JPS61205136A - Flame-retardant transfer material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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. For this reason, conventionally, flame retardants have been added to the resin constituting the transfer material to make it a flame-retardant resin, or the surface of the transfer material has been coated with a substantially transparent flame-retardant resin after being transferred to the transfer surface. The transfer material or transfer body is made flame retardant by coating with a flammable resin or the like. 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 such 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. It was discovered that a flame-retardant transfer material using this resin coating as a flame-retardant layer of a transfer material has excellent flame retardancy, and the present invention was achieved.

(Structure of the Invention) The first flame-retardant transfer material according to the present invention includes a base film;
A transparent or translucent mold release agent layer laminated on one side, a first flame-retardant resin layer laminated on top of this, and a second resin layer laminated on this flame-retardant resin layer. and a heat-sensitive adhesive layer laminated on the second resin layer, and the flame-retardant resin layer has a phosphorus content of 15 parts by weight of phosphoric acid ester based on 100 parts by weight of vinylidene chloride resin. ~10(1
15 to 15 parts by weight and bromine content of brominated epoxy resin
It is characterized by comprising a resin composition containing 100 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, and polyethylene, and laminates thereof are preferably used. If necessary, cellophane or glassine paper may also be suitably used.

A transparent or translucent mold release agent 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, rosin and its derivatives, and styrene can be used. One or a mixture of two or more of these resins 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, tris (chloroethyl) phosphate, and tris (dicalolopropyl). ) phosphates, etc., but are not limited to these. The phosphoric acid ester has a phosphorus content of 15 to 100 parts by weight, preferably 3 parts by weight, based on 100 parts by weight of the vinylidene chloride resin.
It is contained in an amount of 0 to 60 parts by weight. When the phosphorus content is less than the above 15 parts by weight, a sufficient flame retardant effect is obtained, while when it exceeds 100 parts by weight, undesirable physical properties such as burning of the coating tend to occur.

Further, 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
~20% is used.

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 preferably contained in an amount of 30 to 50 parts by weight.

If the bromine content is less than 15 parts by weight, sufficient flame retardancy due to the synergistic effect with chlorine and phosphorus cannot be obtained;
If the 0-heavy area increases too much, the performance of the formed flame-retardant resin layer coating tends to deteriorate.

The flame-retardant resin composition used in the present invention contains the above-mentioned components, and further contains desired resins, antioxidants, anti-aging agents,
A lubricant, pigment, filler, 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. Then, a flame-retardant film-forming liquid composition was prepared, and this was coated with a Taravia roll coater.
Coat on the release agent layer using a reverse roll coater or spray gun, and dry.

On top of such a flame retardant resin layer as the first resin layer,
A second resin layer 4 is laminated. This second resin layer usually contains a dye and/or a pigment and is colored depending on the purpose of transfer. The dye or pigment used for this coloring is a commonly used organic solvent soluble dye or organic/inorganic pigment, and examples of the pigment include extender pigments,
Examples include fluorescent pigments, phosphorescent pigments, pearlescent pigments, temperature-indicating pigments, microencapsulated liquid crystals, metal powders, and metal vapor deposited layers. The resin of this second resin layer includes acrylic resin,
Thermoplastic or thermosetting resins made of one or a mixture of two or more of vinyl chloride-vinyl acetate copolymer resins, polyurethane resins, urea resins, melamine resins, polyester resins, epoxy resins, etc. are 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. At this time, 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. Also,
Monofunctional as photosensitizer, reactive diluent, if necessary.
A polyfunctional monomer, 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 the heat-sensitive adhesive, those conventionally used in the production of transfer materials are appropriately used, such as vinyl acetate, vinyl chloride-vinyl acetate copolymer, acrylic resin, ethylene-vinyl acetate copolymer, Examples include adhesives such as thermoplastic resins or thermosetting resins such as rubber derivatives, epoxy resins, polyester resins, polyurethane resins, rosin resins, and petroleum 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 above-mentioned flame-retardant and flame-retardant resin layer has a phosphorus content of 15 parts by weight of phosphoric acid ester based on 100 parts by weight of vinylidene chloride resin.
-100 parts by weight and a resin composition containing 15 to 100 parts by weight of a brominated epoxy resin as a bromine content.

A base film in the second flame-retardant transfer material, a release agent layer,
The flame-retardant resin layer, the second resin layer, and the heat-sensitive adhesive layer are the same as those described for the first flame-retardant transfer material.

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 in any way,
It is formed on the second resin layer by a conventionally known method. Thus, for example, aluminum, silver, gold, copper,
In addition to single metals such as zinc, nickel, and chromium, their alloys and various compounds can be deposited as needed using vacuum evaporation methods, high-frequency induction heating methods, electrical resistance heating methods, sputtering methods, ion blating methods, electronic It is deposited by a method such as a wire heating method.

(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 heat-sensitively adhered 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 is also
It protects the resin layer from combustion, and further protects the internal adhesive layer and transfer target together with the metal vapor deposited layer.

(Example) Examples of the present invention are shown below. In the examples, parts indicate parts by weight.

Example 1 40 parts of vinylidene chloride resin, 10 parts of diethyl phosphate
0 parts and 100 parts of a brominated epoxy resin were dissolved in 475 parts of a mixed solvent of equal amounts of methyl ethyl ketone and toluene to prepare a flame-retardant film-forming liquid composition. This composition corresponds to containing 50 parts by weight of phosphorus and 50 parts by weight of bromine per 10 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 placed on a release agent layer laminated on a polypropylene resin film and a polyester resin film,
It was coated using a gravure coater and then dried to form a flame-retardant resin layer, which is the first resin layer. Next, on this flame-retardant resin layer, ultraviolet curable resin coating compositions A to A having the compositions shown in Table 1 were prepared and applied.
The resin was cured by irradiation with a high-pressure mercury lamp of 0 W/mouth to form a second resin layer. 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 was transferred onto the surface of an ABS resin and polyacetal resin (Duracon) molded product using a foil stamping transfer machine, and the flame retardance of this transfer body was examined. Flame retardancy was determined by igniting the transfer material from the transfer material side with a lighter and determining the number of ignitions until ignition and the self-extinguishing property when ignited.

The second resin layer contains an ultraviolet radiation having the composition shown in Table 1 A.
1 Table 2 shows the results when surface-curing 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, a mold release agent layer was applied to one side of a polypropylene resin film and a polyester resin film, and a first resin made of the same H flammable film-forming liquid composition as in Example 1 or its diluted solution was applied. layer, the second layer is made of UV-curable resin paint.
resin layers were laminated.

Next, a metal vapor deposited aluminum layer and a heat-sensitive adhesive layer were sequentially laminated on the second resin layer to obtain a second flame-retardant transfer material of the present invention.

The obtained flame retardant transfer material was transferred onto the surface of an ABS resin and polyacetal resin (Duracon) molded product using a foil stamping transfer machine, and the flame retardance was examined in the same manner as in Example 1. .

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 2 (Note) AAAA: No ignition even after ignition 7 times.

AAA: It does not ignite even after ignition 6 times, and self-extinguishes after 7 times. A^: It will not ignite even after igniting it 5 times, and will self-extinguish after the 6th time. A: It won't ignite even after igniting it 4 times. ^-
B: Burns after 3 ignitions.

B: Burns with two ignitions. C: Burns with one ignition.

As shown in Table 3, 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 made by mixing equal amounts of methyl ethyl ketone and toluene, 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 a coating layer of the resin liquid acid or diluted liquid, a second resin layer, a metal vapor deposition layer, and a heat-sensitive adhesive layer.

The above transfer material was transferred to transfer objects made of ABS resin and polyacecool resin, and the flame retardance was examined in the same manner as in Example 1.

Table 4 The results are shown in Table 4. With the transfer materials of this comparative example, flame retardancy could not be imparted 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,
Using the obtained resin liquid and its diluted liquid, in the same manner as in Example 1, a release agent layer, a coating layer of the resin liquid acid or diluted liquid, a second resin layer, and a metal vapor deposition layer were formed on the base film. A transfer material was obtained by sequentially laminating the layers and the heat-sensitive adhesive layer.

The above transfer material was transferred to transfer objects made of ABS resin and polyacecool 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 an 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 liquid and its diluted liquid were used in a reverse roll coater.
A release agent layer, a coating layer of the resin liquid acid or diluted solution, a second resin layer made of an ultraviolet curable resin, and a heat-sensitive adhesive layer were sequentially laminated on the base film to obtain a transfer material.

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.

In this comparative example as well, the flame retardant effect was extremely small compared to the flame retardant transfer material according to the present invention, similar to comparative example 2.

[Brief explanation of drawings]

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. DESCRIPTION OF SYMBOLS 1... Base film, 2... Mold release agent layer, 3... Flame retardant resin layer, 4... Second resin layer, 5... Metal vapor deposition layer, 6... Heat sensitive adhesive layer. Figure 1 Figure 2

Claims (4)

[Claims] (1) A base film, a transparent or semi-transparent mold release agent layer laminated on one side of the base film, and a flame-retardant first layer laminated thereon.
a 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, and the flame-retardant resin The layer is made of a resin composition containing 15 to 100 parts by weight of a phosphoric acid ester as a phosphorus content and 15 to 100 parts by weight as a bromine content of a brominated epoxy resin based on 100 parts by weight of a vinylidene chloride resin. Flame retardant transfer material. (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 of the base film, and a flame-retardant first layer laminated thereon.
a second resin layer laminated on this flame-retardant resin layer, a metal vapor deposition layer deposited on this second resin layer, and a second resin layer laminated on this metal vapor deposition layer. and a heat-sensitive adhesive layer, and the flame-retardant resin layer is made of vinylidene chloride resin 1.
00 parts by weight, 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. Transfer material. (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.