JPS59166574A - Overcoating resin composition for heat transfer paper - Google Patents

Abstract

PURPOSE:The titled composition for coloring ceramics, glass, and enameled wares, having improved printing workability, especially stringing, showing improved china-painting workability, blocking resistance, etc., obtained by copolymerizing a specific (meth)acrylic (co)monomer with ethyl cellulose. CONSTITUTION:(A) 40-98wt% (meth)acrylic (co)monomer (e.g., methyl methacrylate, n-butyl methacrylate, etc.) shown by the formula I (R1 is H, or methyl; R2 is 1-12C aliphatic group, or alicyclic group) is copolymerized with (B) 2- 60wt% ethyl cellulose, to give the desired overcoating resin composition. The above-mentioned composition can be blended with phthalic ester shown by the formula II (R3 and R4 are 1-12C aliphatic group, alicyclic group, alkyl ether alkyl, or hydroxypolyoxyalkylene), adipic acid alkyl ester, etc. as a plasticizer. EFFECT:Having improved baking properties.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an overcoat resin composition for coloring transfer paper for ceramics, glass, enamel, etc., which has excellent printing workability and film properties.

In the nitrogen industry, the single-paper painting method, which uses transfer paper, has been widely used to add patterns to the surfaces of window products such as ceramics, glass, and enamel. This transfer paper is made by coating one side of the mount with a water-soluble glue, then printing a pattern on it with a printing ink used for ceramics, glass, enamel, etc., and then using acrylic resin or cellulose. It is obtained by applying an overcoat resin such as a type resin. The single paper painting method involves dipping the transfer paper in water to dissolve the glue layer on the backing paper, transferring the pattern to a resin layer, pasting this resin layer on a predetermined position on the object, then drying and baking. It is something to do.

As described above, the overcoat resin is printed on a transfer paper on which a pattern has been printed using a printing ink for decoration, and after drying, it is applied to an object to be transferred by a single-sheet painting method. After further drying, it is fired, but the physical properties of the overcoat resin at this time are as follows:
(1) Excellent printing workability, (a) No stringiness during printing, (b) No foaming during printing, (c) Good leveling on the surface of the pattern during printing. (2) There is no adhesion (blocking) with the back side of the upper transfer paper that occurs when the dried transfer paper is stacked and stored after printing, and ceramic products of various shapes can be produced using the single-sheet painting method. (3) Excellent film physical properties (transfer painting properties) (a) High film strength (must be easily torn during transfer painting) (b) Flexibility and flexibility (4) Good firing properties; (a) Completely smooth when fired; (b) When fired, the design must be fixed and sagged at the specified position (no pinholes, run-off, etc. in the fired design); (c) The leveling and coloring of the fired design must be beautiful. , is required.

Cellulose resins have heretofore been used as overcoat resins for ceramic transfer papers, but although the firing properties are good, the physical properties of the film and printing workability are poor. In terms of physical properties, the film has very good strength, but it lacks flexibility, flexibility, and elongation, making it almost impossible to attach it to curved surfaces, and it also has poor weather resistance, and the resin may change orally. This has the disadvantage that the overcoat resin deteriorates.

However, on the other hand, this resin has very good blocking resistance when used as an overcoat resin.
This has the advantage that there is no need to insert interleaf paper to prevent blocking.

Regarding printing workability, the overcoat resin used in printing is usually used in the form of a solution, but the cellulose resin used as the overcoat resin has a low concentration and high viscosity. In order to form a resin solution, a very high viscosity resin solution is used during printing, which is extremely difficult to handle, and depending on the product, it may be necessary to print twice as the film is not as thick as expected. It has the following disadvantages.

In recent years, acrylic and methacrylic resins have been used to solve the problem of film properties, especially flexibility, but although they give good results in terms of film properties, especially painting workability and firing workability, they have poor printing workability. In particular, it is poor in terms of stringability and foaming, and is inferior in blocking resistance, which is an advantage of Matter 1 = luulose resin.

Therefore, we have been studying the characteristics of cellulose resin and acrylic for some time.
In order to take advantage of the characteristics of methacrylic resin, we mixed the two to make the film surface semi-glossy (matte), and researched to obtain an overcoat resin with good blocking resistance, flexibility, and sinterability (4). ), but this attempt resulted in poor compatibility between the mixed cellulose resin and acrylic and methacrylic resins, and the product stability of the overcoat resin solution was very poor, so the cellulose resin and the cellulose resin deteriorated over time. The result is that the acrylic and methacrylic resins separate and the composition of the resin differs depending on the location of the overcoat resin solution. Also,
Regarding printing workability, in recent years, in order to improve productivity, the amount of transfer paper that can be printed is no more than 35 sheets per minute.
There was no significant difference in printing workability compared to acrylic and methacrylic resins.

The inventors of the present invention have conducted intensive research to obtain an overcoat resin that has very good printing workability, especially threadability, and film properties, especially blocking resistance, painting workability, and firing performance. By copolymerizing a certain type of acrylic or methacrylic monomer or comonomer with a cellulose resin, printing workability (especially threadability) is very good, and film physical properties (especially painting workability) are improved. ), an overcoat resin with good blocking resistance, sinterability, and solution stability (separation over time) was obtained. This overcoat resin has no stringiness in terms of printing workability, and has a workability that can withstand printing of 40 to 45 sheets per minute in tests using a cylinder printing machine. It has a film, has very high film strength, has excellent blocking resistance, and also has good results in firing properties.

That is, the overcoat resin composition for transfer paper according to the present invention has the following formula: A, general formula (wherein R1 is H or a methyl group, R2 is
40 to 98% by weight of a monomer or co-q surplus having at least one structural unit represented by (aliphatic group or alicyclic group) is copolymerized with B and 2 to 6% by weight of ethyl cellulose. This is what happens.

In the above, examples of compounds forming the constituent units of the monomer ψ and comonomer of component A include methyl acrylate, ethyl acrylate, acrylate η-propyl, 1so-propyl acrylate, and n-acrylate. -butyl, 1So-butyl acrylate, 2-ethylhexyl acrylate,
Dodecyl acrylate, methacrylate, ethyl methacrylate, n-propyl methacrylate, 1so-propyl methacrylate, n-butyl methacrylate, 1so-butyl methacrylate, methacrylic acid i;
6rt-butyl, 2-ethylhexyl methacrylate,
Cyclohexyl methacrylate, dodecyl methacrylate, etc. are alkyl esters of acrylic acid, methacrylic acid, etc. each having 1 to 12 carbon atoms in the alkyl group, and have a linear or iso-isomer or alicyclic shape. can give.

(7) In addition, as the ethyl cellulose of component B, for example, Ethocel MID-10, 20, 50, 7 manufactured by Dow Chemical Company
0,100 and 5TD-4,7,10,20,45,1
Ethylce/l10-1 manufactured by 00 and Hachi-Cures
4,50,100,200,5000 and N-4,7,
Examples include T-10, 14, 22, 50, 100, 200, 300 and T-10, 50, 1,00, 200.

The above-mentioned overcoat resin composition according to the present invention may contain, for example, a plasticizer of the general formula (sub) (3:07 (wherein, R8 and R4 are each independently Phthalate esters, adipic acid alkyl esters, citric acid alkyl esters, etc. represented by aliphatic groups to alicyclic groups having 1 to 12 carbon atoms and alkyl ether alkyl groups to hydroxypolyoxyalkylene groups are usually used in appropriate amounts. It is mixed.

The raw material composition ratio of the copolymer in the resin composition according to the present invention is A component: B component = 40-98: 60-2 (wt%)
(8) Excellent performance is exhibited within this composition range. When the B component is less than 2%, the sinterability and blocking resistance, which are the characteristics of ethyl cellulose, are poor, and when it exceeds 60%, the copolymerization of the A component is inhibited, resulting in poor stability in the resin solution. Sexuality becomes poor. Also,
Within the above composition range, a product having good printing workability for high-speed use in a cylinder printing machine can be obtained.

Furthermore, when a monomer with a low glass transition point is used as component A, such as acrylic esters or methacrylic esters having an alkyl group of 6 or more carbon atoms,
When the blending ratio of the components is low, it is almost unnecessary to add a plasticizer, but on the other hand, when the glass transition point of the A component is high or the blending amount of the B component is large, the addition of a plasticizer is necessary. More and more come. Even in this case, the formed film becomes matte, so the physical properties of the film are lower than that of conventional overcoat resins.
Particularly excellent in blocking resistance.

The resin composition according to the present invention is usually used in the form of a solution, and the solvent used is cellosolve, their esters, and solvent naphtha, and the concentration of the solution is 20 to 60%. is common.

The content of the present invention will be illustrated below with examples, but the present invention is not limited thereto.

[Example 1] Ethyl cellulose prepared to a concentration of 20% by weight (Ethocel 5TD-20 manufactured by Dow Chemical Company) was placed in a four-bottle flask equipped with a stirrer, condenser, nitrogen blowing tube, and thermometer.
Added 125 parts by weight of ethylene glycol monoethyl ether acetate solution, and further added 40 parts by weight of methyl methacrylate and 160 parts by weight of n-butyl methacrylate.
and 0.2 parts by weight of azobisisobutyronitrile were charged, and the reaction was carried out at a temperature of 80°C in a nitrogen atmosphere for 3 hours, and further 0.5 parts by weight of azobisisobutyronitrile was added. After the reaction was completed, 239 parts by weight of ethylene glycol monoethyl ether acetate was added to obtain a resin solution having a solid content of 40% by weight.

To 100 parts by weight of this resin solution, 4 parts by weight of dioctyl phthalate as a plasticizer, 0.5 parts by weight of an antifoaming agent, and 0.05 parts by weight of an oil-soluble dye for coloring the overcoat resin printed on the transfer paper. and 44 parts by weight of ethylene glycol monoethyl ether acetate to obtain a solution viscosity suitable for screen printing on a cylinder printing press, resulting in a viscosity of 2000 cps (20°C) and a solids content of 30% by weight. An overcoat resin solution was prepared.

This resin solution was run at 45 min per minute on a cylinder printing machine. After sufficiently drying the resulting transfer papers, they were stacked one on top of the other, and after applying a pressure of 50 g/aJ at a humidity of 50°C for 7 days, the transfer papers were peeled off from each other, but no blocking was observed. Ta. Furthermore, this transfer paper was pasted on a white ceramic plate by the single paper painting method, and the physical properties of the film were very good, and no problems such as tearing or cutting of the film occurred during pasting.

Also, heat this earthenware dish to a temperature of 800'C, (1
l) When it was cooled, the resin layer was completely burned out, and the pattern was fired as a beautiful MK without any pinholes or flow.

[Example 2] Using the same apparatus as in Example 1, 8Q parts of n-7' methyl methacrylate, 41 parts of ethyl cellulose (ethyl cellulose N-4 manufactured by Vercules), 120 parts by weight, and Tsurupez #1-00 (manufactured by Esso) were prepared. 100 parts by weight of high s point naphtha) and 0.2 parts by weight of benzoyl peroxide were charged, and the reaction was carried out at a temperature of 80'C in a nitrogen atmosphere for 3 hours, and further 0.5 parts by weight of benzoyl peroxide was added. The reaction was carried out for 4 hours, and after the reaction was completed, 200 parts by weight of Tsurpetsui 100 was added to obtain a resin solution with a solid content of 40% by weight.

To 100 parts by weight of this resin solution, 25 parts by weight of dioctyl adipate as a plasticizer, 0.5 parts by weight of an antifoaming agent, 0.05 parts by weight of an oil-soluble dye, and 60 parts by weight of Tsurupetsu 100 were added to give a viscosity of 1700 cps ( An overcoat resin solution according to the present invention was prepared at a temperature of 20° C. and a solid content of 35% by weight.

This resin solution was tested in the same manner as in Example 1 (l 2
) As a result, good results were obtained in terms of printing workability, anti-blocking properties, film properties, and firing properties.

[Example 3] Using the same apparatus as in Example 1, 100 parts by weight of n-butyl methacrylate, 76 parts by weight of 1so-butyl methacrylate, 20 parts by weight of n-butyl acrylate, and ethyl cellulose (Ethocel manufactured by Dow Chemical Company) were added. MED-100) 4 parts by weight, 100 parts by weight of ethylene glycol monoethyl ether acetate, and 0.2 parts by weight of methylcyclohexanone peroxide were charged, and the reaction was carried out at a temperature of 80'C under a nitrogen atmosphere for 3 hours. 0.5 parts by weight of oxide was added and the reaction was carried out for 4 hours. After the reaction was completed, 200 parts by weight of Tsurupetz #100 was added to obtain a resin solution with a solid content of 40% by weight.

The film made of this resin solution has good flexibility and elongation, and there is no need to improve the film properties with a plasticizer.
To 100 parts by weight of this resin solution, 0.5 parts by weight of an antifoaming agent, 0.05 parts by weight of an oil-soluble dye, and 1 part by weight of Solbetsuso were added.
Added 55 parts by weight, viscosity 1700 cps (20'C
), an overcoat resin solution according to the present invention having a solid content of 35% by weight was prepared. This resin solution was tested in the same manner as in Example 1, and as a result, the printing workability, blocking resistance, film physical properties, and firing properties were all good.

[Example 4] Using the same equipment as in Example], ethyl methacrylate]
-80 parts by weight, 130 parts by weight of a Tsurupetz 41:100 solution of ethyl cellulose (ethyl cellulose T-10 manufactured by Vercules) prepared to a concentration of 15% by weight, and 0.2 parts by weight of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen atmosphere. The reaction was carried out at a temperature of 80'C for 3 hours, and 0.5 parts by weight of azobisisobutyronitrile was further added and the reaction was carried out for 4 hours.
0 part by weight was added to obtain a resin solution with a solid content of 40% by weight.

To 100 parts by weight of this resin solution, 8 parts by weight of butylbenzyl phthalate as a plasticizer, 0.5 parts by weight of an antifoaming agent, 0.05 parts by weight of an oil-soluble dye, 3.0 parts by weight of ethylene glycol monoethyl ether acetate. o Weight 9 added, viscosity 18
An overcoat resin solution according to the present invention was prepared at 00 cps (20°C) and a solids content of 35% by weight. When this was tested in the same manner as in Example 1, good results were obtained in terms of printing workability, blocking resistance, film physical properties, and firing properties.

[Example 5] Using the same equipment as in Example 1, 10 parts by weight of 2-ethylhexyl methacrylate, 20 parts by weight of dodecyl methacrylate, 70 parts by weight of methyl methacrylate, 90 parts by weight of n-butyl methacrylate, 10 parts by weight of ethyl cellulose (Ethocel 5TD-45 manufactured by Dow Chemical Company), 10 parts by weight of 1s○-propyl alcohol, 150 parts by weight of Tsurpet'l OO and 0.2 parts by weight of benzoyl peroxide were heated at 80° under a nitrogen atmosphere. The reaction was carried out for 3 hours at a temperature of A resin solution having a solid content of 40% by weight was obtained.

Since this resin does not require a plasticizer as in Example 3, 0.5 parts by weight of an antifoaming agent and 0.05 parts by weight of an oil-soluble dye were added to 100 parts by weight of this resin solution, and the viscosity was 1500.
cps (20° C.) and an overcoat resin solution according to the present invention having a solid content of 40% by weight. Regarding this, a test was conducted in the same manner as in Example 1, and it was found that printing workability,
Good results were obtained in blocking resistance, film physical properties, and sintering properties.

[Example of scolding]] Using the same equipment as in Example 1, methacrylic acid is.

-138 parts by weight of butyl, 60 parts by weight of methyl methacrylate, ethyl cellulose (5TD-4 manufactured by Dow Chemical Company)
2 parts by weight, 200 parts by weight of Tsurpets 100 and 0.2 parts by weight of azobisisobutyronitrile were charged, and the reaction was carried out at a temperature of 80°C for 3 hours in a nitrogen atmosphere. Add .5 parts by weight to 4
Perform the reaction for a period of time, and after the reaction is completed, Tsurpets: #100
101 parts by weight (16) was added to obtain a resin solution with a solid content of 40% by weight.

To 100 parts by weight of this resin solution, 20 parts by weight of dioctyl fucurate, 0.5 parts by weight of antifoaming agent, and 0.05 parts by weight of oil-soluble dye.
Parts by weight and 39 parts by weight of Tsurpets" 100 were added to prepare an overcoat resin solution with a viscosity of 2000 cps (20'C) and a solid content of 38% by weight. When this resin solution was tested in the same manner as in Example 1, the resistance Although the blocking and firing properties were good, there were too many threads in the printing process, making it impossible to continue printing.Furthermore, regarding the physical properties of the film, it lacked flexibility and elongation, making it difficult to print on pottery. Pasting was difficult.

[Comparative Example 2] Using the same equipment as in Example 1, n-butyl acrylate 6o
iits, ethyl cellulose (ethyl cellulose K' manufactured by Vercules) 140 m by weight, 250 parts by weight of ethylene glycol monoethyl ether acetate and 0.2 parts by weight of azobisisobutyronitrile,
The reaction was carried out at a temperature of 80'C for 3 hours under a nitrogen atmosphere,
Furthermore, 0.5 parts by weight of azobisisobutyronitrile was added and the reaction was carried out for 4 hours. After the reaction was completed, 51 parts by weight of ethylene glycol monoethyl ether acetate was added to obtain a resin solution with a solid content of 40% by weight. .

To 100 parts by weight of this resin solution, 0.5 parts by weight of an antifoaming agent and 0.05 parts by weight of an oil-soluble dye were added.
cps (20°C) and an overcoat resin solution having a solid content of 40% by weight was prepared. When this resin melt was tested in the same manner as in Example 1, good results were obtained regarding printing workability and film physical properties, but poor firing performance was observed as there were many pinholes in the pattern.

[Comparative Example 3] Using the same equipment as in Example 1, ethyl methacrylate 20
0 parts by weight, 150 parts by weight of Tsurupetz Ni 100, and 0.2 parts by weight of benzoyl peroxide, and 80 parts by weight in a nitrogen atmosphere.
The reaction was carried out for 3 hours at a temperature of A resin solution was obtained.

For 100 parts by weight of this resin solution, 1 part dibutyl phthalate
0 parts by weight, 0.5 parts by weight of antifoaming agent, 0.05 parts by weight of oil-soluble dye and 10 parts by weight of Tsurpetz"l OO, viscosity 1300 cps (20'C), solids content 42 wt@% overcoat. A resin solution was prepared. When this resin solution was tested in the same manner as in Example 1, good results were obtained regarding film properties, printing workability, and firing properties, but regarding blocking resistance, the entire surface of the overcoat resin were stuck and could not be peeled off from each other.

Table 1 shows a comparison of the physical properties of each resin in Examples 1 to 5, Comparative Examples 1 to 3, and conventional products.

(The following is the margin of this page) (Note) Regarding the evaluation method in Table 1 (1) Printing workability (a) For stringability, a cylinder printing machine was used to print at a printing speed of 45 sheets per minute, and 1000 sheets were printed. Observe the amount of resin threads generated at the bottom of the screen at the time of printing. Those that were not threaded at all (◎), those that were hardly threaded (○), and those that were threaded (△). Items in which a large amount of thread was threaded and printing could not be continued were marked with an (x).

(b) Regarding defoaming properties, at the time of the test in (a), those that defoamed immediately after printing were marked as (○), and those that foamed immediately after printing but disappeared within 10 seconds were marked as (△). , Those that foamed immediately after printing and did not defoam were rated (x).

(C) Regarding leveling, at the time of testing (a,), the overcoat resin becomes flat and uniform on the pattern immediately after printing (○), and the overcoat resin becomes flat and uniform within 10 seconds. Those that did not become flat even after drying were designated as (x).

(2) Blocking resistance Tests were conducted under the same conditions as in Example 1. Those with no blocking at all (◎), those with almost no blocking (○), and those with partially blocked patterns ( △), most of the pattern is blocked (
x).

(3) Firing properties (a) Regarding wrinkles, each Orvercode resin was printed on a flat pattern of 2m x 3c1n, and the number of pinholes generated on the surface of the pattern was counted when it was fired as in Example 1. Ta.

(b) Regarding color development and leveling, those with the desired color development and flat and uniform leveling (○), those with good color development but poor leveling, or those with poor color development and good leveling (
△), and those with poor color development and leveling were marked as (x).

(C) Regarding total firing, total firing was performed as in Example 1 using gold paste such as 5G-N8 manufactured by Noritake Company and 642A manufactured by Nippon Yoiri Co., Ltd., and 7114708 manufactured by Kenkagakusha Co., Ltd. Items with no haze (cloudiness) on the surface (○), items with a small amount (△)
, Those that occur in large amounts are marked (×).

(4) Separation stability of resin solution Regarding the presence or absence of separation when left at 50°C for one month,
Those with no separation at all were rated as (○), and those with a tendency to separation or separation were rated as (x).

that's all Agent Patent Attorney Atsushi Yasufuji (23)

Claims (1)

[Claims] (]-) ]A, in the general formula, R is H or a methyl group, and R2 has 1 to 1 carbon atoms.
40 to 98% by weight of a monomer or comonomer having at least one kind of structural unit represented by B, which is an aliphatic group or an alicyclic group, is copolymerized with B, 2 to 60% by weight of ethyl cellulose. Overcoat resin composition for transfer paper.