present inventors conducted intensive research with the aim of developing a transfer material having good flame retardancy. The liquid resin composition as the main component forms a resinous film after evaporation of the solvent, and the resinous film exhibits good flame retardancy due to the synergistic effect with halogen and phosphorus, and also has good adhesion and transparency. The present inventors have discovered that a flame-retardant transfer material using this resin coating as a flame-retardant layer of a transfer material has excellent flame retardancy, leading to the present invention. (Structure of the Invention) The first flame-retardant transfer material according to the present invention includes a base film, a transparent or semi-transparent mold release agent layer laminated on one side of the base film, and a flame-retardant film laminated thereon. It consists of a first resin layer, a second resin layer laminated on this flame-retardant resin layer, and a heat-sensitive adhesive layer laminated on this second resin layer. In the resin layer, the phosphoric acid ester has a phosphorus content of 15 to 100 parts by weight and the brominated epoxy resin has a bromine content of 15 to 100 parts by weight, based on 100 parts by weight of vinylidene chloride resin.
It is characterized by comprising a resin composition containing parts by weight. The flame retardant transfer material according to the present invention will be explained below based on the drawings showing examples. FIG. 1 is a sectional view of a main part of a first transfer material according to the present invention. The base film 1 to be used is not particularly limited, but usually, flexible synthetic resin films such as polyester, polyamide, polyimide, polycarbonate, polyvinyl chloride, polypropylene, polyethylene, etc., and laminates thereof are preferably used. If necessary, cellophane or glassine paper may also be suitably used. A transparent or semi-transparent release material layer 2 is laminated on one side of such a base film 1. The mold release agent is not particularly limited, and various conventional mold release agents such as silicone resins, fluorine resins, fatty acid esters, fatty acid amides, acrylic resins, waxes, cellulose resins, rosins and their derivatives, etc.
One kind or a mixture of two or more kinds of styrenic resins and the like can be used as appropriate. The release agent layer is usually formed by applying a solution of these release agents to one side of a base film and drying it. In the first transfer material according to the present invention, a substantially transparent flame-retardant resin layer 3 is laminated as a first resin layer on such a release agent layer. This flame-retardant resin contains vinylidene chloride, phosphate ester, and brominated epoxy resin, and has good flame retardancy due to the synergistic effect of chlorine, phosphorus, and bromine. Examples of phosphoric acid esters contained in the flame-retardant resin include diethyl phosphate, dimethyl phosphate, triethyl phosphate, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, trioctyl phosphate, and tris(chloroethyl). Examples include, but are not limited to, phosphate, tris(dichloropropyl) phosphate, and the like. The phosphoric acid ester is contained so that the phosphorus content is 15 to 100 parts by weight, preferably 30 to 60 parts by weight, based on 100 parts by weight of the vinylidene chloride resin. If the phosphorus content is less than 15 parts by weight, sufficient flame retardant effect will not be achieved, and if it exceeds 100 parts by weight, undesirable physical properties such as burning of the film will tend to occur. Furthermore, the brominated epoxy resin contained in the flame retardant resin is not particularly limited, and for example, an epoxy resin polymerized by blending brominated bisphenol A with a bromine content of 18 to 20% is used. It will be done. The brominated epoxy resin has a bromine content of 15 to 100 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of the vinylidene chloride resin. If the bromine content is less than 15 parts by weight, sufficient flame retardancy cannot be obtained due to the synergistic effect with chlorine and phosphorus, and if it is more than 100 parts by weight, the performance of the formed flame-retardant resin layer may deteriorate. more likely to occur. Although the flame-retardant resin composition used in the present invention contains the above-mentioned components, desired resins, antioxidants, anti-aging agents, lubricants, pigments, fillers, etc. may be added as appropriate. In order to laminate the above flame retardant resin layer on the mold release agent layer, the required amounts of vinylidene chloride resin, phosphoric acid ester and brominated epoxy resin are dissolved in an organic solvent such as methyl ethyl ketone or toluene or a mixture thereof. A flame-retardant film-forming liquid composition is obtained, which is applied onto the release agent layer using a Clavia roll coater, reverse roll coater, spray gun, or the like, and dried. A second resin layer 4 is laminated on the flame-retardant resin layer as the first resin layer. This second resin layer usually contains a dye and/or a pigment and is colored depending on the purpose of transfer. The dyes or pigments used for this coloring are commonly used organic solvent-soluble dyes or organic/inorganic pigments, and examples of the pigments include extender pigments, fluorescent pigments, luminescent pigments, pearl pigments, thermochromic pigments, Examples include microencapsulated liquid crystal, metal powder, and metal vapor-deposited powder. The resin for this second resin layer may be one or a mixture of two or more of acrylic resin, vinyl chloride-vinyl acetate copolymer resin, polyurethane resin, urea resin, melamine resin, polyester resin, epoxy resin, etc. A thermoplastic or thermosetting resin is used. Alternatively, a solvent-free or solvent-added ultraviolet curable resin coating may be applied and cured by ultraviolet irradiation, and this may be used as the second resin layer. In this case, as the ultraviolet curable composition, prepolymers or oligomers such as acrylic ester, epoxy, urethane, polyester, and alkyd resins may be used alone or in mixtures. Further, a photosensitizer, a monofunctional and polyfunctional monomer as a reactive diluent, a polymerization initiator, a stabilizer, an organic solvent, etc. are added as appropriate. Further, a heat-sensitive adhesive layer 6 is laminated on the second resin layer. As a heat-sensitive adhesive,
Those conventionally used in the production of transfer materials can be used as appropriate, such as vinyl acetate, vinyl chloride-vinyl acetate copolymer, acrylic resin, ethylene-vinyl acetate copolymer, rubber derivative, epoxy resin, polyester. Adhesives include thermoplastic resins such as resins, polyurethane resins, rosin resins, petroleum resins, and thermosetting resins. Alternatively, since the above-mentioned flame-retardant film-forming liquid composition used in the present invention has good adhesive properties, it may be adjusted to an appropriate viscosity and used as an adhesive. The adhesive may contain pigments such as titanium oxide, calcium carbonate, barium sulfate, magnesium carbonate, lithopone, talc, clay, white carbon, extender pigments, etc. as fillers, if necessary. Next, a second flame-retardant transfer material according to the present invention will be explained. The second flame-retardant transfer material according to the present invention includes a base film 1, a transparent or translucent release agent layer 2 laminated on one side of the base film 1, and a flame-retardant first layer laminated thereon. A resin layer 3, a second resin layer 4 laminated on this flame-retardant resin layer, a metal vapor deposition layer 5 deposited on this second resin layer, and a metal vapor deposition layer 5 on this metal vapor deposition layer. It consists of a laminated heat-sensitive adhesive layer 6, and the flame-retardant resin layer has a phosphorus content of 15 to 15 parts by weight of phosphoric acid ester based on 100 parts by weight of vinylidene chloride resin.
100 parts by weight and a brominated epoxy resin containing 15 to 100 parts by weight as a bromine content. The base film, release agent layer, flame-retardant resin layer, second resin layer, and heat-sensitive adhesive layer in the second flame-retardant transfer material are the same as those described in the first flame-retardant transfer material. The same is true. The metal vapor deposition layer laminated on the second flame-retardant transfer material includes not only a metal but also a metal oxide vapor deposition layer, and the method for forming this metal vapor deposition layer is not limited at all, and may be any conventional method. It is formed on the second resin layer in a more known manner. Therefore, for example, in addition to single metals such as aluminum, silver, gold, copper, zinc, nickel, and chromium, alloys and various compounds of these can be deposited using vacuum evaporation methods, high-frequency induction heating methods, electric It is deposited by a resistance heating method, a sputtering method, an ion plating method, an electron beam heating method, or the like. (Effects of the present invention) As described above, the first flame-retardant transfer material according to the present invention has a substantially transparent flame-retardant resin layer between the second resin layer and the release agent layer. Therefore, when this transfer material is thermally bonded to the desired transfer surface and the base film is removed, that is, when the transfer is performed, the flame-retardant resin layer covers the transfer body and the internal resin layer is protected from combustion. and protect the transferee. In particular, the flame-retardant transfer material of the present invention exhibits an excellent flame-retardant effect due to the synergistic effect of the elements chlorine, phosphorus, and bromine in the laminated flame-retardant resin. Since the resin is vinylidene chloride and epoxy resin, the second resin layer has good adhesion and excellent transparency, and does not impair the function of the transfer material at all. Further, in the second flame-retardant transfer material according to the present invention, the flame-retardant resin layer protects the second resin layer from combustion, as in the first flame-retardant transfer material, and the metal vapor-deposited layer also protects the second resin layer from combustion. It also protects the internal adhesive layer and the object to be transferred. (Example) Examples of the present invention are shown below. In the examples, parts indicate parts by weight. Example 1 A flame-retardant film-forming liquid composition was prepared by dissolving 40 parts of vinylidene chloride resin, 100 parts of diethyl phosphate, and 100 parts of brominated epoxy resin in 475 parts of a mixed solvent of equal amounts of methyl ethyl ketone and toluene. This composition corresponds to containing 50 parts by weight of phosphorus and 50 parts by weight of bromine based on 100 parts by weight of vinylidene chloride resin. This liquid composition and a diluted liquid composition obtained by diluting it 1 to 3.5 times are applied onto a release agent laminated on a polypropylene resin film and a polyester resin film using a gravure coater machine,
Then, it was dried to form a flame-retardant resin layer, which is a first resin layer. Next, on this flame-retardant resin layer, UV-curable resin coating compositions A to D having the compositions shown in Table 1 are prepared and applied.
Irradiate with an 80W/cm high-pressure mercury lamp to cure the second
A resin layer was formed. Furthermore, a heat-sensitive adhesive layer was laminated on the second resin layer to obtain the first flame-retardant transfer material of the present invention. The obtained flame-retardant transfer material is printed on ABS using a foil stamping transfer machine.
The flame retardance of the transferred body was examined by transferring it onto the surface of a molded product made of resin and polyacetal resin (Dyuracon). Flame retardancy was determined by igniting the transfer material from the transfer material side with a lighter, and based on the number of ignitions until ignition and the self-extinguishing property when ignited. UV rays having the composition shown in Table 1 A in the second resin layer

[Table] Table 2 shows the results when curable resin was used. As shown in the table, the transfer bodies to which the flame-retardant transfer material of the present invention was transferred had good flame retardancy regardless of whether the transfer target was an ABS resin or a polyacetal resin. Example 2 In the same manner as in Example 1, on one side of a polypropylene resin film and a polyester resin film,
A mold release agent layer, a first resin layer made of the same flame-retardant film-forming liquid composition as in Example 1 or its diluted solution, and a second resin layer made of an ultraviolet curable resin paint were laminated. Next, a metal vapor deposited aluminum layer and a heat-sensitive adhesive layer are sequentially laminated on the second resin layer,
A second flame-retardant transfer material of the present invention was obtained. The obtained flame-retardant transfer material is printed on ABS using a foil stamping transfer machine.
Example 1 Regarding the transfer body obtained by transferring onto the molded product surface of resin and polyacetal resin (Dyuracon)
Flame retardancy was examined in the same manner. Table 3 shows the results when an ultraviolet curable resin having the composition shown in Table 1 A was used for the second resin layer.

【table】

[Table] As shown in the table, good flame retardancy was also observed in the transfer material to which the second flame-retardant transfer material of the present invention was transferred. Comparative Example 1 40 parts of vinylidene chloride was dissolved in 160 parts of a solvent in which methyl ethyl ketone and toluene were mixed in equal amounts, and the resulting resin solution and its diluted solution were used to release the mold onto a base film in the same manner as in Example 1. A transfer material for comparison was obtained by sequentially laminating the agent layer, the coating layer of the resin liquid or diluted liquid, the second resin layer, the metal vapor deposition layer, and the heat-sensitive adhesive layer. The above transfer material was transferred to transfer objects made of ABS resin and polyacetal resin, and the flame retardance was examined in the same manner as in Example 1.

[Table] The results are shown in Table 4. In the transfer material of this comparative example,
It was not possible to impart flame retardancy to any of the transfer bodies. Comparative Example 2 40 parts of brominated epoxy resin was dissolved in 160 parts of a mixed solvent of equal amounts of methyl ethyl ketone and methyl isobutyl ketone, and the resulting resin solution and its diluted solution were used to coat a base film in the same manner as in Example 1. a mold release agent layer, a coating layer of the resin liquid or diluted liquid, and a second layer.
A transfer material was obtained by sequentially laminating a resin layer, a metal vapor deposited layer, and a heat-sensitive adhesive layer. The above transfer material was transferred to transfer objects made of ABS resin and polyacetal resin, and the flame retardance was examined in the same manner as in Example 1. In the transfer material made of the transfer material of this comparative example, only slight flame retardance was observed only when the undiluted resin liquid was used. Comparative Example 3 40 parts of diethyl phosphate was dissolved in 160 parts of a mixed solvent of equal amounts of methyl ethyl ketone and xylene, and the resulting resin solution and its diluted solution were used to form a release agent layer on a base film using a reverse roll coater. A transfer material was obtained by sequentially laminating a coating layer of the above resin liquid or diluted resin, a second resin layer made of an ultraviolet curable resin, and a heat-sensitive adhesive layer. The obtained transfer material was transferred to transfer objects made of ABS resin and polyacetal resin, and the flame retardance was examined in the same manner as in Example 1. Similarly to Comparative Example 2, in this comparative example, the flame retardant effect was extremely small compared to the flame retardant transfer material according to the present invention.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a main part of a first flame-retardant transfer material according to the present invention, and FIG. 2 is a cross-sectional view of a main part of a second flame-retardant transfer material according to the present invention. 1...Base film, 2...Release agent layer, 3...
Flame retardant resin layer, 4... second resin layer, 5... metal vapor deposited layer, 6... heat sensitive adhesive layer.

Claims (1)

[Scope of Claims] 1. A base film, a transparent or translucent mold release agent layer laminated on one side of the base film, a flame-retardant first resin layer laminated thereon, and a flame-retardant first resin layer laminated thereon; It consists of a second resin layer laminated on the resin layer and a heat-sensitive adhesive layer laminated on the second resin layer, and the flame-retardant resin layer is made of 100 parts by weight of vinylidene chloride resin. On the other hand, the phosphorus content of phosphoric acid ester is 15~
A flame-retardant transfer material comprising a resin composition containing 100 parts by weight and a brominated epoxy resin with a bromine content of 15 to 100 parts by weight. 2. The flame-retardant transfer material according to claim 1, wherein the second resin layer is made of a cured coating film of an ultraviolet curable resin coating. 3 A base film, a transparent or translucent mold release agent layer laminated on one side thereof, a flame-retardant first resin layer laminated thereon, and a flame-retardant first resin layer laminated on this flame-retardant resin layer. a second resin layer deposited on the second resin layer, a metal deposition layer deposited on the second resin layer, and a heat-sensitive adhesive layer laminated on the metal deposition layer; The phosphoric acid ester layer has a phosphorus content of 15 to 100 parts by weight of vinylidene chloride resin.
A flame-retardant transfer material comprising a resin composition containing 100 parts by weight and a brominated epoxy resin containing 15 to 100 parts by weight as bromine content. 4. The flame-retardant transfer material according to claim 3, wherein the second resin layer is made of a cured coating film of an ultraviolet curable resin coating.