JPH01171978A - Thixotropic ink binder resin composition for transfer sheet - Google Patents

Abstract

PURPOSE:To provide fluidity when print is made, to provide good elongation on a screen plate and to enable print of a delicate pattern, by mixing a specific thixotropic agent with a binder resin mainly composed of acrylic resin, thereby providing thixotropy. CONSTITUTION:0-80wt.% of plasticizer and 5-60wt.% of thixotropic agent are mixed with 100wt.% of thermoplastic acryl polymer having glass transition temperature higher than -10 deg.C. Any wax providing may be employed as a thixotropic agent, and preferably castor oil series wax added with hydrogen, castor oil amide series wax doped with hydrogen and the like are employed. Preferably, single or two or more types of waxes are mixed with an acryl (co)polymer through hot blend, high speed dispersion machine, three rolles and the like. Thixotropy is insufficient in 5wt.% or lower of thixotropic agent while film strength lowers in 60wt.% or higher of thixotropic agent and the like thus produced solidifies to cause defective print.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is for forming patterns by printing on transfer paper used for painting on ceramics, glass, enamel, tiles, and other ceramics (hereinafter referred to as ceramics, etc.). The present invention relates to a resin composition for an ink binder.

[Prior Art] Conventionally, a painting method using a transfer paper for painting using a frame silk screen printing method or an offset printing method has been widely used for decorating ceramics and the like. This transfer painting method includes multiple paper painting methods and single paper painting methods, but recently the single paper painting method has been widely used due to its quality and productivity.

The method involves first placing starch, dextrin,
Synthetic glue, (single) oligosaccharides, etc. are applied uniformly over the entire surface and dried to form a glue layer. On top of this, letters, pictures, figures, and other designs are printed using ink containing cedar wood for painting. Form a pattern layer. Next, an overcoat resin is applied to the entire surface of this pattern layer and dried to obtain a transfer paper. The transfer paper created in this way is immersed in water or hot water to dissolve the glue layer on the base paper, and the pattern layer protected by the overcoat with some of the glue adhered is slide-transferred to the transfer target. However, when it is dried and fired, the glue, ink binder, and one overcoat resin burn, decompose, and scatter, leaving only the pigment fixed on the transfer object.

Examples of resins for painting include acrylic resins and cellulose resins, but in recent years acrylic resins have been mainly used for both ink binder resins and overcoat resins.

Acrylic resin is rich in four types of raw material monomers and can be arbitrarily copolymerized, so resins with a wide range of glass transition temperatures and molecular weights can be freely obtained, making it suitable for printing and blocking resistance required for painting methods. This is because it is possible to obtain an excellent transfer paper that is well-balanced in terms of properties, film properties, painting workability, firing properties, etc.

[Problems to be solved by the invention] The ink that forms the pattern layer of transfer paper generally needs to have increased fluidity in order to achieve maximum printability, but this causes the ink printed on the transfer paper to spread. As a result, the mesh of the pattern was crushed, creating tiers in solid printing, making it impossible to print fine lines and dots, and making it impossible to print delicate patterns. In addition, in ordinary printing, multi-color printing is carried out in multi-color printing in which the three primary colors and black, as well as paints from light and dark to intermediate colors, are classified in detail. was. Therefore, it has been desired to develop a species-modified ink with excellent printability.

[Means for solving the problems, their actions, and effects of the invention]

Since the performance of ink other than color is controlled by the ink binder, the present inventors conducted research to develop an ink binder resin suitable for printing thin lines and dots, especially halftone printing, and found that acrylic resin By kneading a specific species modifier into a binder resin mainly consisting of
It has fluidity during printing, spreads well on the screen plate, does not clog, and has good pigment dispersibility, and does not flow into the printed pattern at all, allowing for fine patterns such as fine lines and dots. We have succeeded in developing a resin composition for ink binder that can be used for printing.

In the present invention, 100 parts by weight of a thermoplastic acrylic (co)polymer having a glass transition temperature of 110°C or higher, 0 to 80 parts by weight of a plasticizer and 5 to 50 parts by weight of a species modifier are added. The present invention provides a resin composition for a seed-modified ink binder for transfer paper, which is characterized by a resin composition that can be used as a seed-modified ink binder for transfer paper.

First, a (meth)acrylic acid alkyl ester in which the alkyl group has 1 to 1 carbon atoms and a monovinyl monomer copolymerizable therewith are polymerized or copolymerized into the thermoplastic acrylic (co)polymer used in the present invention. can be obtained. Specific examples of (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 18 carbon atoms include stile, methyl (meth)acrynote, ethyl (meth)acrylate%n-butyl (meth)acrylate, inbutyl (meth)acrylate, t-Butyl (meth)acrylate, 7chlorohexyl (meth)acrylic V-), 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)
Examples include acrylate. Specific examples of copolymerizable monovinyl monomers include α, β-monoethylenically unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, itaconic acid, and crotonic acid, 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl(meth)
Hydroquinoalkyl (meth)acrylates such as acrylates, styrene, aromatic monovinyl monomers such as α-methylsulfonate, vinyl acetate, vinyl propionate,
Examples include (meth)acrylonitrile.

In the production of resins, 1 to 20% by weight of cellulose resins such as nitrocellulose, cellulose acetate phthalate, and ethyl cellulose, which have been conventionally used and have good firing properties and blocking resistance, are blended or in the coexistence of cellulose resins. The above monomers can be polymerized.

The glass transition temperature of the (co)polymer in the resin composition of the present invention must be -10°C or higher, but the blocking resistance becomes poor below 0-10°C. On the other hand, if the temperature exceeds 10° C., the flexibility and elongation of the film will decrease, resulting in poor adhesion properties, and it will therefore be necessary to use a plasticizer if necessary. R+n of the plasticizer represents hydrogen, an alkyl group having 8 or more carbon atoms, a cyclohexyl group, an O-, m-, p-substituted cucurohex7AI group, a benzyl group, an o+, m+, p-substituted penzyl group, R,
H Alkyl group having 8 or more carbon atoms, cyclohexyl group, O-
, m-, p-substituted 7 chlorohexyl group, benzyl group, o-
Examples include phthalic acid esters, adipic acid alkyl esters, citric acid alkyl esters, trimellitic acid esters, etc. represented by +m-, p-substituted pendyl groups, etc.

0 parts by weight of acrylic (co)polymer as plasticizer
~80 parts by weight is required. If the plasticizer exceeds 80 parts by weight, the coating film will stretch too much, causing the pattern to collapse, drying to be poor, and blocking resistance to be poor. The amount of plasticizer is particularly preferably 5 to 25 parts by weight.

As the lateral change agent for the thixotropic ink binder resin composition used in the present invention, any wax that imparts thixotropy can be used, but in particular, hydrogenated castor oil wax and hydrogenated castor oil amide wax can be used. , hydrogenated castor oil clay-based wax, higher fatty acid nitrogen derivative wax, fatty acid amide-based wax, long-chain fatty acid ester-based wax, etc. are suitable, and these may be used alone or in combination with ta2! m
In the above combination, it is preferable to knead 5 to 60 parts by weight with respect to 100 parts by weight of the acrylic (co)polymer using a hot blend or a high-speed disperser, three rolls, or the like. If the amount of the transverse change agent is less than 5 parts by weight, thixotropy is insufficient, and if it is more than 60 parts by weight, the strength of the coating decreases and the resulting ink hardens, resulting in poor printing. Particularly preferred is 5 to 30 parts by weight.

The acrylic (co)polymer of the present invention can be manufactured according to known polymerization methods such as liquid polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, but since it is used as a solution during printing, Solution polymerization is preferred.

As the solvent is usually applied by screen printing or planographic printing, it is preferable to use a solvent with a relatively high point in consideration of evaporation rate, dissolving power, odor, etc., such as solvent naphtha-based solvents, lactate-based solvents, and cellosolve-based solvents. , tetrahydronaphthalene, etc. are used.

As an ink binder resin composition for lateral modification transfer, it is suitable for frames, viscosity stability during printing, sharpness of paint, pigment dispersibility, good overcoating and halftone printing, no foaming, good drying properties after printing, and sintering properties. Good quality is required. In order to satisfy these requirements, auxiliary agents such as (co)polymers, transverse modifiers, leveling agents, and pigment dispersants can be used.

The viscosity of the paint during painting is 500 to 2000 cps.

The solid content is preferably 30 to 60%, and the (co)polymer content needs to be at least 2-0 weight ratio.

If the content is less than 20 parts by weight, defects may occur in firing properties,
There is a risk of printing defects and the strength and elongation of the coating becoming unbalanced.

The method for creating and painting transfer paper sheets using the ink binder of the present invention is to first uniformly apply a water-soluble glue onto the base paper, and then apply a cedar material for painting coated with the ink binder of the present invention. This creates patterns and designs. Next, a regular overcoat is applied over the entire surface of this pattern and dried to create a transfer paper for decoration.

Immerse the above-mentioned transfer paper in water or hot water and apply it from the mount (161)
jd, the ink layer, and the overcoat layer are separated as one body, slide transfer is performed on a predetermined position of the transfer target, air and water between the transfer target and the film layer are removed, and after drying, baking is performed at a predetermined temperature. By doing so, a product 5; in which a desired pattern is painted on ceramics or the like is obtained.

〔Example〕

Examples are shown below, but the present invention is not limited thereto. In the examples, parts represent parts by weight, and % represents dead weight %.

Example 1 80 parts of tetrahydronaphthalene was added to a 7' (4 tube) flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas blower, and the temperature was raised to 90°C.

After adding 20 parts of methyl methacrylate, 80 parts of n-butyl methacrylate, and 2 parts of benzoyl peroxide over a period of 3 hours while flowing a small amount of nitrogen gas at an internal temperature of 90°C,
Dissolve 0.1 part of benzoyl peroxide in 3 parts of tetrahydronaphthalene every hour, add 4 times, hold for another 2 hours, and after completion of polymerization, add 18 parts of tetrahodronaphthalene and 40 parts of butyl lactate.
A resin solution with a solid content of 40% was obtained.

For 100 parts of this resin solution, 8 parts of dioctyl 7-talate
part, antifoaming agent 1) 4 parts, synthetic wax A8mu T-75IP
5 parts (manufactured by Ito Oil Co., Ltd.) and 10 parts of tetrahydronaphthalene for adjustment were added, finely dispersed with a high-speed disperser, and crushed with three rolls after setting to obtain a thixotropic resin solution with a solid content of 43%.

When we screen-printed a printing ink made by kneading 70 parts of this resin solution and 100 parts of pigment on a 250-mesh nylon screen using a cylinder printer, there was no clogging even when printing SOO sheets, and halftone dots were reproduced. The properties were also good. Slide transfer of this onto white ceramic using a wet method,
After drying, the pottery was fired at 800°C, resulting in a very beautifully painted Nenware pottery with no cracks, pinholes, or runs. The evaluation results are shown in Table-1.

Example 2 Using the same equipment as in Example 1, 8 parts of Norpetz φ150 (high boiling point naphtha made by Esso), 23 parts of methyl methacrylate, 77 parts of n-butyl methacrylate and benzoyl peroxide (2 parts of LO) were added, and the internal temperature The temperature was raised to 90°C. After heating, 6 parts of benzoyl peroxide αO was dissolved in 30 parts of Rubesso ◆ 150 to a diameter of 3° and added dropwise over a period of 3 hours. Furthermore, benzoyl peroxide Q was added dropwise every hour. , 2 parts dissolved in 3 parts of Norpetz ◆ 150 f was added three times, and after holding for 2 hours, 26 parts of Fulvetsusona 150 and 25 parts of Terpineol were added to obtain a resin solution with a solid content of 57%.

To 100 parts of this resin solution, 15 parts of dimethylcyclohexyl phthalate, 14 parts of an antifoaming agent, and 3 parts of diamond wax (hydrogenated and mustard oil wax manufactured by Shin Nihon Rikagaku Co., Ltd.) were added, and the same method as in Example 1 was carried out. As a result of making it into a paint, a thixotropic resin solution with a solid content of 48% was obtained.

When this resin solution was made into ink using the method described in the example and a printing test was carried out, as shown in Table 1, printability, halftone property,
The firing properties were good.

Example 3 Using the same equipment as in Example 1, tetrahydrofuran 80
Add 50% of the water and raise the temperature to 90℃. While flowing a small amount of nitrogen gas at an internal temperature of 90°C, 19.5 parts of methyl methacrylate, 80 parts of n-butyl methacrylate, 5 parts of α methacrylic acid, and 2 parts of benzoyl peroxide were added over a period of 3 hours.
Dissolve benzoyl peroxide (1 part of L in 3 parts of tetrahydronaphthalene, add 4 times, and hold for another 2 hours.) After adding and dissolving 4 parts of synthetic wax, 18 parts of dioctyl phthalate, 194 parts of antifoaming agent,
Swazolna 1800 (High boiling point naphtha made by Maruzen Oil) 42
As a result, a thixotropic resin solution with a solid content of 48% was obtained.

When this resin solution was formed into an ink using the method of Example 1 and subjected to a printing test, the printability, halftone dot quality, and sinterability were good as shown in Table 1.

Example 4 To 100 parts of the same resin solution as in Example 2, 15 parts of dimethyl cyclohetalytate, 4 parts of antifoaming agent Q, and 10 parts of diamond wax were added, and the mixture was treated in the same manner as in Example 1. When made into a paint, a thixotropic resin solution was obtained. This was made into an ink and printed, and as shown in Table 1, it showed good performance in printability, dotting and firing properties.

Example 5 To 100 parts of the same resin solution as in Example 2, 15 parts of dimethyl phthalate, 4 parts of antifoaming agent α, and 20 parts of diamond wax were added, and a coating was made in the same manner as in Example 1. A somewhat hard thixotropic resin solution was obtained.

When this was made into an ink and printed, as shown in Table 1, the printability, halftone dot quality, and firing performance were relatively good.

Example 6 A thixotropic resin solution was obtained in exactly the same manner as in Example 1 except that 20 parts of methyl methacrylate was replaced with 20 parts of butyl acrylate and 8 parts of octyl phthalate was not added. This was made into an ink in the same manner as in Example 1, and its performance was evaluated. As shown in Table 1, the printability, halftone dot quality, and firing performance were good, and the blocking property was also good.

Comparative Example 1 To 100 parts of the same resin solution as in Example 2, 15 parts of dimethylcyclohexyl phthalate, 0.4 part of antifoaming agent, and 1 part of diamond wax were added, and a coating was made in the same manner as in Example 1. However, a transversely modified resin solution could not be obtained.
When this was converted into ink and printed, halftone dot printing was insufficient.

Comparative Example 2 To 100 parts of the same resin solution as in Example 2, 15 parts of dimethylcyclohexyl phthalate, 14 parts of antifoaming agent, and 30 parts of diamond wax were added, and a coating was prepared in the same manner as in Example 1. However, it hardened and the printing was poor.

Comparison row 3 20 parts of methyl methacrylate of Example 1 (!: Aku')
20 parts of the fluorine was replaced with 5 parts of butyl methacrylate and 5 parts of butyl acrylate, and 8 parts of octyl phthalate was added.
A thixotropic resin solution was obtained in exactly the same manner except that no part was added. This was made into ink in the same manner as in Example 1, and its performance was evaluated. As shown in Table 2, printability,
The halftone dot properties and firing properties were good, but the blocking resistance was poor.

Table-1 Example Table-2 Comparative Example Note) Based on the mixing ratio &! It shows the weight ratio of fat to solid content jOD weight parts.

The performance evaluation method and criteria for the actual M f4J and the comparative example were as follows.

(A) Those that solidify when left for more than one day after being made into a laterally modified paint, and become fluid when shearing force is applied, are marked with a circle. Those showing no fluidity were marked with an X, those with no fluidity were marked with an X, and those between O and × were marked with a Δ.

CB) Pigment dispersion When the pigment is kneaded and made into ink, if it is smooth, mark it as ○.
Those with no smoothness or fluidity were marked with an X. Moreover, the value between ○ and × was marked as Δ.

(03rd OPI, 250 mesh stripe pattern was printed, and after drying, a regular overcoat was printed. When held vertically, the one with a clear outline was marked with an ○, and the one with a dripping mark was marked with an X. Also, the mark between ○ and X was designated as Δ.

(D) Properties of on-plate ink Print 500 sheets using a cylinder printing machine with a nylon 250-mesh screen at a printing speed of 55 sheets per minute. I marked it with an X. Also, the mark between O and × was marked Δ.

(to)) When printing 500 sheets under the printing conditions of halftone dot quality φ), those with good halftone dot reproducibility and firm edges are marked with ○, and those where the halftone dot pattern is faded or The crushed ones are marked with an X. Moreover, the value between ○ and × was marked as Δ.

(Use) When 500 sheets were printed under the printing conditions of clogging property (D), those with good screen clearance and no clogging were marked with an X mark. Also O
The middle point between and × was marked as Δ.

(G) Printed with a 250-mesh screen made of warp-resistant nylon and dried in a drying oven at a temperature of 40°C. When 500 sheets are piled up in a bar, those that do not form a tank are marked O, and those that do not form a tack,
The sticky material was marked with an X. Moreover, the value between ○ and × was marked as Δ.

(Shin) Firing property: The transfer is carried out using a wet method on white earthenware, and after drying, it is fired at 800℃. If the ceramic is beautifully painted without any defects, it is marked with an ○, and there are no wrinkles, pinholes, runs, etc. Those with defects were marked with an X, and those between ○ and × were marked with a Δ.

(1) Glass transition temperature of pace resin After completely drying the resin solution obtained by polymerizing it by vacuum drying, cut it into small pieces and use a differential calorimeter to measure the temperature when the temperature was raised at a rate of 15°C/min. The intersection point between the tangent of the rising portion of the endothermic curve and the baseline was determined, and this was taken as the glass transition temperature.

Claims (2)

[Claims] (1) Transfer paper characterized by combining 100 parts by weight of a thermoplastic acrylic (co)polymer with a glass transition temperature of -10°C or higher, 0 to 80 parts by weight of a plasticizer, and 5 to 60 parts by weight of a thixotropic agent. A resin composition for a thixotropic ink binder. (2) As a thixotropic agent, hydrogenated castor oil wax, hydrogenated castor oil clay wax, hydrogenated castor oil amide wax, higher fatty acid nitrogen derivative wax, fatty acid amide wax, long chain fatty acid ester polymer wax Claims characterized in that at least one of the following is used (
The resin composition for a thixotropic ink binder for transfer paper as described in item 1).