JPH09302289A - Antifogging ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifogging ink composition not suffering the dew condensation on the surface of the applied ink even when the composition is used in a high-temperature and high-humidity place or at the boundary between places having greatly different temperatures by using a specified polymer. SOLUTION: This composition contains a polymer comprising polyorganosiloxane units. This polymer can be synthesized by radical- copolymerizing at least one ethylenically unsaturated monomer in the presence of a polyorganosiloxane compound having at least one mercapto group and constituting a polyorganosiloxane unit. The exemplified polyorganosiloxane compound has the main chain of a polysilsesquioxane or a polydialklsiloxane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an anti-fogging ink composition containing a polymer having a polyorganosiloxane unit.

[0002]

2. Description of the Related Art Vegetables, processed meat foods of bacon and ham,
Packaging materials such as, product name, manufacturer, distributor, date of manufacture,
Shelf life, price, barcode, etc. are printed, and various inks are used. However, when the characters printed with these currently used inks are used in hot and humid places or at boundaries with large temperature differences, dew condensation occurs on the surface, which makes the printed characters difficult to read. There is such a problem. In particular, a bar code consisting of a large number of bars that encodes a lot of information about products must be read by a photoelectric element from outside the packaging container, and if condensation occurs on the bar code, the bar code However, there is a problem that the contrast for surely reading the image is lowered, but there has been no attempt to give the ink itself antifogging property against such a problem.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and prevents dew formation on the ink surface even when used in a hot and humid place or on a boundary surface with a large temperature difference. It is to provide a cloudy ink composition.

[0004]

Accordingly, the present inventors have
As a result of intensive studies to solve the above problems, on the packaging materials such as fruits and vegetables, processed meat foods of bacon and ham, etc., product name, manufacturer, distributor, manufacturing date, expiration date, price, barcode In the ink used to print etc.,
By blending a polymer with a polyorganosiloxane unit, even when used in hot and humid places or on boundaries with large temperature differences, condensation does not occur on the ink surface, making it possible to read printed characters. The inventors have found what can be done and have reached the present invention. That is, the present invention provides 1) an antifogging ink composition characterized by containing a polymer having a polyorganosiloxane unit, 2)
The antifogging ink composition according to 1 above, wherein the printed film surface has a silicon concentration of 6% or more, and 3) the antifogging ink composition according to 1 above, wherein the polyorganosiloxane is polysilsesquioxane. 4) The antifogging ink composition as described in 1 above, wherein the polyorganosiloxane is a polydialkylsiloxane.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The antifogging ink composition of the present invention will be described in detail below. The polymer having a polyorganosiloxane unit used in the antifogging ink composition of the present invention contains one or more kinds of ethylenically unsaturated monomers and one or more mercapto groups that induce the polyorganosiloxane unit. It can be synthesized by radical copolymerization in the presence of a polyorganosiloxane compound.

The polyorganosiloxane-containing polymer used in the antifogging ink composition of the present invention is considered to have the following structure. In other words, when one mercapto group is present at the molecular end of the polyorganosiloxane, the polyorganosiloxane unit becomes a block polymer added to one end of the ethylenically unsaturated monomer polymer, and the mercapto group becomes the polyorganosiloxane. In the case where there is one mercapto group, a graft copolymer is obtained. Furthermore, when a large number of mercapto groups are present in one molecule, a comb-shaped copolymer is obtained.

As the ethylenically unsaturated monomer used in the synthesis of the polyorganosiloxane-containing polymer used in the antifogging ink composition of the present invention, generally any one having radical polymerization ability can be used. For example, (meth) Acrylic esters [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid etc.], styrenes [eg styrene, methylstyrene etc.], aliphatic vinyl esters [eg vinyl acetate, vinyl propionate etc.], vinyl chloride, N, N-diethylacrylamide, N- (meth) acrylmorpholine , N-vinylpyrrolidone, N-vinylacetamide, N-vinyl N-methylacetate Amides, vinyl methyl ether, polyethylene glycol monomethacrylate,
Methoxy polyethylene glycol monomethacrylate,
Polypropylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, (meth) acrylamide, N, N-dimethyl Acrylamide, N-isopropylacrylamide, N-vinylformamide, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, maleic acid, maleic anhydride, vinyloxazoline, n-
Typical examples are (1,1-dimethyl-3-oxobutyl) (meth) acrylate and the like.

Among such ethylenically unsaturated hydrophilic monomers, (meth) acrylic acid esters [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic) Acid 2
-Ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid, etc.],
Styrenes [eg styrene, methylstyrene, etc.], N-
Vinylpyrrolidone, N- (meth) acrylmorpholine, polyethylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monomethacrylate,
Polyethylene glycol polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, (meth) acrylamide, N,
N-dimethylacrylamide, N-isopropylacrylamide, N-vinylformamide and the like are preferable.

Examples of the polyorganosiloxane compound containing at least one mercapto group in the present invention include polysilsesquioxane or polydialkylsiloxane having a main chain skeleton. When the main chain skeleton is polysilsesquioxane, the polysilsesquioxane containing at least one mercapto group has a mercapto group introduced into the side chain (a) and an end introduced into the main chain. (b) exists.

A polysilsesquioxane (a) having at least one mercapto group in its side chain has a structure represented by the following formula (A), where R ^m and R ⁿ are It is a side chain organic group, -OR ^q , -OR ^r , -OR ^s , and -OR ^t are terminal groups of the main chain, and p is a repeating unit.

Embedded image Mercapto group-containing polysilsesquioxane according to the present invention
In (a), the main chain end group (in formula (A), -OR ^q , -OR ^r ,
-OR ^s , -OR ^t ) is trialkylsilylated, and a trialkylsilyloxy group (-O-SiR ¹ R ² R ³ : R ¹ , R ² , R ³ is
Which are the same or different from each other).

Further, a side chain organic group (in the formula (A), -OR ^m ,
-OR ⁿ ) is present in at least one or more in the polysilsesquioxane containing a mercapto group, and these side chain organic groups are each selected from an alkyl group, an aralkyl group and a substituted or unsubstituted phenyl group. (A)
Containing a mercapto group represented by the following formula [I]
Both (c) and ((a) (c)) exist. In the mercaptan group-containing polysilsesquioxane, such a mercapto group [I] is usually 5.0 or less, and preferably 3.2 or less, on average per molecule among all side chain organic groups.
And more preferably 1.6 or less. —R ⁴ —SH ... [I] (In the formula [I], R ⁴ represents an alkyl group, an alkenyl group, an aralkyl group, or a substituted or unsubstituted phenyl group)

The number average molecular weight of the mercapto group-containing polysilsesquioxane according to the present invention is 500 to 5
2,000, preferably 1,000 to 10,000
0. The method for producing a polysilsesquioxane (a) having a mercapto group introduced into its side chain is described in Japanese Patent Application No.
It can be manufactured by the method described in 337571. A polysilsesquioxane (b) having at least one mercapto group at the end of its main chain is represented by the following formula
(B) has a structure represented by the formula, wherein R ^m and R ⁿ are side chain organic groups, and -OR ^u , -OR ^v , -OR ^w , and -OR ^y are main chains. It is a terminal group and p is a repeating unit.

[0013]

Embedded image The mercapto group-containing polysilsesquioxane according to the present invention, the main chain terminal groups (formula ^{(B), -OR u, -OR} v, -OR
^w , -OR ^y ) is a trialkylsilyl group or at least one of the main chain terminal groups is a trialkylsilyloxy group containing a mercapto group. The terminal trialkylsilyloxy group containing no mercapto group is
-O-SiR ¹ R ² R ³ (R ¹ , R ² and R ³ represent the same or different alkyl groups from each other), and the trialkylsilyloxy group containing a mercapto group is represented by -O-Si ( R ¹ R ² ) R ⁴ SH (R ⁴ represents an alkyl group, an aralkyl group, or a substituted or unsubstituted phenyl group). The mercapto group in the main chain terminal group is usually 4.0 or less on average per molecule in the polysilsesquioxane,
Preferably 3.2 or less, more preferably 1.6 or less. The number average molecular weight of the mercapto group-containing polysilsesquioxane according to the present invention is 500 to 500.
50,000, preferably 1,000 to 10,000
00.

The polysilsesquioxane (b) having a mercapto group introduced at its terminal can be produced by a method similar to that of the polysilsesquioxane (a) having a mercapto group introduced into its side chain. The amount of water for hydrolysis and condensation, the type of catalyst, the amount of catalyst, and the reaction temperature during the production are the same as those described in Japanese Patent Application No. 7-337571 by the applicant. In the case of producing a polysilsesquioxane (b) having a mercapto group introduced into a terminal, a point different from the polysilsesquioxane (a) having a mercapto group introduced into a side chain will be described. A trialkoxysilane and / or trichlorosilane that can be used in the production of a polysilsesquioxane (b) having a mercapto group introduced at the terminal are an alkyl group, an alkenyl group, an aralkyl group, a substituted or unsubstituted phenyl group. It is a trialkoxysilane and / or a trichlorosilane having ## STR4 ## and it is not necessary to use a trialkoxysilane and / or a trichlorosilane having a mercapto group. In addition, a polysilsesquioxane having a mercapto group introduced at the terminal
The silylating agents that can be used in the production of (b) are both those described in Japanese Patent Application No. 7-337571 by the applicant and silylating agents having a mercapto group, depending on the amount of mercaptan to be introduced. You can adjust each proportion. Examples of the silylating agent having a mercapto group include 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane, dimethylmercaptopropylmethoxysilane, dimethylmercaptopropylchlorosilane and the like.

When the main chain skeleton is a polydialkylsiloxane, the polydialkylsiloxane containing at least one mercapto group is a polydialkylsiloxane in which a mercapto group is introduced into the side chain (side chain type) or a polydialkylsiloxane. One with a mercapto group introduced at both ends (both ends), one with a mercapto group introduced at one end of polydialkylsiloxane (one end), and one having a mercapto group at both the side chain and both ends of polydialkylsiloxane Some (side chain both ends type). If you show a representative example,

Embedded image And the like. The number of mercapto groups in the mercapto group-containing polydialkylsiloxane is usually 4.0 or less, preferably 3.2 or less, and more preferably 1.6 or less on average per molecule in the polydialkylsiloxane. desirable. The number average molecular weight of the mercapto group-containing polydialkylsiloxane according to the present invention is 500 to 50,000, preferably 1,
000 to 10,000. The above mercapto group is 1
The amount of the polyorganosiloxane compound to be contained in an amount of 0.1 or more is usually selected in the range of 0.1 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer.

The polymer having a polyorganosiloxane unit according to the present invention can be synthesized according to the following procedure. That is, a polyorganosiloxane compound containing one or more mercapto groups in a predetermined ratio is blended with the above-mentioned ethylenically unsaturated monomer, and polymerization is carried out under the usual conditions in the presence of a radical polymerization initiator. The above-mentioned radical polymerization initiator can be generally used as long as it is used as a general radical polymerization reaction initiator,
For example, an azo-based polymerization initiator [eg 2,2′-azobis (isobutylnitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2-cyano-2-
Propylazo-formamide, dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-hydroxymethylpropionitrile), etc.], peroxide type polymerization initiator [eg isobutylperoxide] , 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxide, t-butyl cumyl peroxide, t-butyl hydroperoxide, etc.] and the like, and they can be used in combination. .

The above-mentioned polymerization reaction is usually carried out in the presence of an organic solvent. Examples of the organic solvent include hydrocarbons [eg, benzene, toluene, xylene, cyclohexane, etc.], esters [ethyl acetate, butyl acetate, amyl acetate, etc.], ketones [acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.], Ethers [tetrahydrofuran, 1,4-dioxane, etc.], alcohols [eg methanol, ethanol,
Isopropyl alcohol, butyl alcohol, 1, 2,
6-hexanetriol, glycerin, etc.], amides [eg, n, n-dimethylformamide, n-methylformamide, n, n-diethylformamide, n-methylacetamide, n, n-dimethylacetamide, n-methylpropionamide, etc. ], Pyrrolidones [eg 1-methyl-2-pyrrolidone, 2-pyrrolidone, ε-captralactam, etc.],
Glycols [eg ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol,
Polyethylene glycol, etc.], glycol ethers [2-methoxyethanol, 2-ethoxyethanol,
2- (methoxymethoxy) ethanol, 2-propoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, 1-
Methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, etc.] and the like. .

When it is used as an ink additive solution for an antifogging ink composition, the solvent used in the antifogging ink composition can be used as it is, so that it dissolves the pigment and resin described below. It is preferable to use a solvent that is excellent in volatility and does not remain in the ink after coating,
Alcohols, ketones and esters are preferred. The reaction temperature is not particularly limited as long as it is a temperature at which the radical polymerization reaction initiator is decomposed, and is usually preferably 50 to 180 ° C., and a method of gradually increasing from low temperature to high temperature may be employed. The reaction time is not particularly limited, but usually 1 to 24
Time is preferred. The amphiphilic polymer having a polyorganosiloxane unit thus obtained has a weight average molecular weight of 5,000 to 100,000, preferably 6,000 to 30,000.

Materials that can be used in the antifogging ink composition used in the present invention will be described below.
The antifogging ink of the present invention is prepared by blending the above-mentioned polymer having a polyorganosiloxane unit with a printing ink, and the printing ink used is usually a printing ink used for printing food packaging materials. Is used as is. Organic pigments or inorganic pigments are usually used as pigments for printing inks.
An example is one having a composition of 50% by weight and 0 to 8% by weight of additives. The pigment that can be used in the antifogging ink composition used in the present invention is selected from pigments that are permitted as food additives, and examples thereof include Food Red No. 2, Food Red No. 2 Aluminum Lake, Food Red No. 3. , Edible Red No. 3 Aluminum Lake, Edible Red No. 102, Edible Red No. 104
No. 6, food red No. 105, food red No. 106, food yellow 4
No. 4, food yellow No. 4 aluminum lake, food yellow No. 5,
Edible yellow No. 5 aluminum lake, edible green No. 3, edible green No. 3 aluminum lake, edible blue No. 2, edible blue No. 2 aluminum lake, iron oxide, iron chlorophyllin sodium, copper chlorophyll, copper chlorophyllin sodium, titanium oxide, norbi Examples include xin potassium, norbixin sodium and natural pigments. These pigments can be used alone or in combination of two or more. The resin component is a resin whose use is recognized as a food container or a packaging material, and examples thereof include maleic acid resin, petroleum resin, cured rosin, nitrocellulose, chlorinated rubber, acrylic resin, polyamide resin, chlorinated polypropylene, polyurethane. It can be selected from resins, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers and the like.

Other antifungal agents, antifoaming agents, viscosity modifiers, penetrants and the like may be added as required. The polymer having the polyorganosiloxane unit is blended in the range of 0.05% to 30% by weight of the total ink composition, preferably the range of 0.1% to 10% by weight of the total ink composition. When the amount of the polymer is too large, the color of the ink itself becomes light and the display effect is reduced. On the contrary, when the amount is too small, the anti-fogging effect is lost. The antifogging ink composition used in the present invention is prepared by crushing and dispersing with a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic monogenizer, pearl mill, wet jet mill or the like. Reached by. Using an ink in which a polymer having a polyorganosiloxane unit is blended in a predetermined amount, a method such as gravure printing or roll coating is used, and for example, polyethylene, polypropylene, polystyrene, pomimethyl methacrylate, polyethylene terephthalate, nylon, ethylene-vinyl acetate copolymer is used. When printed on a synthetic resin film such as a polymer or vinylon, the coating surface of the formed image or character has a high polyorganosiloxane concentration, that is, a silicon concentration due to the surface segregation property of the polyorganosiloxane itself. Due to its structure, polyorganosiloxane exhibits water resistance or water repellency, and as a result, when used in hot and humid places or at interfaces with large temperature differences, water droplets grow into large droplets even if dew condensation occurs on the ink surface. The water droplets will then fall off the surface.
Therefore, if the silicon concentration on the coating surface of the formed image or character is high, the antifogging property is enhanced, and the silicon concentration on the coating surface formed by the printed image or character in the present invention is 6% or more. It is preferably 10% or more. The concentration of silicon on the surface of the formed coating film can be measured by a commonly used surface analysis method and is not particularly limited. For example, X-ray photoelectron spectroscopy, Auger electron spectroscopy or secondary ion mass spectrometry. The law etc. can be mentioned. For evaluation of antifogging property, a sample in which images and characters were printed on a synthetic resin film was left in an atmosphere of 20% humidity and 5 ° C for 30 minutes, and then taken out in an atmosphere of 80% humidity and 30 ° C. After that, it can be performed by observing the state of dew condensation.

[0021]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of mercapto group-containing polysilsesquioxane In a 500 cc flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 9.98 g (50.87 mmol) of 3-mercaptopropyltrimethoxysilane, Methyltriethoxysilane 199.55 g (1119.13)
mmol), phenyltrimethoxysilane 5.95 g (3
0.00mmol) and pure water 64.87g (3600mmo)
l) was charged and the temperature of the solution was kept at 5 ° C. while stirring under a nitrogen stream. 10% hydrochloric acid aqueous solution 1 with stirring
2. After dropping 15g over 30 minutes, the solution temperature was adjusted to 10
C. for 1 hour. Next, the temperature of the solution was raised to 70 ° C. and the reaction was carried out for 3 hours. Then, 29.16 g of hexaethyldisiloxane (179.60 mmol) was added, and stirring was continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C., 13.47 g of a 5% methanol solution of potassium hydroxide was added, and the mixture was stirred at room temperature for 2 hours and left standing for 12 hours. The lower layer is extracted and after adding 150 g of butyl acetate, it is concentrated with stirring at 40 ° C. under a reduced pressure of 200 mmHg.
After distilling off 50 g of the liquid, 200 g of butyl acetate was further added at normal pressure, and the mixture was stirred for 1 hour. The resulting solution was filtered and then concentrated under reduced pressure to obtain 82.68.
g of a colorless transparent viscous liquid was obtained. The number average molecular weight of this product was 3,300 as measured by GPC. I
2560 cm from R spectrum and Raman spectrum
Absorption based on the mercapto group appeared near ^-1 . Let the obtained polymer be the polymer A.

Synthesis Example 2 Synthesis of Polysilsesquioxane-Containing Polymer In a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube, 12.33 g of methyl methacrylate (123.15 mmol), 12.33 g. 83 g of styrene (126.85 mmol), 47.74 g of Bremmer PME-400 (manufactured by NOF CORPORATION) (98.52 mmo)
l), 31.80 g of Polymer A was added, and the mixture was stirred under a nitrogen stream for 30 minutes. The solution thus prepared is called a mixed monomer. 23.6 in a 300 cc flask equipped with a thermometer, stirrer, nitrogen inlet tube and reflux condenser.
6 g of mixed monomer and 102.13 g of 3-methoxy-
3-Methyl-1-butanol was added, and the mixture was stirred under a nitrogen stream at room temperature for 30 minutes. 10 weight percent of dimethyl 2,2'-azobisisobutyrate 3-methoxy-3-methyl-1-
Add 8.7 g of butanol solution, raise the temperature with stirring under a nitrogen stream, keep at 80 ° C for 30 minutes, and then add 8 more.
1.03 g of mixed monomer was added over 3 hours. Again, 4.4 g of a 10% by weight dimethylacetic acid 3-methoxy-3-methyl-1-butanol solution in dimethyl 2,2'-azobisisobutyrate (4.4 g) was added, and the reaction was continued at 90 ° C for 3 hours. After cooling to room temperature, 207 g of a colorless transparent solution was obtained. Its number average molecular weight was 14,000. Polymer A
The absorption due to the mercapto group in the vicinity of 2560 cm ⁻¹ in the Raman spectrum due to the above disappeared. ¹ H-NMR
The ratio of methyl methacrylate, styrene, and Blemmer PME-400 measured was 1: 1: 0.8, and the content of polymer A was 30 wt%. Let the obtained polymer be the polymer B.

Synthesis Example 3 Synthesis of Both Polymers Containing Polysilsesquioxane In a 500 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube, methyltriethoxysilane 199.55 g (1119.13 mmol), 5.95 g (30.00 mmol) of phenyltrimethoxysilane and 64.87 g (3600 mmol) of pure water were charged and the temperature of the solution was kept at 5 ° C. while stirring under a nitrogen stream. 12.15 g of 10% hydrochloric acid aqueous solution was added dropwise with stirring over 30 minutes, and the solution temperature was kept at 10 ° C. for 1 hour. Next, after raising the temperature of the solution to 70 ° C. and reacting for 3 hours, 50.75
g of 1,3-bis (3-mercaptopropyl) tetramethyldisiloxane (179.60 mmol) was added and stirring was continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C. and a 5% solution of potassium hydroxide in methanol was added to 13.4.
After adding 7 g, the mixture was stirred at room temperature for 2 hours and left standing for 12 hours. After extracting the lower layer portion and adding 150 g of butyl acetate, the mixture was concentrated with stirring at 40 ° C. under a reduced pressure of 200 mmHg, 150 g of the liquid was distilled off, and then 200 g of butyl acetate was further added at normal pressure to give 1 Stir for hours.
The obtained solution is filtered and then concentrated under reduced pressure,
84.3 g of a colorless transparent viscous liquid was obtained. The number average molecular weight of this product was 3,200 as measured by GPC. 25 from IR spectrum and Raman spectrum
Absorption based on the mercapto group appeared at around 60 cm ^-1 . Let the obtained polymer be polymer C-1.

In a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 20.02 g
Methyl methacrylate (199.96 mmol), 20.
83 g of styrene (20.00 mmol), 48.46 g
Blemmer PME-400 (manufactured by NOF CORPORATION) (1
(0.00 mmol), 10.06 g of Polymer C-1 were added, and the mixture was stirred under a nitrogen stream for 30 minutes. The solution thus prepared is called a mixed monomer. In a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 19.87 g of the mixed monomer and 96.91 g of 3-
Methoxy-3-methyl-1-butanol was added, and the mixture was stirred under a nitrogen stream at room temperature for 30 minutes. 10 weight percent of dimethyl 2,2'-azobisisobutyrate 3-methoxy-3-
Methyl-1-butanol solution (8.2 g) was added, the temperature was raised with stirring under a nitrogen stream, and the temperature was kept at 80 ° C. for 30 minutes.
An additional 79.50 g of mixed monomer was added over 3 hours. Again 10% by weight of 4.1 g of dimethyl 2,2′-azobisisobutyrate 3-methoxy-3-methyl-1-butanol solution was added and the reaction was continued at 90 ° C. for 3 hours. After cooling to room temperature, 200 g of a colorless transparent solution was obtained.
The weight average molecular weight of this product was 30,000. Raman spectrum 2560c due to polymer C-1
The absorption based on the mercapto group near m ^-1 disappeared. Also
The ratio of methyl methacrylate, styrene, and Blemmer PME-400 measured by ¹ H-NMR is 1: 1: 1.5.
And the content of polymer C-1 was 9 wt%. The obtained polymer is set to polymer C-2.

Synthesis Example 4 Synthesis of Polymer Containing Polydimethylsiloxane In a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 12.33 g of methyl methacrylate (123.15 mmol), 12.83 g of Styrene (126.85 mmol), 47.74 g of Bremmer PME-400 (manufactured by NOF CORPORATION) (98.52 mmo)
l), 31.80 g of polydimethylsiloxane X-22-167B (manufactured by Shin-Etsu Chemical Co., Ltd.) having a mercapto group introduced at both ends was added, and the mixture was stirred under a nitrogen stream for 30 minutes. The solution thus prepared is called a mixed monomer.
In a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 23.66 g of mixed monomer and 102.13 g of 3-methoxy-3-methyl-1-
Butanol was added, and the mixture was stirred under a nitrogen stream at room temperature for 30 minutes. 10 weight percent of dimethyl 2,2′-azobisisobutyrate dimethyl 3-methoxy-3-methyl-1-butanol solution 8.7 g was added and the temperature was raised with stirring under a nitrogen stream,
After keeping at 80 ° C. for 30 minutes, another 81.03 g of mixed monomer was added over 3 hours. Again, 4.4 g of 10 weight percent dimethyl 2,2′-azobisisobutyrate in 3-methoxy-3-methyl-1-butanol acetate was added and the reaction was continued at 90 ° C. for 3 hours. After cooling to room temperature,
207 g of a colorless transparent solution was obtained. The number average molecular weight of this product was 12,000. The absorption based on the mercapto group near 2560 cm ^-1 in the Raman spectrum due to X-22-167B disappeared. In addition, methyl methacrylate, styrene, and blemmer PM by ¹ H-NMR measurement
The E-400 ratio was 1: 1: 0.8 and the polydimethylsiloxane content was 30 wt%. Let the obtained polymer be the polymer D.

Examples 1 to 3 Preparation of Inks and Evaluation of Antifogging Property 31% by weight of titanium oxide (titanium white), 17% by weight of vinyl chloride-vinyl acetate copolymer, 3% by weight of acrylic resin, 33% by weight of isopropyl alcohol. , 100% by weight of a white printing ink consisting of 16% by weight of ethyl acetate, and 1.0% by weight and 2.0% by weight of the polymer solution having the polyorganosiloxane unit prepared in the above Synthesis Examples 2 to 4, respectively.
0 wt% was added and mixed at room temperature for 10 hours. The ink containing the polymer having a polyorganosiloxane unit thus prepared was gravure-printed on a polyethylene terephthalate resin with images, characters and the like, and dried at room temperature for 1 day. The antifogging property was evaluated by leaving the printed sample in an atmosphere having a humidity of 20% and a temperature of 5 ° C. for 30 minutes, and then a humidity of 80% and a temperature of 3
It was taken out in an atmosphere of 0 ° C., the state of dew condensation was observed, and the following judgment criteria were used. "○ ... No condensation, △ ... Slight condensation, X ... Strong condensation"

[0027]

[Table 1]

Comparative Examples 1 to 3 The conditions of dew condensation of the samples printed using the inks prepared without blending the polymer having the polyorganosiloxane unit in Examples 1 to 3 were as follows.

[0029]

[Table 2]

[0030]

Since the antifogging ink composition of the present invention contains a polymer having a polyorganosiloxane unit, a printed image printed with the printing ink has a hot or humid place or a boundary surface with a large temperature difference. Even when used in, the dew condensation does not occur on the ink surface and the printed characters can be read, and the present invention provides an excellent anti-fogging ink.

Claims (4)

[Claims] 1. An antifog ink composition comprising a polymer having a polyorganosiloxane unit. 2. The antifogging ink composition according to claim 1, wherein the surface of the coating film formed by printing has a silicon concentration of 6% or more. 3. The antifogging ink composition according to claim 1, wherein the polyorganosiloxane is polysilsesquioxane. 4. The antifogging ink composition according to claim 1, wherein the polyorganosiloxane is a polydialkylsiloxane.