JPS5920464B2 - heating transfer decorative materials - Google Patents

Description

[Detailed description of the invention] The present invention relates to a heat transfer method for resetting.

It concerns high-quality, multicolored and chemically resistant decorative materials to be applied, inter alia, to glass, ceramic, metal or heat-stable plastic surfaces. Techniques for heat transfer decoration are very old, such as the early U.S. Pat. No. 103 issued to McKerr0w.
It is described in the specification of No. 0908.

It describes a heat transfer reticle having a paper backing, a transfer layer made of resin or wax, and a printed and colored pattern applied to the transfer layer. However, McKerr0w and later e.g. U.S. Pat.
Transfer layers such as those described in No. 71 and No. 2,667,003 were not entirely satisfactory for a number of reasons. An improved thermal transfer reticle based on the use of an oxidized wax as a release layer has been substantially commercialized and is disclosed in U.S. Pat. No. 2,862,832 to Shepard, which The present invention discloses a heat transfer reticle comprising a release layer of wax on a carrier, an ink layer on the release layer, and a heat-activatable plastic adhesive layer on the ink layer.

Although such heat transfer reticles are commercially available in considerable quantities, they have some disadvantages. for example,
When transferred to a clean, transparent surface such as plastic or glass, a portion of the melted wax releasable layer transfers with the label. When solidified, this wax coating forms a "haze" around the design print, clouding the transparent areas and detracting from the appearance of the design print. Other examples of transfer resetting, particularly for glass and ceramics and relatively recent, include U.S. Pat. No. 3,015,557 to J. Gobel
As described in Specification No. 4, the pattern printing is done by finally baking ceramic type ink onto glass or ceramic products.
terSlideoff allows you to raise the moon-shaped pattern transfer.

Resetting techniques using direct dry heat transfer followed by baking of ceramic ink are also known and are disclosed, for example, in Canadian Patent No. 919,521 to R.A. Keelimg et al. Similarly, solvent-activated retardation is also known, in which release is aided by activation of the solvent by a carrier sheet or web (see U.S. Pat. No. 3,298,850 to J. Reed et al. (see US Pat. No. 3,728,210 to J. PirOn) or by direct activation of the adhesive layer by heating and/or pressure of the microencapsulating solvent (see US Pat. No. 3,728,210 to J. PirOn). Finally, another common type of design transfer is precision die-cut design printing using a pressure-sensitive adhesive transfer layer, as disclosed for example in U.S. Pat. No. 3,297,508. . All of the above methods for transferring decorations onto heat-resistant bases such as glass, ceramic or metal have various disadvantages.

The most notable of these is the lack of resistance to chemicals, abrasion and friction when the design printing and adhesive are plastics (partially due to lack of adhesion and cohesion between and within each layer of the transfer label). and the difficulty in obtaining high-quality multicolor designs when the design is printed with ceramic ink having a limited number of colors. Accordingly, one object of the present invention is to provide a stable heat transfer reticle on a heat resistant base.

Another object of the invention is to provide a heat resistant base with a chemical, abrasion and abrasion resistant transfer label.

Yet another object of the present invention is to provide a high quality multicolor design printable, preferably gravure printable, as part of a thermal transfer label.

The present inventor preferably uses certain polymerizable crosslinking agents, which are capable of crosslinking resins in adjacent layers in response to heat to form a strong interlayer chemical bond, as one of the transfer labels. It has been discovered that by use in one or more layers, the resistance to chemicals, abrasion and abrasion is greatly increased resulting in a highly resistant multicolor transfer reticle. In one preferred embodiment, cross-linking occurs between and within layers, so that the cross-linking occurs across the entire thickness of the transfer layer from the outer surface to the surface of the heat-resistant base to which it is applied (including the surface itself). A hardened reticle is obtained which is thermally cured over a period of time.

In this embodiment, not only is the cohesiveness and abrasion resistance of the retsutel superior to that in the prior art, but the retsutel is essentially insensitive to heat. As a result, a glass, ceramic or metal container with a thermoset reticle can be exposed to high temperatures without deleteriously affecting the rettle properties. The present invention is applicable to multilayer decorative transfer labels, such as B. Particularly advantageous is the use of O as disclosed in U.S. Patent Application No. 244,292 filed April 14, 1972 by Asne8, which is hereby incorporated by reference. It is.

This specification includes a releasable layer which may have a support sheet or support layer adhered thereto, a layer of transfer lacquer disposed to be releasably adhered to the releasable layer, and a layer of transfer glaze. A reticle system for thermal transfer is described which consists of a τ pattern printing layer placed in adhesion to the pattern printing layer and an adhesive layer placed in adhesion to the pattern printing layer. The temperature of one layer of lacquer for transfer is 232.2℃, which is much higher than 148.9℃.
It is preferably comprised of a transparent cellulose resin, such as a cellulose ester, having a lower softening point, ie, a cellulose resin that does not appreciably soften or become tacky at the transfer temperature. The pattern printing layer is
one or more colors of conventional heat transfer inks, such as nitrocellulose inks and/or polyamide inks, in which pigments and/or dyes of the desired color are dispersed or dissolved; made from numbers. The last adhesive layer is made from a conventionally used heat-activable adhesive, suitable adhesives being disclosed in the above specification. "Crosslinking agent"
The term refers to chemically reacting with a crosslinkable material, such as polymerizing to form chemical bonds, or crosslinks, between the polymer chains of that material or between the polymer chains of that material and another material. used to refer to materials such as

Included among the "other" materials is the cross-linking agent's own polymer chain or portion thereof. That is, during the polymerization process, the crosslinking agent forms polymer chains that can themselves be crosslinked by the crosslinking agent and/or crosslinked by the crosslinking agent to other crosslinkable materials. May be formed. A preferred embodiment utilizes a number of polymeric crosslinking agents that react with the polymeric crosslinkable material. As used herein, the term "crosslinking" refers to the formation of chemical bonds between chains of a crosslinking agent and one or more crosslinkable materials or between chains of those materials themselves. It means to do something. In fact, both the crosslinkable material and the crosslinking agent actively participate in all reactions that occur between them. The term "crosslinking agent" is used more or less conveniently to refer to the more reactive one of the two. In fact, some materials, such as polymers that undergo substantial crosslinking between themselves at elevated temperatures, are suitable both as crosslinkable polymerizable materials and as crosslinking agents. Crosslinking agents suitable for use in the present invention are those known in the art.

The choice of a particular crosslinking agent will depend on which layer it is used in and the nature of the material in the adjacent layer to which it is desired to crosslink. If a crosslinking agent is used in the transfer coating layer, it must not reduce the release properties of the interface between the coating layer and the release layer. Therefore, it does not have a high enough melting point to not become soft or sticky at the temperature at which the reticle is transferred, so that it does not adhere to the release layer and prevent release. Must not be. Also, it must not crosslink or otherwise react with the material in the release sheet to prevent good release. If a crosslinking agent is used in the adhesive layer, it must not reduce the required adhesive properties of the adhesive layer. Examples of suitable crosslinking agents include blocked isocyanates when the layer in which crosslinking is desired contains polymeric materials, such as cellulosic materials, with available reactive groups such as carboxyl or hydroxyl groups. group, epoxy group or urea formaldehyde group (including substituted urea formaldehyde groups)
primary and secondary amines and polyamines, as well as other materials known in the art.

Cross-linking polymerization also occurs between materials with available urea formaldehyde groups and materials with available epoxy groups, and between materials with available urea formaldehyde groups and materials with available carboxyl groups. It will also occur between the ``blocked'' isocyanate and the material containing epoxy groups.

Generally speaking, suitable crosslinking agents for crosslinking certain polymeric materials are well known to those skilled in the art, and those addressed herein are merely a few examples. By "blocked" isocyanate is meant the reaction product of an isocyanate with an active hydrogen-containing compound that results in an adduct having only limited thermal stability. These compounds are stable at room temperature, but at elevated temperatures they react as if an isocyanate were present. Suitable blocked isocyanates are known in the art, for example San
Examples of suitable protective agents include those disclosed in this book, such as those disclosed in this book, ``Chemistry and Engineering of Polyurethanes'', Vol. 1 (1962), pages 118-121. Phenols, substituted phenols, alkyl mercaptans, aryl mercaptans and other compounds with reactive hydrogen atoms such as alcohols.Commercially available blocked isocyanates suitable for use in this invention include: Various amine imides, especially As
hlandAminimide2lOOl [bis(trimethylamine) sebacimide] and AshlandA
Minimide 2 O 6 O 3 (bis(dimethyl-2-hydroxypropylamine) adipimide), and prolactam-blocked polyisocyanates sold under the trademark IsOnate 123P by the Updillon Company. In a preferred embodiment, a material with blocked isocyanate groups is used as a crosslinking agent in one layer of the transfer lacquer of a multilayer decorative label, and a polymeric material with available hydroxyl groups is used as a crosslinking agent in the adjacent pattern printing layer. Contain.

Preferably, the transfer lacquer layer also contains a polymeric material with available hydroxyl groups. The use of blocked isocyanates as cross-linking agents in transfer layer layers is such that their reactivity is generally low enough to minimize the degree of reaction with the release layer, yet at elevated temperatures. It is particularly advantageous in that it immediately crosslinks materials with available hydroxyl groups. Suitable polymers with available hydroxyl groups include known polyols such as cellulose and modified cellulosic materials such as cellulose esters such as cellulose acetate, cellulose propionate, cellulose acetate butyrate, substituted cellulosic materials such as hydroxyalkyl Polymeric resins based on cellulose, unmodified or modified starches, alcohols such as polyvinyl alcohol, or polymeric resins based on monomers having several hydroxyl groups such as diols and glycols and others known in the art. The following polyols are mentioned. It is preferred to use cellulosic materials, particularly cellulose esters such as cellulose acetate, as a source of hydroxyl substituents in the transfer layer. The amounts of reactive components to be included in the various layers vary widely depending on the particular type of materials used and the properties desired of them in use. For example, the transfer lacquer layer may be made largely of a crosslinkable material such as a cellulose ester, but may contain relatively small amounts of a crosslinking agent such as a blocked isocyanate. Thus, it can contain about 80-99% by weight of cellulose acetate or other cellulosic material and about 0.5-20% by weight of blocked isocyanate. Preferably, this layer comprises about 85-95% by weight cellulose acetate or other cellulosic material and about 5-15% by weight polyisocyanate material. Other materials may also be included in the transfer lacquer layer, such as small amounts of tracer compounds that are normally colorless but fluoresce under ultraviolet radiation. Tracer compounds are useful in facilitating clear lattice registration during the printing process. In layers separated from the release layer by a transfer layer or other layers,
Reactivity and physical properties are not as critical as in the transfer layer.

This is because adhesion to the releasable layer does not pose a problem. These layers may thus be formulated with the goal of optimizing cohesion within the layers and adhesion between the layers. The adhesive bond between the layers in the decorative material of the invention is referred to as an integral bond or integral bond. This is because the cross-linking that occurs between materials in adjacent layers creates an interlayer blend of chemically linked materials at the interface.

For this reason, materials that are significantly more reactive than those used in the transfer lacquer layer may be used in the layers other than the transfer lacquer layer. For example, highly reactive crosslinking agents such as urea formaldehyde or epoxy materials may be used in the graphic printing layer and the adhesive layer. Preferable 1
In one embodiment, the graphic printing layer contains both a crosslinkable material, such as a material with available hydroxyl groups, and a crosslinking agent, such as a urea formaldehyde resin material. The relative amounts of each may be about the same, or one or the other may be predominant. However, the pattern printing layer is made of polyol of about 30-5
5% by weight and about 40% heat-reactive urea formaldehyde binder
-65% by weight. A preferred urea formaldehyde polymer or prepolymer is a substituted urea formaldehyde material, such as a butylated urea formaldehyde material. Preferably, the polyol in the pattern printing layer is a hydroxyl-modified vinyl resin, most preferably a hydroxyl-modified pinyl chloride monovinyl acetate copolymer. The graphic printing layer may also contain the pigments necessary for the desired color and may also include small amounts of additives known in the art. When the adhesive layer is cross-linked according to the invention with the printed layer adjacent to it, it not only acts as an adhesive to bond the decorative pattern to glass, ceramic, metal or other substrates, but also the finished decoration. It must act as a cross-linked and integrated layer in the pattern.

Preferably, it is a heat-activatable adhesive, and the same material that makes it a heat-activatable adhesive is also responsible for the cross-linking between the adhesive layer and the pattern printing layer adjacent thereto. do. Additionally, the material can include one or more crosslinkable materials and one or more crosslinking agents. In one preferred embodiment, the crosslinkable material in the adhesive layer includes a carboxyl-modified vinyl resin, but the adhesive layer is further coated with two epoxy-type crosslinkers, namely highly reactive epoxy-modified vinyl resins. dicrycidyl ether bisphenol A type polyepoxide.

Other additives may also be included, such as small amounts of ultraviolet radiation absorbers, so that the adhesive layer can be easily distinguished from the transfer lacquer layer during printing. Additionally, the required amounts of the various components will depend on the particular components used in the system. In a preferred embodiment, about 35-60% epoxy modified vinyl resin and 1-15% diglycidyl ether bisphenol type A polyepoxide.
and 3565% carboxyl-modified vinyl resin. In fact, ornamental retsutels are used, for example, in the above-mentioned B. 244,292, filed by Asnes, by forming a suitable release layer.

Once the release layer has been formed, a layer of transfer lacquer is applied onto the release layer, preferably by gravure printing. Thereafter, a pattern printing layer and an adhesive layer are successively formed on the transfer lacquer layer, preferably by a printing technique. When applying the finished decorative reticle to a substrate, it is highly preferred to pre-treat the substrate with any known silane adhesion promoter.

Such materials include epoxy silanes (eg, A-187 manufactured by Union Carbide), mercapto silanes (eg A-189, also manufactured by Union Carbide), and the like. It is highly preferred to preheat the substrate prior to applying the decorative reticle. Generally speaking, it has been found advantageous to use a preheating temperature of about 65°C to about 121°C. After preheating, the decorative reticle is brought into contact with the heated substrate and the temporary backing carrying the release layer is heated and pressed to force the adhesive layer to the surface of the substrate. This is preferably carried out in a heat transfer decoration machine as described in US Pat.
No. 2, No. 3,064,714, No. 3,231,448, and No. 3,261,754. After transfer, the substrate with the decorative material is cured by heating, for example, at about 93-148° C. for 10-20 minutes. Then add it further, for example, to about 1
76-232.2 for 10-20 minutes. When cured, it produces a clear, precise decorative reticule that is very strongly bonded to the substrate and has excellent abrasion resistance.

The benefits obtained by the present invention are quite significant.

The applied decorative reticles are far superior in durability, resistance to abrasion and tear, ease of application and appearance compared to hitherto known heat transfer reticles. One of the most important advantages obtained by the invention
One is an increase in decoration speed. Even in the most efficient of comparable prior art systems, the labeling rate was limited to about 20 or only about 30 bottles per minute. Speeds of 60-100 bottles per minute are achieved with the present invention, yet the decorated bottles have the improved appearance and resistance to chemicals and abrasion mentioned above.
Although it is preferred to use some cross-linking agent and/or cross-linkable material to enable reactions between adjacent layers, the present invention provides benefits from even simpler systems. It will be done.

Thus, the same crosslinking agent, e.g. a blocked isocyanate material, is contained in both the transfer lacquer layer and the contact layer, and the two components react on both sides with the only crosslinkable material in the pattern printing layer, e.g. a polyol. It is also possible to use a reaction system consisting of: The same materials would work similarly if the crosslinking agent was placed in the graphic printing layer and the crosslinkable material was placed in the transfer lacquer layer and the adhesive layer. It is also preferred that each layer contain both a crosslinkable material and a crosslinking agent.

Intra-layer cohesion between the materials contained within each layer is then improved by cross-linking, and inter-layer cohesion and therefore overall cohesion is reduced by the action of the cross-linking agents in both adjacent layers. improved by In fact, the decorative material is heat-cured throughout each layer and between each layer as described above. However, some benefits are obtained even when one or more of the layers contains only one reactive material, be it a crosslinkable material or a crosslinking agent. To summarize the most preferred embodiment:
Both the crosslinkable material and the crosslinking agent are contained within the transfer lacquer layer, the graphic printing layer and the adhesive layer.

In the transfer layer, the preferred cross-linkable material is cellulose acetate and the preferred cross-linking agent is SOnate 123P, a prolactam-blocked polyisocyanate available from Updition Company. In the graphic printing layer(s), the preferred crosslinkable material is a hydroxyl-modified vinyl chloride monoacetate resin and the preferred crosslinking agent is a butylated urea formaldehyde polymer. In the adhesive layer, the preferred crosslinkable material is a carboxyl-modified vinyl chloride H-sulfur acid vinyl resin, and the two epoxy-based crosslinking agents are an epoxy-modified vinyl chloride monovinyl acetate copolymer resin and a diglycidyl ether bisphenol resin. It is preferred to use type A polyepoxide. 93.3-232.
At a curing temperature of 2 DEG C., it is believed that the polyisocyanate in the transfer lacquer layer becomes unblocked and reacts with both the hydroxyl groups of the cellulose acetate in the transfer lacquer layer and the hydroxyl groups of the hydroxyl-modified resin in the pattern printing layer.

Similarly, the butylated urea-formaldehyde in the pattern printing layer will react with the same hydroxyl groups in the transfer layer and the pattern printing layer, and at the same time both epoxides will also react with the carboxyl groups in the adhesive layer. Conceivable. In order to complete this transfer, the hydroxyl groups of the hydroxyl-modified resin in the pattern printing layer are combined with the polyisocyanate released from blocking in the transfer layer, and with the butylated urea-formaldehyde in the pattern printing itself. Both epoxy compounds in the adhesive layer react. The present system, which includes a variety of crosslinking agents and crosslinkable materials, provides particularly strong, cohesive, and damage resistant decorative labels. In the following, the invention will be further clarified by means of illustrative examples.

Example 1 A heat transfer decorative material is made as follows.

Multilayer printing is applied using rotogravure onto a suitable release surface according to the method described in the aforementioned US Pat. No. 2,442,92.

This multilayer printing consists of (1) 9.8 parts of cellulose acetate dissolved in 80 parts of methyl ethyl ketone and 8.9 parts of acetone, 0.4 parts of fluorocent dye [substituted phenylbenzotriazole, trade name 1 mtraw]
ite0B (IntracOlOrCO.)] and blocked isocyanate polymer (IsOnatel2
3PUpjOhnCO. ) a printed layer of a transparent lacquer containing 1.0 part; and (2) a printed layer of butylated urea applied over (and within the area of) the first printed and dried transparent lacquer layer. - 15.3 parts of formaldehyde resin solution (Resimene U-920, MOn
sOnt), 12.5 parts of ethyl acetate, n-
11.5 parts of hydroxy-modified vinyl chloride vinyl acetate copolymer resin (according to VAGD. UniOnCarbide) dissolved in 34.2 parts of propyl acetate, 16.6 parts of toluene and 3.2 parts of isopropanol and 0.1 part of silicone resin (S-10, Uni
Reactive yellow ink [by OnCarbide]
6.5 parts of Sumatra yellow pigment manufactured by Hercules was added to CO
dispersed in the solution with the wles solubilizer and the mixture was mixed in a bowl or mill with X). 8 Hegman] and (3) applied on top of this pattern printing and within the area of the first layer of transparent lacquer.
13.9 parts of epoxy group-modified vinyl chloride-vinyl acetate copolymer resin (VERR, UniOnCarbi
de), 13.9 parts of carboxyl-modified vinyl chloride-vinyl acetate copolymer resin (VMCA) dissolved in 34.6 parts of ethyl acetate and 34.6 parts of toluene
．． UniOnCarbide), and 2.8 parts of diglycydilyether bisphenol A epoxy resin (ER
L2774, UniOnCarbide) and 0.2 part of ultraviolet absorber (UvinulD-50.Genera
1Ani11neandFi1m), a transparent, curable, heat-activatable adhesive layer.

The heat-activatable adhesive layer thus applied is dried to the point where it is not tacky but is thermally active. In order to monitor the printed matter thus obtained, after the final correction of the pressing process, a dye was added to the transparent transfer layer (the first layer) so that this layer could be clearly seen. Irradiates ultraviolet light to produce fluorescence. The overlying transparent adhesive layer (the last layer) appears darker than the first lower layer due to the UV absorbers in it. This means that the two transparent lacquer layers and the ink printing layer can be perfectly aligned. The resulting patterned reticle is transferred to a glass pin by the method described above.

aminoalkoxysilane or gamma before decoration.
Aminopropyltriethoxysilane (0.05% in toluene-ethanol) (A-1100,.Uni0nCa
rbide) is applied to the surface to be decorated. Applying silane to the ware provides sufficient water resistance to the markings on the ware. The utensils are then heated to 66°C to 121°C, using a Denison TDIB thermal transfer decoration machine to produce approximately 60°C per minute.
Creates patterns at individual speeds. The patterns on the utensils are heated to 93℃
Place in the oven at ~149°C for 10-20 minutes and then heat to 177°C.
Place in a kiln at ~232°C for 10-20 minutes. After the material is completely cured, the layer of lacquer that surrounds and protects the ink print is transparent and invisible. The resulting pattern is not completely removed by 40 rubs with methyl ethyl ketone, and is only very slightly removed by Scotch tape after 30 minutes of soaking in boiling water and scratching with a razor.

Example 2 A reactive white ink can be printed over the yellow ink described in Example 1 before applying the adhesive layer.

Then, when the pattern is transferred to the utensil, the transparent yellow tone becomes opaque. The reactive white ink was 0.1 parts of Resimene U-9201 dissolved in 8.3 parts of ethyl acetate, 22.6 parts of n-propylacetate, 11.0 parts of toluene, and 2.1 parts of isopropanol, VAGD 7.7.
part and 0.05 part of S-10 silicone resin. 38 parts of titanium dioxide (0R-580.Cyanamid)
are dispersed and ground as described in Example 1. Printing, decoration and curing are carried out as described in Example 1. Example 3 A reactive transparent blue ink can be printed on top of the yellow ink according to Example 1 and in a matching manner, and the white ink according to Example 2 can also be printed over it.

The reactive blue ink was prepared using Resimene U-- dissolved in 11.6 parts of ethyl acetate, 31.9 parts of n-propyl acetate, 15.5 parts of toluene, and 3.0 parts of isopropanol.
92014.2 Part AGDlO. It consists of 8 parts and S-100.1 part. MOnarch blue pigment CERX-336
9 (Hercules) are dispersed and ground according to the method described in Example 1. Printing, decoration and curing are carried out as in Example 1. The test results are similar to those in Example 1. Example 4 The reactive transparent red ink was replaced with the yellow ink described in Example 1, Example 3
The blue ink described in Example 2 can be printed over and matched, and the white ink described in Example 2 can also be printed over it.

The reactive red ink was Resimene U9 dissolved in 11.9 parts of ethyl acetate, 32.5 parts of n-propyl acetate, 15.8 parts of toluene, and 3.1 parts of isopropanol.
2Ol 4.5 parts VAGDlO. 9 parts and SlOO. l
Consists of departments. Sparta red pigment (Herculea
) 10.9 parts are dispersed and ground according to the method described in Example 1. Printing, decoration and curing are carried out analogously to Example 1. Test results similar to Example 1 are obtained. Although embodiments of the invention have been described, it will be obvious to those skilled in the art that variations and improvements may be made therein without departing from the invention. Therefore, only specific examples are provided herein and are not intended to limit the method of the present invention. Although the present invention has been described in detail above, specific examples of the present invention are summarized as follows. (1) The temperature of the crosslinking substance is about 90℃~
Heat transfer decorative material according to the preceding claims, which reacts and crosslinks at 232°C.

(2) The heat transfer decorative material according to item (1) above, which contains a substance that reacts and crosslinks between the layers.

(3) The heat transfer decorative material described in the preceding paragraph (I), which contains a substance that reacts and crosslinks between the layers in the pattern printing layer. (4) The adhesive layer contains a substance that reacts and crosslinks between the layers. Previous section (1
) The heat transfer decorative material described in ). (5) The heat transfer decorative material according to item (1), wherein each of the layers comprises a crosslinkable material and a heat-activatable crosslinking agent.
(6) The heat transfer decorative material according to the preceding item (5), in which the crosslinking agent is selected from "blocked" polyisocyanates, urea-formaldehyde resins and polyepoxide resins.

(7) The heat transfer decorative material according to item (5), wherein the crosslinkable material in at least one of the layers includes a polymeric substance having a hydroxyl group.

(8) A polymeric substance in which the single layer of the lacquer has a hydroxyl group and
The heat transfer decorative material according to the preceding item (1), comprising a crosslinking agent having a "blocked" isocyanate substituent.

(9) The heat transfer decorative material according to item (8), wherein the polymeric substance having hydroxyl groups contains a cellulose ester.

Q1: The heat transfer decorative material according to the above item (8), which contains a crosslinkable material and a crosslinking agent in the pattern printing layer.

aυ The process described in Q1 above, in which the crosslinkable material contains a polymeric substance with hydroxyl groups and the crosslinking agent is selected from "blocked" polyisocyanates, urea-formaldehyde resins, and polyepoxide resins. Heat transfer decorative material.

The heat transfer decorative material according to the above item (8), which contains a crosslinkable material and at least one crosslinking agent in the AO adhesive layer.

The A3 pattern printing layer contains an alkylated urea-formaldehyde resin and a polymeric substance having a hydroxyl group, and the adhesive layer contains a polymeric substance having a carboxyl group and at least one
The heat transfer decorative material according to the above item (9), which contains a seed epoxide resin.

A゜The heat transfer decorative material according to the preceding item Q, further comprising a support for the releasable surface and a releasable surface.

aω consisting of a crosslinkable material and a crosslinking agent;
1. A method for decorating a ware, which comprises gluing a decorative material with a plurality of layers onto the ware and subjecting the resulting pattern to reaction conditions such that cross-linking occurs between adjacent layers in said material.

1 Powder The method described in the preceding item αW, in which the reaction conditions are set to a temperature of 93° to 232°C.

Q'rl consists of a raw material and a cured material with multiple layers of polymeric material bonded to the raw material, with the multiple layers of polymeric material bonded between adjacent layers by chemical cross-linking. A utensil made to look like a living room.

Claims (1)

[Claims] 1. A heat transfer decorative material consisting of a lacquer layer, at least one pattern printing layer and a heat-activable adhesive layer, containing a substance which reacts with at least one of these layers and crosslinks between the layers.