JPH0280411A - Overcoat resin for transfer paper - Google Patents

Abstract

PURPOSE:To obtain a resin with a good balance among printing processability, coating characteristics and baking properties by polymerizing a mixture consisting of an alkyl methacrylate, a styrenic monomer and, if necessary, a copolymerizable monoethylenic vinyl monomer. CONSTITUTION:An overcoat resin for a transfer paper with a glass transition temp. of 10-90 deg.C is obtd. by polymerizing a monomer mixture consisting of 50-98wt.% 1-18C alkyl methacrylate (A), 1-50wt.% one or more monomer (B) selected from styrene and alpha-methylstyrene, and a monoethylenic vinyl monomer (C) copolymerizable with both components A and B [e.g. methyl acrylate, hydroxyethyl (meth)acrylate, vinyl propionate etc.]. It is possible to prepare an overprinting lacquer with a good balance among printing processability, coating characteristics and baking properties from this resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an overcoat resin for transfer paper for coloring ceramics, glass, enamel, metals, etc.

[Conventional technology]

In the ceramic industry, there are patterns on ceramics, glass, enamel, metal, etc.
One method is to use transfer paper to color the designs. Binding method 1 using this transfer paper is as follows: (1) Apply 1laNi to the entire surface of the base paper, print a pattern on it with decorative printing ink, and after drying, peel off the base paper and place it in a predetermined position. (2) Apply a water-soluble glue to the entire surface of the water-absorbing mount. Then, a pattern is printed on it using decorative printing ink, and then a cellulose resin or acrylic resin is overcoated by screen printing, and then the resulting transfer paper is immersed in water. Wet transfer involves dissolving the glue on the mount paper, separating the overcoat of the supporting layer that is integrated with the pattern layer, and slidingly transferring it to a predetermined position on the transfer target such as ceramics, drying, and then firing. There is a method known as single-sheet painting.Currently, the latter single-sheet painting method is used because of its high quality and productivity.

The overcoat resin for decoration is an overprinting lacquer (hereinafter referred to as OPL) that is coated on the pattern by screen printing to protect the pattern printed with the printing ink for decoration as a transfer paper and to serve as a support during slide transfer. The following properties are required for this lacquer: (1) Printing workability l) No long threads and no scattering on the mount or around the printing press cylinder 2) No foaming 3) Good coatability on the pattern (・4) Does not damage the pattern layer 5) Good drying balance (no increase in viscosity due to drying during printing (good drying after printing <opL layer) (2) Physical properties of the coating 1) The coating should have a good balance of strength and elongation (it should be strong and not stretch properly 2) It should not deteriorate over time 3) The transfer paper should not be damaged during packaging and storage. Good bronking resistance (3) Firing performance l) No sludge remains after firing 2) No creasing or pinholes in designs due to rapid firing (3) Beautiful and glossy color development of pigments, gold, etc. The above-mentioned trianium is essential as an OPL.

Cellulose resins conventionally used as components of OPL have the drawbacks of poor coating film properties and deterioration over time, so acrylic resins have been used in recent years. However, it is difficult to fully satisfy the three necessary OPL elements at the same time, and in particular, the required performances of printability and coating film properties are contradictory.

In other words, increasing the resin content improves the physical properties of the coating, but
Workability such as stringiness and scattering deteriorates, and lowering the degree of polymerization improves stringiness and scattering, but reduces coating film strength.

[Problem to be solved by the invention]

The present invention aims to provide a well-balanced resin for OPL that can simultaneously satisfy the triad properties of printing workability, coating film properties, and sinterability.

[Means for resolving the sewing order]

The present invention comprises [A] 50-98 methacrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms] (i%, 1 to 50% by weight of at least one monomer selected from LBI styrene and α-methylstyrene; Obtained by polymerizing a monomer mixture consisting of 0 to 3 ON!% of a monoethylenically vinyl monomer that can be combined with (C) and (A:], (B:) g.Glass transition temperature (
It relates to an overcoat resin for transfer paper at a temperature of 10°C to 90°C (hereinafter abbreviated as T/).

The monomer [A) used in the resin of the present invention forms the backbone that gives coating film properties to OPL, and specific examples of the monomer [A] include methyl methacrylate-4, ethyl methacrylate, n Methacrylic acid alkyl esters such as -butyl methacrylate, quantity-butyl methacrylate, 1-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-propyl methacrylate, and l-propyl methacrylate can be mentioned. These can be used alone or in combination of two or more. The content of monomer (A) is 50 to 983 [ii
%, and if the content is less than 50M1k%, the strength and elongation of the coating film may be out of balance.

By copolymerizing the monomer CB"l used in the resin of the present invention with (A), it is possible to form a thread by screen printing (
, the firing properties are improved. As the monomer [B], styrene,
Examples include aromatic vinyl compounds such as α-methylstyrene. The content of monomer [B] is preferably 1 to 503 (i%); if the content is less than 1% by weight, it will not be effective in improving stringiness, and if it exceeds 50'N content, it is recommended to There is a risk that the strength will be insufficient.

The monomer [C] used in the resin of the present invention is [A),
It is a monoethylenic vinyl monomer that can be combined with component (B), and is 0 to 30i to suit the μ-philicity of OPL.
:l:% can be used in appropriate combination. Specific examples of the monomer (C) include methyl acrylate, ethyl acrylate, n-7' lobyl acrylate, ■-globyl acrylate, n-bunal acrylate, 1-butyl acrylate, and 2-ethylhexyl acrylate. Acrylic acid alkyl esters of 1 to 18; hydroxyl group-containing vinyl monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; (meth)acrylic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, etc. α,β-ethylenically unsaturated compounds; examples include lower saturated fatty acid novinyl esters having 1 to 8 carbon atoms such as vinyl propionate, vinyl acetate, and vinyl butyrate.

The resin of the present invention is a copolymer obtained by combining (A), CB:l, and (C) monomer mixture, and the TP of this copolymer is 10°C to 90°C, preferably 20°C. ℃～80℃
It is. If the Ti temperature is lower than 10°C, the coating will become sticky, which is undesirable.On the other hand, if the Ti temperature is higher than 90°C,
This is not preferable because the flexibility of the coating film becomes poor and the balance between strength and elongation is lost.

(A), [B]t [C] As for the monomer mixture, any of the known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. When printing patterns with printing ink, it is used as an organic bath solution, so
Preferably, the bath solution 1 method is used.

The printing method is usually screen printing, so the viscosity is 600 to 2000 cps (25℃), which is suitable for screen printing.
), with solid content in the majority range of 35 to 45%. Since the drying speed of the solvent is moderately slow during printing (and the drying speed is moderately slow after printing, and a balance is required), solvents with relatively low boiling points such as petroleum naphtha-based, higher alcohol-based, cellosolve-based and their esters are recommended. Bath additives are used alone or in combination, taking into consideration the viscosity stability of the opaque compound during printing, but the use of polar solvents that corrode the image on the transfer paper must be avoided as much as possible. .

In order to balance the strength and elongation of the coating film, the above-mentioned copolymer may be used with the addition of 0 to 5% plasticizer depending on the Ti content. For plasticizer binding, phthalate ester, adipate ester, trimectate ester, fatty acid ester, phosphate ester, citric acid ester, etc. are effective.

In particular, from the viewpoint of the balance between strength and elongation of the coating film, strong blocking properties, and sinterability, -a large amount (wherein RI t R1 is an aliphatic group having 1 to 12 carbon atoms, an alkyl group, a cyclohexyl group, Phthalate esters represented by (representing a benzyl group) are commonly used.

Also, auxiliary agents such as antifoaming agents, leveling agents, slipping agents, and small amounts of oil bath dyes can be used to color differentiate the printed OPL.

Hereinafter, the content of the present invention will be explained in detail using Examples 1
°ru

Example 1 In a four-way flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas blowing tube, Tsurupets #1 was placed.
00 (petroleum naphtha manufactured by Esso) 200i1CJi parts, methacrylic acid/l/methyl acid 501 parts, methacrylic acid n
-Butyl 140:! A 100.2 ml 1 t part of 1 rim and 1 ft was placed in a nitrogen atmosphere, and the temperature was raised to 90°C in 1 hour. Further, while maintaining the temperature at 90°C, 1.6 parts by weight of benzoyl peroxide was added in portions. The reaction was continued for 8 hours. After the reaction is complete, add 100i of Tsurpets #100.
A 1U'lL portion was added to obtain a resin solution with a solid content of 40% and a Ti content of 41°C. This resin bath liquid is 100%! Part i contains dioctyl fuculate 4N lid part, antifoaming agent 0. 2 parts by weight, 6 parts of Solperan #100 for viscosity adjustment, 0.21 parts of oil bath dye to be able to determine OPL, and viscosity 1000.
cps (25°C), 40% solids opL was prepared.

When this OPL was printed on a screen printer at a speed of 2,500 sheets per hour, there were no strings or scattering (no foaming, no foaming,
Printability on the pattern was also good. When the transfer paper thus obtained was wet-transferred onto a piece of ceramic to be transferred, the physical properties and adhesion properties of the coating film were good. This transferred ceramic is fired at a temperature of 8
As a result of firing at 00°C, the firing properties were good, and there were no pinholes or wrinkles in the design (and a beautifully colored product was obtained).

Example 2 Using the apparatus of Example 1, Nlupesso #100 was heated to 20.
iJi part, 100 parts by weight of n-butyl methacrylate, 100 parts by weight of styrene, 0.21111 parts of benzoyl peroxide
The mixture was heated to 90° C. in a nitrogen atmosphere for 1 hour, and reacted for 9 hours while adding benzoyl peroxide JMLfIk portion in portions. After the reaction is completed, Tsurpets#
100'& 3201 parts added, solid content 37%, T155
°C tree & solution was obtained. To 100 parts by weight of this resin solution,
Adding 5ffii parts of dioctyl fucurate, 0.2 parts by weight of an antifoaming agent, and 0.2 parts by weight of an oil bath dye, the viscosity was 700 c.
ps (25° C.) and OPL with a solid content of 39% was obtained. This O
As a result of conducting the test in the same manner as in Example 1 using PL,
Printing workability and sinterability were good, but the balance between tensile strength and elongation of the coating film was somewhat unsatisfactory.

Example 3 Using the apparatus of Example 1, 100! Amount of Solben#
A flask was charged with 180 Nf of ethyl methacrylate, heated to 90°C for 1 hour, and 180 Nf of ethyl methacrylate was added in a nitrogen atmosphere.
it W'A, styrene 2032! : MfW and azobisin butyronitrile 0.41 was placed under the surface c=-
The mixture was added dropwise over a period of 4 hours, and the reaction was allowed to proceed for 4 hours without discarding 1 liter of azopisisonthyronitrile in portions. After the reaction, 200M parts of Nrubesso #100 and 40]L parts of diacetone alcohol were added to reduce the solid content to 3.
A 7%, T770°C 6fJJ'# solution was obtained. To 100 parts of this resin solution were added 91 parts of didecyl phthalate, 0.2 parts by weight of an antifoaming agent, and 0.15 parts of oil-soluble dye to obtain an OPL with a viscosity of 1000 cps (25°C) and a solid content of 42%. Obtained. Using this OPL, tests were conducted in the same manner as in Example 1, and as a result, the printing workability, physical properties of the ζ film, and hardening properties were good.

Example 4 Using the apparatus of Example 1, 14 Sorpene #100
0JiEii parts, 1401 parts of ethyl methacrylate,
50 parts by weight of methyl methacrylate, 10 parts by weight of styrene, and a portion of benzoyl peroxide and IN were charged into a flask, and the temperature was raised to 90°C in 1 hour in a nitrogen atmosphere, and then 1.6 parts of benzoyl peroxide was added. The mixture was reacted for 8 hours while being added in portions. After the reaction is complete, add Solben #10o
220 parts and 4ONi of isobutyl alcohol
A resin solution having a solid content of 33% and a temperature of 778° C. was obtained. Add 100 liters of dibutyl chloride to this resin solution.
Parts by weight, 0.4 parts by weight of antifoaming agent, and 0.2 parts by weight of oil-soluble dye were added to give a viscosity of 1200 cps (25°C) and solid content of 3.
A 9% OPL was prepared.

Using this OPL, tests were carried out in the same manner as in Example 1, and as a result, the printing workability, physical properties of the coating film, and sinterability were good.

Comparative Example 1 Using the apparatus of Example 1, 25% of Solben #100 was used.
0! ji part, 60 parts by weight of methyl methacrylate, 140 parts by weight of methyl methacrylate! fit part and benzoyl peroxide 0.05! is was charged into a flask, the temperature was raised to 90° C. over 1 hour in a nitrogen atmosphere, and the mixture was reacted for 8 hours while adding 2 parts by weight of benzoyl peroxide in portions. After the reaction was completed, 76N parts of Nluben #100 was added to obtain a resin solution with a solid content of 32% and a temperature of 741°C. To 100 ml of this resin solution, 4 ml of dioctyl phthalate,
Added 0.2 parts by weight of antifoaming agent and 0.2 parts by weight of oil-soluble dye, resulting in a viscosity of 1100 cps (25°C) and a solid content of 40%.
The OPL of was manufactured by rA. Using this OPL, Example 1
As a result of conducting a test in the same manner as above, the physical properties of the eardrum were good, but stringiness occurred and continuous printing of 1000 sheets or more was not possible.

Comparative Example 2 Using the apparatus of Example 1, 180
3 [i part, methacrylic awakening #140 sword tit also μ,
Methyl methacrylate 6ON parts and benzoyl peroxide 0.1. 1 part was placed in a flask, heated to 90°C in a nitrogen atmosphere for 1 hour, and reacted for 8 hours while adding 1.8 M parts of benzoyl peroxide in portions. After completion of the reaction, add 180 TILi parts of Tsurpets #100,
Add 40x parts of diacetone alcohol to 33% solids
, T/78°C resin solution was obtained. 100ml of this resin solution
To part Jm, 1 part of dioctyl phthalate and 0.0 part of antifoaming agent were added.
41 parts by weight and 0.2M part by oil-soluble dye were added to make the viscosity 120.
OPL was prepared at 0 cps (25° C.) and 39% solids. Using this OPL, tests were carried out in the same manner as in Example 1. As a result, the physical properties and firing properties of the coating film were good, but stringiness occurred and continuous printing of 1000 sheets or more was not possible.

The evaluation results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1.

1 ◎ ◎ △○ ○ ○ Very good Good Slightly poor Poor [Effects of the invention] Using the uninvented overcoat resin for transfer paper creates an overprinting lacquer with a good balance of printing workability, physical properties of the coating film, and firing properties. can be made.

Claims (1)

[Scope of Claims] [A] 50 to 98% by weight of an alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms, [B] 1 to 50% by weight of at least one monomer selected from styrene and α-methylstyrene. % by weight, obtained by polymerizing a monomer mixture consisting of 0 to 30% by weight of monoethylenic vinyl monomer copolymerizable with [C] and [A], [B] components, glass transition temperature 10 Overcoat resin for transfer paper at temperatures between ℃ and 90℃.