JPS60260397A - Overcoating resin composition for transfer paper - Google Patents

Abstract

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

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention provides an overcoat for transfer paper with excellent blocking resistance for coloring ceramic products such as ceramics, glass, and enamel. The present invention relates to a coat resin composition.

[Conventional technology and its problems]

In the ceramic industry, a single-paper painting method using transfer paper has been widely used to add patterns to the surface of ceramic products such as ceramics, glass, and enamel. However, this transfer paper is
A water-soluble glue is applied to one side of the mount, a pattern is printed on it using printing ink for painting ceramic products, and acrylic or methacrylic resin is applied on top to maintain the shape during transfer of the pattern. Obtained by printing and applying an overcoat resin such as cellulose resin. Here, the single paper painting method refers to dipping the transfer paper in water, dissolving the glue layer on the mount, peeling off the pattern and overcoat resin from the mount, pasting it on a predetermined position on the transfer object, and then drying it. , to be fired.

The following physical properties are required for the overcoat resin for transfer paper as described above. First, since the overcoat resin is stored, printed, and applied in the form of a solution, (1) the overcoat resin solution must have excellent storage stability, that is, the overcoat resin and the solvent will not separate over time; , because the additives in the resin property modification tank do not precipitate or separate, and because they are screen printed by a screen printer when printing and coating on transfer paper, (2)
) It is required to have excellent printing workability, that is, no stringiness during printing, bubbles disappear quickly during printing, and good leveling on the surface of the pattern during printing.

After printing, when the dried transfer paper is stacked and stored, the upper transfer paper adheres to the back side (blocking).
(3) It has excellent blocking resistance, and it can be attached to ceramic products of various shapes by the single-sheet painting method. (4) It has excellent film properties (transfer painting properties). Being there,
In other words, the film must have a strength that will not tear during the transfer process, it must have good softness and flexibility, and it must have an appropriate amount of elongation.Finally, the painted and dried transfer material is fired to create the design. (5) Good firing properties, that is, the resin composition is completely burned off when fired, the pattern is completely fixed to the transferred object when fired, and leveling and coloring are prevented. Beautiful things, such as tips for painting ceramic products of various shapes) When painting the entire circumference of a cylindrical object such as a cylindrical object, if the edge of the pattern and overcoat resin overlaps the other edge (overlapping) ), it is required to be baked beautifully without any problems, etc.

Conventionally, cellulose resins or acrylic/methacrylic resins have been widely used as overcoat resins for ceramic-related transfer papers. However, the former cellulose resin has good blocking resistance and sinterability;
Although there is no practical problem in terms of printing workability, there are drawbacks in the physical properties of the film, particularly in flexibility, elongation, etc. In addition, the latter acrylic/methacrylic resin has good firing properties and film properties, and has no practical problems in printing workability, but has a drawback in blocking resistance.

To solve these problems, we have been mixing cellulose resins and acrylic/methacrylic resins to take advantage of their respective characteristics, making the film surface semi-glossy (matte), improving blocking resistance, and improving the film's anti-blocking properties. Attempts have been made to create an overcoat resin with good physical properties and sinterability. However, in this attempt, the compatibility between the mixed cellulose resin and acrylic/methacrylic resin was poor, and the two separated over time, resulting in poor storage stability of the overcoat resin solution. However, the overcoat resin solution has the inconvenience of having to be stirred to make it uniform throughout before printing.

Furthermore, improvements have been made to acrylic methacrylic resins by adding finely powdered matting agents such as cornstarch, methylcellulose, and polyethylene to mattify the film surface and improve blocking resistance. However, this method also tends to have worse sinterability than the original overcoat resin due to the addition of a matting agent, and there are also problems with storage stability.
The matting agent often settles or floats over time. Note that some products with added polyethylene etc. have no problems with storage stability or blocking resistance.
There is a problem with firing properties, especially stacking firing properties, and 1.
It has drawbacks such as pinholes occurring in overlapping patterns or not completely adhering to the transferred object.

[Problem to be solved by the invention]

The present invention solves the above-mentioned drawbacks of the conventional technology, and provides an overcoat resin composition for transfer paper that has good storage stability, printing workability, and film properties, and has particularly excellent freonking resistance and sintering properties. This is what we are trying to provide.

(, b) Structure of the Invention [Means for Solving the Problem] As a result of intensive research to solve the above problem, the inventors of the invention discovered that a certain type of fatty acid amide was coated with a certain type of acrylic/methacrylic overcoat. By adding it to the resin,
It has been found that good results can be obtained. The present invention was completed based on this knowledge.

That is, the present invention provides a copolymer having at least one structural unit represented by the general formula (wherein, hydrogen or methyl group, & is an aliphatic group or alicyclic group having 1 to 12 carbon atoms). Combined (A) 80 to 99% by weight and general formula % formula % or general formula OHHO (wherein, the circle is a saturated aliphatic group or unsaturated aliphatic group having 5 to 21 carbon atoms, & is hydrogen or a methylol group, The present invention provides an overcoat resin composition for transfer paper, which contains 1 to 20% by weight of fine powder of at least one fatty acid amide (B) represented by methylene group or ethylene group.

In the above, examples of the compound forming the structural unit of the copolymer of component (A) include methyl acrylate, ethyl acrylate, n-propyl acrylate,
so-propyl, n-butyl acrylate, acrylic acid 1
so-butyl, 2-ethylhexyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, 1so- methacrylate
Propyl, n-butyl methacrylate, methacrylic acid 1s
O-butyl, tert-butyl methacrylate, buty-2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, etc. are alkyl esters such as acrylic acid and methacrylic acid each having 1 to 12 carbon atoms in the alkyl group. Examples include those having a shape or an isoform and an alicyclic shape.

In addition, fatty acid amide of component (B) (including N-methylol fatty acid amide, N,N'-methylenebis fatty acid amide, N,+r'-ethylenebis fatty acid amide)
Examples include caproic acid amide, eronic acid amide, caprylic acid amide, pelargonic acid amide, capric acid amide, undecane acid amide, lauric acid amide, tridecanoic acid amide, myristic acid amide, bentadecanoic acid amide, palmitic acid amide, heptadecanoic acid amide, stearic acid amide, oleic acid amide, elaidic acid amide, linoleic acid amide, lycylic acid amide, stearolic acid amide, lysyl acid amide, arachidic acid amide, behenic acid amide, erucic acid amide, brassic acid amide, and N-methylolcaproic acid amide, N
-Methylol capunic acid amide, N-methylol caprylic acid amide, N-methylol pelargonic acid amide, N-methylol capric acid amide, N-methylol undecanoic acid amide, N-methylol lauric acid amide, N-methylol tridecanoic acid amide, N
-Methylol myristate amide, N-methylol pentadecanoic acid amide, N-methylol palmitic acid amide, N-methylol heptadecane amide,
N-methylolstearamide, N-methylololeic acid amide, N-methylolelaidic acid amide, N-methylollinoleic acid amide, N-
Methylololeic acid amide, N-methylolstearolamide, N-methylollysylureinamide, N-methyl9-ruarachic acid amide, N-
Methylolbehenic acid amide, N,-methylolerucic acid amide, N-methylolbrasidic acid amide, and N,N'-methylenebiscaproic acid amide, N,N'-methylenebisalanic acid amide, N,N'
-Methylenebiscaprylic acid amide, N,N'-methylenebispelargonic acid amide, N,N'-methylenebiscaprylic acid amide, N,N'-methylenehisundecanoic acid amide, N,N'-methylenebislauric acid amide , N, N'-methylene bistridecanoic acid amide, N, N'-methylene bismyristic acid amide, N, N'-methylene bispentadecanoic acid amide, N
, N'-methylenebispalmitic acid amide, N,
N'-methylenebisheptadecanoic acid amide, N, *-
Methylenebisstearamide, N,N'-methylenebisoleic acid amide, N,N'-methylenebiselaidic acid amide, N,N'-methylenebislinoleic acid amide, N,N'-methylenebisoleic acid amide, N,N'-methylenebisstearolamide, N,N'-methylenebislycylinamide, N,N'-methylenebisarachamide, N,N
'-methylene bisbehen butyamide, N,N'-7 tyrene bis-ercinamide, N,N'-methylene bisbrasidic acid amide, and N,N'-ethylene biscaproic acid amide, N,N'-ethylene Bis-erunic acid amide, N, N'-ethylene biscaprylic acid amide, N, N'-ethylene bispelargonic acid amide, N,
N'-ethylenebiscapric acid amide, N,N'-ethylenebisundecanoic acid amide, N,N'-ethylenebiscapric acid amide, N,N'-ethylenebistridecanoic acid amide, N,N'-ethyl, 73 ．． □、Eyo Tsuo Ai、・1.・-(bispentadecanoic acid amide, N,N'-ethylene bispalmitic acid amide, N,N'-ethylene bisheptadecanoic acid amide,
N, N'-ethylene bisstearamide, N,
N'-ethylene bisoleic acid amide, N, N'-
Ethylene biselaidic acid amide, N, N'-ethylene bisrinol amide, N, N'-ethylene bis erucic acid amide, N, N'-ethylene bis stearolic acid amide, N, N'-ethylene bislycylin, Acid amide, N,N'-ethylene bis-a-rachinic acid amide, N,N'-ethylene bis-behenic acid amide,
N,N'-ethylenebisersic acid amide, N,N'
- Examples include ethylene bisbrasidic acid amide.

As for the properties of the fine powder of fatty acid amide as the component (B), it is desirable that the melting point is 100° C. or more and the particle size is 50 L or less. Here, the melting point is less than 100℃ ('
Regarding component B), when it is added to the overcoat resin of component (A), there is no problem with storage stability, printing workability, film physical properties, and sintering properties, but there is a difference in blocking resistance from the original overcoat resin. It will be inferior in comparison. Regarding component (B) with a particle size exceeding 50 JL, although the blocking resistance is improved when it is added to the overcoat resin of component (A), the film surface becomes too rough and the physical properties of the film are particularly affected. Flexibility and elongation deteriorate, and furthermore, sinterability becomes poor.

Constituting the overcoat resin composition according to the present invention (A
The blending ratio of component ) and component (B) is 80 to 8 for component (A).
It is required that the amount of component (B) be 1 to 20% by weight relative to 9% by weight, and within this range, the desired excellent effects are exhibited.

Here, when the content of component (B) is less than 1% by weight, the anti-blocking property, which is the desired effect of the present invention, will be poor.
If the amount exceeds 20% by weight, the physical properties of the film, especially flexibility and elongation, will deteriorate, and the sinterability will also deteriorate.

In the overcoat resin composition according to the present invention, if necessary, as a plasticizer, the general formula (in the formula, circles and & are each independently an aliphatic group having 1 to 12 carbon atoms, 1 to 12 carbon atoms, 12 alicyclic groups, alkyl ether alcohols or polyalkylene glycols), such as phthalbutyrinthyl, adipate alkyl esters, citric acid alkyl esters, etc., are usually used in appropriate amounts.

The addition of these plasticizers is based on copolymers with a low glass transition point (hereinafter referred to as Tg) as component (A), such as acrylic esters and methacrylic acid in which di is an alkyl group having 6 or more carbon atoms. When using esters, (B
) is almost unnecessary when the blending ratio of component (A) is low, but on the other hand, it becomes necessary when the Tg of component (A) is high or the blending ratio of component (B) is high. It goes without saying that even when a plasticizer is used in this way, the resin composition of the present invention has superior blocking resistance compared to conventional overcoat resins because the formed film forms a mantle.

Since the overcoat resin composition for transfer paper according to the present invention is usually used in the form of a solution, cellosolve-based solvents, their esters, and nruben/tonaftha-based solvents are generally used. The concentration is 20-6
0% by weight is suitable.

[Examples and comparative examples]

Next, the present invention will be specifically explained by showing Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition to each overcoat resin related to these examples and comparative examples, Table 1 also lists cellulose resin and acrylic resin, which are conventional overcoat resins, to facilitate mutual performance comparison. There is.

Incidentally, % and parts described in the Kinomio side and comparative examples mean % by weight and parts by weight, respectively.

Example 1 In a four-hole flask equipped with a stirrer, condenser, nitrogen blowing tube, and thermometer, 40 parts of cyclohexyl methacrylate 150 parts of n-butyl methacrylate 10 parts of ethyl acrylate 1 Solvetun $1100 (Solvent naphtha, manufactured by Esso) 150 parts of benzoyl peroxide o, 2 fIB were charged and the reaction was carried out at a temperature of 70°C for 3 hours in a nitrogen atmosphere, and then 0.5 part of benzoyl peroxide was added and the reaction was carried out for 4 hours until the reaction was completed. Thereafter, 150 parts of ethylene glycol mono:thyl ether acetate was added to obtain a copolymer solution of 7 g and 28° C. with a solid content of 40%.

Next, 100 parts of this copolymer solution was added with Slipax E
(N,N'-ethylene bisstearamide, melting point 140'C, manufactured by Nippon Kasei Co., Ltd.) 3 parts fine powder (pulverized to a particle size of 40 mm), 2 parts dibutyl phthalate as a plasticizer
1 part, 0.5 part of antifoaming agent, and 0.05 part of oil-soluble dye to colorize the overcoat resin printed on the transfer paper.
Furthermore, in order to make the solution viscosity suitable for screen printing with a cylinder printing machine, 7 parts of Tsurupetz 5too (solvent naphtha, manufactured by Esso) was added, resulting in a viscosity of 1400 cp.
s (20° C.), an overcoat resin solution with a solid content of 40% was prepared.

Next, this resin solution was screen printed on transfer paper with a pattern printed on it, and after sufficiently drying, they were stacked together and left at a temperature of 50°C and a pressure of 50g/cj for 7 days, and then the transfer papers were placed on each other. Although it was peeled off, no blocking was observed. Furthermore, this transfer paper was pasted onto a white ceramic plate using the single-sheet 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.

Furthermore, in the same way as in step 1, the pattern was pasted on top of the previously painted pattern on the ceramic plate, and after drying, the ceramic plate was heated at a temperature of 800°C for 3 hours, and then cooled. The resin layer was completely burnt out, there were no pinholes in the design and the overlaid design, and the adhesion to the ceramic plate and color development were extremely good.

Example 2 Using the same equipment as in Example 1, 10 parts of ethyl methacrylate, 20 parts of lauryl methacrylate, 20 parts of butyl acrylate, 150 parts of Tsurpetz 11100 (solvent naphtha, manufactured by Esso), and 0.2 parts of benzoyl peroxide were added. The reaction was carried out in an atmosphere at a temperature of 80°C for 3 hours, and 0.5 parts of benzoyl peroxide was further added and the reaction was carried out for 4 hours.
100 (Nrubento naphtha, manufactured by Esso) was added to obtain a copolymer solution of 7 g and 42° C. with a solid content of 40%.

Next, fatty acid amide S was added to 100 parts of this copolymer solution.
(Stearamide, melting point 100-105°C9
10 parts of fine powder (pulverized to a particle size of 20 to 40 l) (manufactured by Kao Soap Co., Ltd.), 5 parts of dioctyl adipate as a plasticizer
1 part, antifoaming agent 0.5 parts, oil-soluble dye 0.05 parts, and Tsurpets #1 (solvent naphtha, manufactured by Esso) 3
0 parts was added to prepare an overcoat resin solution with a viscosity of 1700 cps (20° C.) and a solid content of 38%.

Subsequently, this resin solution was subjected to the same test as in Example 1, and the blocking resistance was determined.

Good results were obtained in both film properties and sinterability.

Example 3 Using the same equipment as in Example 1, 80 parts of methyl methacrylate 35 parts of isobutyl methacrylate 100 parts of butyl acrylate ) fine powder (pulverized to a particle size of 50 l or less) 5
150 parts of Tsurpetz L100 (solvent naphtha, manufactured by Esso) 0.2 parts of benzoyl peroxide were charged, the reaction was carried out at 70°C for 3 hours in a nitrogen atmosphere, and further 0.5 parts of benzoyl peroxide was added. After the reaction was completed, 150 parts of ethylene glycol heptanoethyl ether acetate was added to obtain a copolymer composition solution with a solid content of 40% and a Tg of 20°C.

The film of this copolymer composition solution had good flexibility, elongation, etc., and there was no need to improve the physical properties of the film with a plasticizer. Therefore, in 100 parts of this copolymer composition solution,
Antifoaming agent 0.5 part, oil-soluble dye 0.05 part, Tsurpets 1
1100 (Solvent naphtha.

15 parts (manufactured by xso) was added, and the viscosity was 1300 cps.
(20°C), an overcoat resin solution of 2:35% solids was prepared.

Subsequently, this resin solution was subjected to the same tests as in Example 1, and as a result, the blocking resistance, film physical properties, and sinterability were all good.

Comparative Example 1 100 parts of a copolymer solution obtained using the same equipment, raw material composition, blending ratio, and reaction method as in Example 1 was added with Frocene uF-2o (fine polyethylene powder).

Melting point: 110°C, particle size: 75p or less, manufactured by Seitetsu Kagaku Kogyo Co., Ltd.)
3 parts, 2 parts of dibutyl phthalate as a plasticizer, 0.0 parts as an antifoaming agent.
5 parts of oil-soluble dye, 0.05 part of oil-soluble dye, and 7 parts of Tsurpetz #10° (solvent naphtha, manufactured by Esso) were added, and the viscosity was 14.
An overcoat resin solution of 00 cps (20° C.) and 40% solid content was prepared.

When this resin solution was subjected to the same test as in Example 1, the blocking resistance was good, but the film properties and firing properties were poor.

Comparative Example 2 Copolymer solution 1 (10 parts) obtained using the same equipment, raw material composition, blending ratio, and reaction method as in Example 2, and 10 parts of Mermaid M-200 (Yi2 powder, Shikishima Starch Co., Ltd.) ,
5 parts of dioctyl adipate as a plasticizer, 0.5 parts of an antifoaming agent
part, oil-soluble dye 0.05 part, Tsurpets +1100 (
3.0 parts of solvent naphtha (manufactured by Esso) were added to prepare an overcoat resin solution having a viscosity of 1700 cps (20°C) and a solid content of 38%.

Subsequently, this resin solution was subjected to the same tests as in Example 1, and although there were no problems with the film physical properties and blocking resistance, the sinterability was poor.

(Hereinafter referred to as wood margin) Note) Regarding the evaluation method in Table 1 (1) Storage stability of overcoat resin solution: 1 at room temperature
The samples were left for a month and judged based on the presence or absence of precipitates or floating substances.

Items with sediment or suspended matter...Old...×Sediment,
No floating objects...0(2) Printing workability in screen printing Printing at a printing speed of 30 sheets per minute with a Nijilinda printing machine, and the bottom of the screen when printing 1000 sheets. This occurs between the paper and the transfer paper. Resin thread (
The amount of stringiness (referred to as stringiness), leveling properties on the pattern, and defoaming properties were tested.

No stringing occurred at all, and the antifoaming and leveling properties were good. 0. Stringing occurred, but the antifoaming and leveling properties were good.・・・・Δ Stringing occurs and the defoaming and leveling properties are poor.
...Self...X (3) Pro-king resistance: Tested by the method shown in Example 1.

Things that did not block at all...0
Items with slight reversal blocking ・・・・・・・・・O Items with about half of the pattern blocked Items with complete blocking and transfer paper could not be peeled off from each other ・・・・・・・・・×(4) Firing Characteristics: ■Pinholes: Each overcoat resin was printed on a flat pattern of 2cm x 3cm+, and the number of pinholes generated on the surface of the pattern when painted and fired as shown in Example 1 was counted.

Number of pinholes 0 to 10 ・・・・・・・・・0
Items with 11 to 30 pinholes...
Items with 0 pinholes of 31 to 70...
・Those with Δ pinholes of 71 to 150...
・・・×Things with 151 or more pinholes ・・・・・・
...XX■Color development and leveling: A test was conducted as shown in Example 1, and judgment was made visually.

Good coloring and leveling ・・・・・・・・・0
The coloring is good, but the leveling is a little poor.
.....DELTA. Poor coloring and shrinkage ---...× ■Overlap printing f&: The test was conducted as shown in Example 1, and only the overlapping areas were evaluated. .

Less peeling than pinholes and ceramic plates...
...O There will be a small amount of pinholes, but there will be no peeling compared to ceramic plates.
・・・・・・・・・Δ Items with more pinholes and more peeling than ceramic plates ・・・
・・・・・・× ■Gold firing; Example 1 using a commercially available kiln and gold paste for coloring the draft product.
Firing was performed as shown in Figure 2, and judgment was made based on the presence or absence of cloudiness and cracking on the surface of the gold pattern.

Items with no clouding and cracking...O Items with a small amount of clouding and cracking 0 ・Φe... △ Items with a large amount of clouding and cracking... ... × (C) Effect of the invention As described above, the overcoat resin composition for transfer paper according to the present invention has good storage stability, printing workability, and film physical properties, and particularly has excellent blocking resistance. Since it has excellent sinterability, it has all the major physical properties required of an overcoat resin for transfer paper, and overcomes the problems of the prior art as described above.

that's all Agent Patent Attorney Atsushi Yasufuji

Claims (1)

[Claims] (1) A copolymer (A ) 80 to 98% by weight and general formula or general formula (wherein, approximately is a saturated aliphatic group or unsaturated aliphatic group having 5 to 21 carbon atoms, & is hydrogen or a methylol group, & is a methylene group or an ethylene group An overcoat resin composition for transfer paper containing 1 to 20% by weight of a fine powder of at least one fatty acid amide (B) represented by the following.