JP2992856B2 - Printing ink composition for transfer paper and transfer paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to transfer paper and a printing ink composition for transfer paper. The transfer paper according to the present invention is particularly useful for transferring a pattern when patterning ceramics (mugs, cups, etc.), glassware (cups, bowls, etc.), metal products, and the like.

[0002] In this specification, "%" and "parts" mean "% by weight" and "parts by weight", respectively.

[0003] In the case of transferring a multicolor print layer to a porcelain or the like by using a transfer paper, a water slide method has been widely used conventionally. In this method, first, a water-soluble glue layer is provided on release paper, and a multicolor picture layer is formed thereon,
If necessary, a picture support layer is provided thereon. When the transfer paper thus obtained is immersed in water, the water-soluble glue layer is dissolved and removed, and the pattern layer is peeled off from the release paper. After that, water existing between the picture layer and the transfer object is removed by using a jig such as a squeegee, and the picture layer is dried by leaving it. After the drying is completed, the object to be transferred is baked at a high temperature of about 1000 ° C. so that the transferred picture layer is completely adhered to the object to be transferred. In this method, baking at a high temperature of about 1000 ° C. is indispensable, so that the use of ink lacking heat resistance is restricted, and as a result, there is a problem that diversification such as color tone and number of colors is restricted. .

Accordingly, the present invention provides a novel transfer paper which can use an ink lacking heat resistance and can perform multicolor transfer by a simple process at a relatively low temperature, and a printing ink composition therefor. Its main purpose is to:

[0005]

Means for Solving the Problems The present inventor has made intensive studies in view of the state of the art as described above, and as a result, by blending two types of curing agents having different reaction temperatures into an epoxy resin, It has been found that technical problems are greatly reduced.

That is, the present invention provides the following printing ink composition for transfer paper and a transfer paper having a printing layer made of this composition: An epoxy resin, a first curing agent which cures by reacting with the epoxy resin at room temperature, and 80 to 2
A printing ink composition for transfer paper, comprising a second curing agent that reacts and cures at 00 ° C.

[0007] 2. Item 2. The printing ink composition for transfer paper according to Item 1, which contains a colorant.

[0008] 3. Item 2. The printing ink composition for transfer paper according to Item 1, comprising a reversible thermochromic composition.

4. Item 2. The printing ink composition for transfer paper according to Item 1, comprising a colorant and a reversible thermochromic composition.

[0010] 5. Item 5. A transfer paper comprising a coating layer comprising the printing ink composition according to any one of Items 1 to 4.

6. Item 6. A transfer paper comprising a coating layer comprising the printing ink composition according to Item 2 and a coating layer comprising the printing ink composition according to Item 3.

7. Item 6. A transfer paper obtained by overcoating and / or undercoating a coating layer comprising the printing ink composition according to any one of Items 2 to 4 with a coating layer comprising the printing ink composition according to Item 1.

8. Transfer paper in which an oil-based ink layer and / or an ultraviolet-curable ink layer is overcoated and / or undercoated with a coating layer comprising the printing ink composition according to any one of the above items 1 to 4.

The epoxy resin used in the present invention includes:
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, brominated epoxy resin, polyglycol type epoxy resin and the like can be mentioned. Among these, bisphenol A having a molecular weight of about 200 to 5000 and an epoxy equivalent of about 100 to 1000
Type epoxy resins are more preferred. Further, bisphenol A type epoxy resins having an epoxy equivalent of about 100 to 500 are often liquid at room temperature, and are particularly preferable. A semi-solid bisphenol A type epoxy resin having an epoxy equivalent of about 500 to 1,000 can also be used by dissolving it in a diluent. In this specification, the epoxy equivalent means (molecular weight of epoxy resin) / (number of epoxy groups in molecule).

In the present invention, a first curing agent that reacts with an epoxy resin at room temperature (hereinafter referred to as a first curing agent) and a second curing agent that reacts with an epoxy resin under heating conditions (hereinafter referred to as a second curing agent). It is essential to use two types of curing agents.

The first curing agent is composed of an epoxy resin and room temperature (10
(Approximately 30 ° C.) at about 30 ° C.) to cure at least the surface of the printing ink composition layer applied to the transfer paper, thereby facilitating subsequent operations. Examples of the curing agent having such an action include the following, and one or more of these are used.

-Aliphatic amines: diethylenetriamine, triethylenetetramine, N-aminoethylpiperazine, diethylaminopropylamine and the like.

Alicyclic amines: isophoronediamine,
3,9-bis (3-aminopropyl) -2,4,8,1
0-tetraoxaspiro [5,5] undecane, 1,3
-Bisaminomethylcyclohexane, m-xylylenediamine and the like.

Aromatic amines: metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, toluylenediamine and the like.

Amine adduct: an adduct obtained by reacting the above-mentioned amine with an epoxy resin having reactivity with the amine.

-Acid anhydrides: aromatic acid anhydrides such as phthalic anhydride, methyltetrahydrophthalic anhydride and trimetic anhydride; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, alkenyl anhydride Cyclic fatty acid anhydrides such as succinic acid and hexahydrophthalic anhydride; aliphatic acid anhydrides such as polyadipic anhydride and polyazeleic anhydride; halogenated acid anhydrides such as chlorendic anhydride and tetrabromophthalic anhydride.

A polyamide resin.

The first curing agent may be liquid or solid as long as it reacts with the epoxy resin at room temperature. Among these first curing agents, amine adducts and polyamide resins are more preferred, and have an active hydrogen equivalent of 20.
About 600, and more preferably liquid at room temperature. In this specification, the active hydrogen equivalent refers to the first curing agent and the second curing agent described below.
It means (molecular weight of curing agent) / (number of active hydrogens in molecule).

The second curing agent reacts with the epoxy resin under a heating condition of about 80 to 200 ° C., and is heated by heating a transfer-receiving member having a picture pattern composed of a printing ink composition transferred from transfer paper. Finally, the pattern is completely cured. As such a curing agent, those known as latent curing agents for epoxy resins can be used as they are.
More specifically, the following are exemplified, and one or more of these are used.

Dicyandiamide and derivatives thereof: dicyandiamide, o-tolylbiguanide, phenylbiguanide, α-benzylbiguanide, α-2,5-dimethylbiguanide, phenylbiguanide oxalate and the like.

Organic acid hydrazide: succinic dihydrazide, adipic dihydrazide, p-oxybenzoic hydrazide and the like.

-Imidazoles: 2-heptadecyl imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazolium isocyanurate and the like.

[0028] - boron trifluoride (BF ₃₎ - amine complex ... BF ₃ complex of monomethylamine, BF ₃ complex of n- hexylamine, etc. BF ₃ complex of triethylamine.

Others: Amine adduct having a melting point of 80 ° C. or higher, diallyl melamine, and a curing agent active at room temperature are included.
A microcapsule that functions as a curing agent when the wall material collapses at 80 ° C. or higher.

Among these second curing agents, dicyandiamide and its derivatives, organic acid hydrazide and amine adduct having a melting point of 80 ° C. or more are more preferable.

The mixing amounts of the first curing agent and the second curing agent with respect to 100 parts of the epoxy resin are based on the theoretical amount calculated as follows based on the epoxy equivalent of the epoxy resin and the active hydrogen equivalent of the curing agent. Determined from a practical point of view. However, when an acid anhydride is used as the first curing agent, the theoretical amount is calculated using an acid anhydride equivalent instead of the active hydrogen equivalent.

Theoretical amount of curing agent = active hydrogen equivalent × 100 /
Epoxy equivalent First, the compounding amount of the first curing agent with respect to the epoxy resin is generally about 40 to 150% of the theoretical amount. If the amount of the first curing agent is too small, the hardening of the printed coating film on the transfer paper does not proceed smoothly, so that the subsequent transfer step becomes difficult. On the other hand, if the amount of the first curing agent is too large, the pot life of the printing ink composition is shortened, and the flexibility required for the printed coating film during transfer cannot be obtained. Practically, the compounding amount may be determined in consideration of the difference in the curing speed depending on the type of the first curing agent, the pot life of the printing ink composition, the curing time required for the coating film, and the like. For example, when using an aliphatic amine having a high curing rate, it is desirable to reduce the amount of the compound, and when using a polyamide resin or an alicyclic amine having a low curing speed, it is desirable to increase the amount of the compound. When the first curing agent having a low curing rate is used, there is no practical inconvenience even if the amount exceeding 100% of the theoretical amount is mixed with the epoxy resin. In addition, the pot life, curing speed, and the like of the printing ink composition can be appropriately adjusted by using two or more first curing agents in combination by utilizing the difference in curing performance depending on the type of curing agent.

The mixing amount of the second curing agent with respect to the epoxy resin is about 10 to 150% of the theoretical amount. If the amount of the second curing agent is too small, curing of the transferred coating film when the transfer object is heated becomes insufficient, and the adhesive strength between the coating film and the transfer object decreases. On the other hand, when the blending amount of the second curing agent is too large, the transfer coating film becomes hard and brittle, and the adhesive strength between the coating film and the transfer receiving body also decreases. As for the second curing agent, the amount of the second curing agent is adjusted according to the difference in curing speed, and the use of two or more kinds as necessary is the same as in the case of the first curing agent.

The total amount of the first curing agent and the second curing agent in the epoxy resin is preferably about 100 to 250% of the theoretical amount. Practically, considering the pot life of the printing ink composition, the curing conditions, the curing speed, the hardness of the final coating film after transfer, the adhesive strength between the coating film and the transfer target, and the like, the ratio of the two is determined. It may be determined appropriately. For example, when the amount of the first curing agent is small, the amount of the second curing agent is increased. In short, in order to completely cure the epoxy resin, the total blending amount of the two should be at least 100% of the theoretical amount. Also, if necessary, the first
As described above, two or more curing agents and / or second curing agents can be used in combination.

When the printing ink composition of the present invention is used in a colorless state, for example, when it is used as an undercoat layer or an overcoat layer described below, it is not particularly necessary to add a coloring agent. When the printing ink composition of the present invention is used by coloring, inorganic and organic coloring pigments used in conventional printing ink compositions for transfer paper can be used as they are. Such color pigments include:
Inorganic pigments such as titanium dioxide, cadmaris golden, cadmium red medium, and high therm black, National Fast Red, Calco Condensation Green AY, Calco Condensation Yellow B7
and organic pigments such as c, bismarck brown and the like. The amount used depends on the type of pigment, etc.
Although not particularly limited, it is usually about 1 to 70 parts (more preferably 5 to 60 parts) with respect to 100 parts of the epoxy resin.
Parts).

In the printing ink composition of the present invention, a reversible thermochromic composition known as a colorant can be used alone or in combination with the above-mentioned colorant. Such a reversible thermochromic composition comprises an electron-donating color-forming organic compound (color-forming agent), an electron-accepting compound (color-developing agent) and a desensitizer, and is described in various documents. ing. Specific examples of the color former, the color developer, and the desensitizer constituting such a reversible thermochromic composition are not particularly limited, but are described in, for example, JP-A-1-174591. . Such a reversible thermochromic composition may be used in a microencapsulated state. The amount used depends on the type and the like, and is not particularly limited, but is usually in the range of about 5 to 70 parts (more preferably about 10 to 60 parts) based on 100 parts of the epoxy resin.

The printing ink composition of the present invention may further contain, if necessary, various known additives such as a reactive diluent, an extender, an adhesion promoter and an antifoaming agent.

Examples of the reactive diluent include glycidyl versatate, phenyl glycidyl ether, allyl glycidyl ether and n-butyl glycidyl ether. The amount used is not particularly limited, but is usually about 5 to 30 parts (more preferably about 5 to 10 parts) based on 100 parts of the epoxy resin.

Examples of the extender include silica, alumina, alumina silicate, calcium carbonate, mica, and quartz powder. The amount used is not particularly limited as long as it is an amount necessary for adjusting the flowability of the composition, and is usually about 2 to 20 parts (more preferably about 2 to 4 parts) with respect to 100 parts of the epoxy resin. It is.

As adhesion promoters, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl)-
Aminopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ
Silane coupling agents such as -chloropropyltrimethoxysilane. The amount used is not particularly limited, but is usually about 0.05 to 5 parts (more preferably about 0.07 to 3 parts) per 100 parts of the epoxy resin.

Examples of the antifoaming agent include known siloxane-based antifoaming agents such as polyether-modified methylalkylpolysiloxane and polyester-modified polydimethylsiloxane. The amount used is not particularly limited,
It is usually about 0.05 to 5 parts (more preferably about 0.07 to 3 parts) based on 100 parts of the epoxy resin.

The transfer paper using the printing ink composition for transfer paper according to the present invention is produced, for example, as follows.

First, additives such as a reactive diluent and extender are added to the epoxy resin, and mixed and stirred by a stirrer.
If a colorant is used, it is also included. Then
Prior to printing on a transfer paper substrate (release paper), a first curing agent, a second curing agent, an adhesion promoter, an antifoaming agent, and the like are added to the above mixture and mixed, whereby printing for transfer is performed. Obtain an ink composition. Next, the obtained printing ink composition is printed as a pattern layer on a water-soluble paste on the surface of a transfer paper base material by a known method such as screen printing, and at least the pattern layer is formed at room temperature by the action of a first curing agent. Cure the surface.
When forming two or more kinds of picture layers having different colors, the same operation is repeated as many times as necessary. Next, a coating layer for protecting the picture layer is formed. This coating layer can be composed of, for example, a silicone resin, an acrylic resin, or the like mixed with silicone rubber or the like as a release agent. This coating layer can be removed after transferring the pattern layer of the transfer paper to a predetermined product surface and curing it.

Alternatively, a transparent printing ink composition of the present invention containing a first curing agent and a second curing agent is printed on a water-soluble paste on the surface of a transfer paper substrate by a silk screen printing machine or the like, A transparent undercoat layer is formed. Next, a solvent-type oil-based ink or an ultraviolet-curable ink is printed on the undercoat layer with a silk screen printing machine or the like to form a picture layer. Next, the same transparent printing ink composition as described above is printed as a top coat layer on the ink layer. Next, a coating layer for protecting the picture layer is formed on the top coat layer.

When the obtained transfer paper is used, the transfer paper is wetted with water according to a conventional method, the water-soluble paste is dissolved, the substrate is removed, and the remaining screen-printed picture layer is replaced with a predetermined product. Paste on the surface and transfer. Then
The transferred printed pattern is cured by the action of the second curing agent under predetermined heating conditions, and the printed pattern is firmly adhered to the product surface.

Hereinafter, the transfer paper according to the present invention will be described in more detail with reference to the drawings.

In FIG. 1 schematically showing a cross section of one example of the transfer paper according to the present invention, a base material for the transfer paper, ie, release paper 1 is provided with a water-soluble material such as dextrin, water-soluble polyester, etc. The paste layer 2 is formed, and the pattern layer 3 is formed thereon by printing using the printing ink composition of the present invention. On the picture layer 3, a second picture layer 4 of the printing ink composition of the present invention containing a reversible thermochromic material is formed. The picture layers 3 and 4 are protected by a coating layer 5 made of silicon resin, acrylic resin, or the like.

In FIG. 2, which schematically shows a cross section of another example of the transfer paper according to the present invention, a water-soluble paste layer 2 is formed on a transfer paper base material 1 and a transparent layer is formed thereon. The undercoat layer 7 of the printing ink composition of the present invention is formed on the entire surface. On the undercoat layer 7, a solvent type oil-based ink (a normal type, a thermochromic type, etc.) or a UV-type curable ink (a normal type,
The coloring layer 8 is formed by, for example, a thermochromic type. Since the coloring layer 8 made of these inks does not have an adhesive strength to the product surface, the undercoat layer 7 ensures the adhesive strength to the product surface. Also,
On the upper surface of the coloring layer 8 made of ink, a transparent overcoat layer 9 made of the printing ink composition of the present invention is entirely formed, and protects the coloring layer 8 having a low surface hardness. Further, the entire overcoat layer 9 is protected by the covering layer 5 as in the case of the transfer paper shown in FIG.

In FIG. 3, which schematically shows a cross section of still another example of the transfer paper according to the present invention, a water-soluble glue layer 2 is formed on a base material 1 for a transfer paper. Has a transparent undercoat layer 7 of the printing ink composition of the present invention formed on the entire surface. On the undercoat layer 7, a coloring layer 8 made of a solvent type oil-based ink or a UV-type curable ink is formed, and a pattern layer made of the printing ink composition of the present invention containing a thermochromic material is formed thereon. 4 are formed. Further, an overcoat layer 9 is formed on the picture layer 4, and the entire overcoat layer is
It is protected by the coating layer 5.

[0050]

According to the present invention, the following remarkable effects are achieved.

(1) Since at least the surface portion of the printing layer is cured by the presence of the first curing agent, even if another printing layer is subsequently formed on the printing layer with another printing ink composition, the printing layer is not cured. Does not occur.

(2) Since the pattern layer can be hardened after transfer at an extremely low temperature as compared with the prior art, no equipment for processing at a high temperature is required when forming patterns on various products. became. As a result, measures and equipment for ensuring safety during high-temperature processing are not required, and thermal energy is also reduced, so that the manufacturing cost of the product is reduced.

(3) Since the curing temperature of the picture layer after the transfer is lower than that of the prior art, it is possible to use inks having poor heat resistance which could not be used conventionally. Therefore,
The color tone and the number of colors can be diversified.

The adhesive strength of the cured picture layer to the product is as high as that of the picture layer obtained by the conventional high-temperature direct printing method.

(4) By adjusting the types and amounts of the first curing agent and the second curing agent, a printing ink composition for transfer and a transfer paper having a transfer property suitable for the surface characteristics of each product are manufactured. can do.

(5) A transfer paper using an oil-based ink printing layer having a low surface hardness can also be manufactured.

(6) Even when an oil-based ink or an ultraviolet curable ink which originally has low adhesion to the product surface is used, a pattern having excellent adhesion can be formed.

[0058]

EXAMPLES Examples are shown below to further clarify the features of the present invention.

The details of each material used in the following examples are as follows.

Epoxy resin Epoxy resin 1: Trade name "Epicoat 828", manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent = about 189 Epoxy resin 2 ... Trademark "Epicoat 807", oiled shell epoxy ( Bisphenol F type epoxy resin, epoxy equivalent = about 170 Epoxy resin 3 ... trademark "Epicoat 834", Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent = about 200 Epoxy resin 4 ... trademark "D.E.N 431", manufactured by Dow Chemical Co., Ltd., novolak type epoxy resin, epoxy equivalent = about 176 epoxy resin 5. Trademark "D.E.R. 511-A8"
0, manufactured by Dow Chemical Co., Ltd., brominated epoxy resin, epoxy equivalent = about 490, first curing agent, first curing agent 1 ... trademark "Technodine TK", manufactured by Taoka Chemical Co., Ltd., polyamide resin, active hydrogen equivalent = About 75 first curing agent 2 ... trademark "Sunmide X-2000", manufactured by Sanwa Chemical Co., Ltd., polyamide resin, active hydrogen equivalent = about 9
0 First curing agent 3: Trade name “Epicure U”, manufactured by Yuka Shell Epoxy Co., Ltd., amine adduct, active hydrogen equivalent = about 4
7 First curing agent 4 ... trademark "Epomate N001", manufactured by Yuka Shell Epoxy Co., Ltd., heterocyclic amine, active hydrogen equivalent =
About 113 first curing agent 5 ... diethylenetriamine, active hydrogen equivalent =
20.7 First curing agent 6: metaphenylenediamine, active hydrogen equivalent = 34, melting point = 62 ° C. First curing agent 7: phthalic anhydride, acid equivalent = 148, melting point = 128 ° C. Second curing agent second curing Agent 1: Trade name "Amicure PN-23", amine adduct, manufactured by Ajinomoto Co., Inc., active hydrogen equivalent = about 38,
Melting point = 100 ° C. Second curing agent 2 ... dicyanamide, active hydrogen equivalent = 21,
Melting point = 210 ° C. Second curing agent 3 ... adipic hydrazide, active hydrogen equivalent =
44, melting point = 180 ° C. second curing agent 4: 2-heptadecyl imidazole, active hydrogen equivalent = about 300, melting point = 90 ° C. second curing agent 5: diallyl melamine, active hydrogen equivalent = 5
1.5, melting point = 142 ° C. Second curing agent 6: o-tolyl biguanide, active hydrogen equivalent =
31.5 Second curing agent 7: boron trifluoride complex of diethylamine,
Active hydrogen equivalent = 143 Reactive diluent: trade name "Kajura E", manufactured by Yuka Shell Epoxy Co., Ltd., fatty acid glycidyl ester, epoxy equivalent = about 250 coloring pigment Color pigment 1: trade name "Gosei Tesgro B-8", triple pigment Co., Ltd. Colored pigment 2: Trade mark "8/0 series yellow 27", manufactured by Sterling Industrial Colors Limited, organic pigments Colored pigment 3: Trademarked "8/0 series orange 5", manufactured by Sterling Industrial Colors Limited,
Organic pigments Color pigments 4 ... Trademark "TC Powder Black", manufactured by Sakura Crepas Co., Ltd. Thermochromic pigments Color pigments 5 ... Trademark "TC Powder Red 15", Co., Ltd.
Sakura Crepas, thermochromic pigment extender extender 1 ... trademark "Aerosil R972", manufactured by Nippon Aerosil Co., Ltd., silica-based pigment extender 2: alumina silicate adhesion promoter trademark "KBM703", manufactured by Shin-Etsu Chemical Co. γ- Chloropropyltrimethoxylane -based defoamer trademark “BYK-077”, manufactured by BYK Japan KK, silicon-based defoamer Example 1 A printing ink composition for transfer paper having the following composition was prepared.

Epoxy resin 1 80 parts Color pigment 1 20 parts First curing agent 1 8 parts (2 in theoretical amount)
5%) First curing agent 2 12 parts (3 of theoretical amount)
1%) Second curing agent 1 3.7 parts (23% of theoretical amount) Second curing agent 2 7.4 parts (83% of theoretical amount) Adhesion promoter 0.2 parts Water solution consisting of dextrin on high quality imitation paper The pattern was screen-printed on the release paper having a conductive paste layer using the composition obtained above, a pattern support coating layer made of silicone resin was formed, and then dried to obtain a transfer paper according to the present invention. .

After the obtained transfer paper was immersed in water to remove the water-soluble glue layer, the pattern print layer was transferred to the outer surface of a ceramic cup and held at 80 ° C. for 15 minutes to perform printing. The layer was completely cured to fix the pattern.

Comparative Example 1 A printing ink composition for transfer paper was prepared in the same manner as in Example 1 except that the second curing agent was not used, and printed on release paper by screen printing to prepare a transfer paper. A pattern was fixed on the outer surface.

Next, the pattern on the outer surface of the teacup obtained in Example 1 and Comparative Example 1 was subjected to a cross-cut test to test the adhesion of the coating film to pottery. That is,
Using a cutter knife, 11 parallel cuts were made at 1 mm intervals in 1 cm ^{2 of} the coating film to form 100 grids, and then cellophane tape was stuck on the grids and pulled. It was examined how many of the squares remained without peeling.

A water cup was immersed in water at room temperature for one day to examine the water resistance.

The results of these tests are as shown in Table 1.

[0067]

[Table 1]

As is clear from the results shown in Table 1, in Example 1 in which the first curing agent and the second curing agent are used in combination, the coating film has good adhesiveness and excellent water resistance. On the other hand, in Comparative Example 1 in which the second curing agent was not used, the adhesion and water resistance of the coating film were low, so that it was not practical.

Comparative Example 2 A printing ink composition for transfer paper was prepared in the same manner as in Example 1 except that the first curing agent was not used, and a transfer paper was prepared by screen printing. The transfer operation could not be performed because it did not cure.

Example 2 A transparent printing paper printing ink composition having the following composition was prepared.

Epoxy resin 1 90.8 parts Reactive diluent 4.7 parts Extender pigment 1 1.8 parts Extender pigment 2 0.5 part First curing agent 3 20.2 parts (90% of theoretical amount) Second Hardener 3 6.3 parts (30% of theoretical amount) Adhesion promoter 1.0 part After printing the obtained composition as an undercoat layer on the entire release paper in the same manner as in Example 1 by screen printing, , And the coating film surface was cured.

(A) Then, on this undercoat layer, a blue ultraviolet curable ink (trade name “TU164FD”)
After forming a pattern of polka dots by screen printing using “SS Ai” (manufactured by Toyo Ink Mfg. Co., Ltd.), the pattern was cured by irradiating ultraviolet rays.

The transfer paper thus obtained was transferred to the outer surface of a ceramic cup in the same manner as in Example 1,
After holding for 5 minutes, the printed layer was completely cured to fix the polka dot pattern.

(B) A blue oil-based ink (trade name “Sericol PS3”) is used in place of the above-mentioned ultraviolet curable ink.
91 ", manufactured by Teikoku Ink Mfg. Co., Ltd.), a polka dot pattern was formed by screen printing on the same undercoat layer as described above, and then dried at room temperature for 5 hours to obtain a transfer paper.

The transfer paper thus obtained was transferred to the outer surface of a ceramic cup in the same manner as in Example 1,
After holding for 5 minutes, the printed layer was completely cured to fix the polka dot pattern.

In both cases (a) and (b), the adhesion of the coating film to the pottery was good and the water resistance was excellent.

Example 3 Thermochromic (black-fluorescent orange) having the following composition
Was prepared.

Epoxy resin 2 65 parts Reactive diluent 3.5 parts Color pigment 2 5 parts Color pigment 3 1 part Color pigment 4 36 parts First curing agent 4 43 parts (1 of theoretical amount)
00%) 12 parts of second curing agent 4 (1 of theoretical amount)
0%) Adhesion promoting agent 1 part Antifoaming agent 2 parts Using the obtained composition, a picture pattern was screen-printed on release paper in the same manner as in Example 1 and left at room temperature for 7 hours. The transparent printing composition obtained in Example 2 was screen-printed on the entire surface as an overcoat layer.
After leaving for 0 hour, transfer paper was obtained.

The transfer paper thus obtained was transferred to the outer surface of a ceramic cup in the same manner as in Example 1,
After holding for 0 minutes, the printed layer was completely cured to fix the pattern.

The pattern of the obtained teacup was black at room temperature, but showed thermochromic properties such that it turned vivid orange upon pouring hot water.

Further, the adhesion of the coating film to the pottery was good, and the water resistance was also excellent.

Example 4 A thermochromic printing ink composition for transfer paper having the following composition was prepared.

Epoxy resin 3 60 parts Reactive diluent 3 parts Extender pigment 1 1 part Color pigment 5 34 parts First curing agent 5 2.5 parts (45% of theoretical amount) Second curing agent 2 3.4 parts ( 2nd curing agent 5 2.1 parts (15% of theoretical amount) Adhesion promotion 1 part Antifoaming agent 1 part Further on the transfer paper having a blue polka dot pattern obtained in Example 2 The composition obtained above was printed so that the polka dots were hidden.

Then, the obtained transfer paper was transferred to the outer surface of a glass cup in the same manner as in Example 1,
After holding for a minute, the coating film was completely cured to fix the coating film.

The obtained glass cup exhibited an indigo polka dot pattern at room temperature, but exhibited thermochromic properties in which a red pattern emerged by pouring cold water.

The adhesion of the coating film to the glass cup was good, and the coating film was excellent in water resistance.

Example 5 A thermochromic (red-yellow) transfer printing ink composition having the following composition was prepared.

Epoxy resin 4 70 parts Reactive diluent 15 parts Color pigment 5 20 parts Color pigment 2 5 parts First curing agent 6 7 parts (5 parts of theory)
0%) 1st curing agent 2 32 parts (1 of theoretical amount)
00%) 6 parts of second curing agent 6 (5 of theoretical amount)
0%) Adhesion promoter 1 part Defoaming agent 1 part Using the obtained composition, screen-print a pattern on release paper in the same manner as in Example 1 and leave it at room temperature for 4 hours. Further, a different pattern was further printed using the thermochromic printing composition obtained in Example 4, and a pattern supporting coating layer made of a silicone resin was formed thereon.

Next, the transfer paper thus obtained was transferred to the outer surface of a glass cup in the same manner as in Example 1, held at 90 ° C. for 10 minutes, and the coating was completely cured to fix the coating.

The obtained glass cup exhibited a thermochromic property in which it exhibited a red pattern at room temperature, but exhibited a yellow pattern when cold water was poured.

The adhesion of the coating film to the glass cup was good, and the coating film was excellent in water resistance.

Example 6 A thermochromic transfer printing ink composition having the following composition was prepared.

Epoxy resin 5 90 parts Reactive diluent 10 parts Color pigment 4 40 parts Color pigment 1 5 parts First curing agent 7 7 parts (2 in theoretical amount)
5%) 1st curing agent 2 14 parts (8 of theoretical amount)
5%) 2nd curing agent 7 3 parts (1 of theoretical amount)
2%) Adhesion promoter 1 part Using the composition obtained in Example 5, screen-printing a pattern on release paper in the same manner as in Example 1, drying at room temperature, and then performing this operation The thermochromic printing composition obtained in the example was applied with a film thickness using a film applicator and dried at room temperature for 8 hours.

Next, the obtained transfer paper was transferred to the outer surface of a ceramic mug in the same manner as in Example 1,
C. for 30 minutes to completely cure the coating and fix the coating.

The obtained thermochromic mug exhibited a thermochromic property in which it was black at room temperature but had a yellow pattern when hot water was poured.

The adhesion of the coating film to the cup was good, and the coating film was excellent in water resistance.

[Brief description of the drawings]

FIG. 1 is a drawing schematically showing a cross section of an example of a transfer paper according to the present invention.

FIG. 2 is a drawing schematically showing a cross section of another example of the transfer paper according to the present invention.

FIG. 3 is a drawing schematically showing a cross section of still another example of the transfer paper according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base material (release paper) 2 ... Water-soluble glue layer 3 ... Picture layer 4 ... Picture layer 5 ... Coating layer 7 ... Undercoat layer 8 ... Ink coloring layer 9 ... Overcoat layer

Continuation of the front page (56) References JP-A-5-104898 (JP, A) JP-A-1-172478 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09D 11 / 00-11/20 B41M 3/12 B44C 1/17

Claims (8)

(57) [Claims] 1. A transfer paper comprising an epoxy resin, a first curing agent that reacts with the epoxy resin at room temperature to cure, and a second curing agent that reacts with the epoxy resin at 80 to 200 ° C. to cure. Printing ink composition. 2. The printing ink composition for transfer paper according to claim 1, further comprising a colorant. 3. The printing ink composition for transfer paper according to claim 1, comprising a reversible thermochromic composition. 4. The printing ink composition for transfer paper according to claim 1, comprising a colorant and a reversible thermochromic composition. 5. A transfer paper provided with a coating layer comprising the printing ink composition according to claim 1. 6. A transfer paper comprising a coating layer comprising the printing ink composition according to claim 2 and a coating layer comprising the printing ink composition according to claim 3. 7. A coating layer comprising the printing ink composition according to any one of claims 2 to 4, which is overcoated and / or undercoated with a coating layer comprising the printing ink composition according to claim 1. Transfer paper. 8. An oil-based ink layer and / or an ultraviolet-curable ink layer is overcoated and / or overcoated with a coating layer comprising the printing ink composition according to any one of claims 1 to 4.
Or undercoated transfer paper.