JPH03244616A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a hypochromic composition which retains the gloss and water resistance of an alkyd resin, excellent in sterilizer solution and acid resistances by reacting a monoepoxy ester compound with a polyhydric alcohol, maleic anhydride and a polybasic acid. CONSTITUTION:A resin composition containing an alkyd resin with a number- average mol.wt. of 1,000-8,000 and a hydroxyl value of 50-300, obtained by reacting 20-60 wt.%, based on the total weight of the components mixed, monoepoxy ester compound with a polyhydric alcohol and 0.1-3.0 wt.%, based on the monoepoxy ester compound, maleic anhydride and other polybasic acids. When the number-average mol.wt. is below 1,000, the water and sterilizer solution resistances are poor, and when it is above 8,000, the alcohol solubility and the compatibility with cellulose nitrate are poor. When the hydroxyl value is below 50, the alcohol solubility is poor, and when it is above 300, the water and sterilizer solution resistances are poor.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a resin that is light in color, has excellent resistance to sterilizing liquid (ethanol) and acid resistance, and is useful as a printing ink used for food packaging, etc. Regarding the composition.

(Prior Art) Conventionally, as a resin for printing ink used for food packaging, etc., a mixed system of alcohol-soluble alkyd resin and nitrified cotton is generally used.

The alkyd resin was modified with vegetable oil or these fatty acids. It has a short to medium oil length, and in order to be easily dissolved in alcohol, a type with a high hydroxyl value and low molecular weight is usually used.

Although these alkyd resins have good gloss and water resistance, they are insufficient in sterilizing liquid resistance and acid resistance, and are required to have even higher performance.

In order to maintain gloss and water resistance and improve antibacterial liquid resistance and acid resistance, the objectives can be achieved by using a sitalkyd resin modified with a monoepoxy ester compound such as monoepoxy ester of versatic acid. Generally, aromatic hydrocarbon solvents cannot be used in resin compositions for printing inks used for food packaging, etc., due to the transfer of odor from the printing ink to the contents and the solvent resistance of printing plates and rolls. Alcohol-based solvent is used as the main component. However, when synthesizing alkyd resins using mono-epoxy ester compounds using a solvent-free method that does not use aromatic hydrocarbons (refluxing solvents for dehydration) such as quidylol or doluol, significant coloring may occur. like this.

When used in light-colored printing inks, etc., problems arise due to the color of the resin.

On the other hand, if a monoepoxy ester compound-modified alkyd resin is synthesized using a refluxing solvent for dehydration such as quidylol or doluol, there is no problem of coloring.

When used for food packaging, etc., it is necessary to remove the refluxing solvent and replace the solvent. This method requires special equipment such as a vacuum desolvation equipment and has an economic disadvantage.

(Problems to be Solved by the Invention) The present invention solves nine or more problems.

The present invention provides a light-colored resin composition that maintains water resistance and has excellent sterilizing liquid resistance and acid resistance.

(Means for Solving the Problems) The present invention provides a monoepoxy ester compound, a polyhydric alcohol, and a monoepoxy ester compound of 20 to 60% by weight based on the total amount of blended components, and O11 to 3.0% by weight based on the monoepoxyester compound.
A number average molecular weight of 1,000 obtained by blending maleic anhydride and other polybasic acids as essential components and reacting with 9.
~8,000. The present invention relates to a resin composition containing an alkyd resin having a hydroxyl value of 50 to 300.

The monoepoxy ester compound used in the present invention is 1
It is an ester compound containing one epoxy group in the molecule.
Monoepoxy esters of synthetic fatty acids such as versatile acid and isoparaffinic saturated fatty acids, monoepoxy esters of aromatic monocarboxylic acids such as paratertiary butylbenzoic acid, and monoepoxy esters of vegetable oil fatty acids such as soybean oil fatty acids and linseed oil fatty acids. , α-olefin monoepoxy esters, etc. As the monoepoxy ester compound used in the resin composition of the present invention, monoepoxy esters of synthetic fatty acids and monoepoxy esters of aromatic monocarboxylic acids are preferred because they have excellent acid resistance and water resistance. α-olefin monoepoxy ester is
Unfavorable from the point of view of odor.

As these monoepoxy ester compounds.

Cardura E (manufactured by Shell Chemical Co., Ltd., versatic acid monoepoxy ester), PE5-10 (manufactured by Fuyo Chemical Industry Co., Ltd., paratertiary butylbenzoic acid monoepoxy ester), and the like are commercially available.

The monoepoxy ester compound is blended in an amount of 20 to 60% by weight, preferably 25 to 45% by weight, based on the total amount of the blended components. If it is less than 20% by weight, the intended carbon chloride resistance and acid resistance will not improve, and if it exceeds 60% by weight, the coating film will become brittle.

Poor water resistance.

The polyhydric alcohols used in the present invention include pentaerythritol, glycerin, trimethylolpropane, trimethylolethane, neopentyl glycol, 1.6
Hexanediol, bisphenol A, hydrogenated bisphenol, cyclohexane dimetatool, 1.3 penonanediol, methylbentanediol, ethylene glycol, diethylene glycol, phlopylene gelicol, cyprohylene glycol, 1.37'tanediol, Examples include spiroglycol, nonanediol, and ε-caprolactone.

In the present invention, maleic anhydride is an essential acid component, and the maleic anhydride is 0.1 to 3.0 weight heavier than the monoepoxy ester compound, preferably 0.5 to 3.0 weight more than the monoepoxy ester compound.
It is considered to be within the range of 201i. If the amount is less than 0.1% by weight, there is no effect of preventing coloring of the resin.

If the weight exceeds 3.0, the alkali resistance will be poor.

Other polybasic acids include phthalic acid, hexahydrophthalic acid, their acid anhydrides, 1.1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, and 1.4-cyclohexanedicarboxylic acid. , adipic acid, azela 4-H, sebacic acid, trimellitic acid, etc.

The blending amounts of the polyhydric alcohol, maleic anhydride, and other polybasic acids are appropriately determined by determining the amount of the monoepoxy ester compound, the desired hydroxyl value, and the molecular weight. Usually, the molar ratio of polyhydric alcohol/maleic anhydride and other polybasic acids is preferably 1.1 to 1.8.

Furthermore, if necessary, some of these fatty acids may be blended with vegetable oil. Vegetable oils or these fatty acids include coconut oil, coconut oil fatty acids, and soybean oil.

Those having an iodine value of 150 or less, such as soybean oil fatty acids and rice bran fatty acids, are preferable, and the ratio of their combined use is preferably 30 weight or less with respect to the monoepoxy ester compound.

The combined use of vegetable oils with an iodine value exceeding 150 or these fatty acids tends to cause coloring of the resin and poor alkali resistance. If the amount of mixed vegetable oil or these fatty acids used in combination exceeds 30% by weight, the antibacterial liquid resistance and acid resistance tend to be poor.

The alkyd resin of the present invention obtained from each of the above components has a number average molecular weight of 1,000 to 8,000. I like it,
Adjusted to 500-5.000. Number average molecular weight is 1,
If it is less than 000, water resistance and sterilization liquid resistance are poor.5. a,oo
If it exceeds o, the alcohol solubility and compatibility with nitrified cotton will be poor. The number average molecular weight referred to herein is a value measured by gel permeation chromatography and converted to standard polystyrene.

In addition, the hydroxyl value (solid content) of the obtained alkyd resin is 5
0-300. Preferably it is adjusted to 80-250. If the hydroxyl value is less than 50, alcohol solubility is poor;
If it exceeds this, water resistance and sterilization liquid resistance will be poor. Furthermore, the acid value (
The solid content is preferably less than 20 since it does not reduce water resistance and sterilizing liquid resistance.

As the method for synthesizing the alkyd resin, a solvent-free method that does not include a refluxing solvent is preferred. Specifically, predetermined materials are charged, reacted for 1 to 2 hours at 180°C under a nitrogen stream, and then reacted for 1 to 2 hours.
It is obtained by raising the temperature to 00 to 230°C and reacting at a desired acid value or viscosity.

The alkyd resin obtained as described above is used as a solvent that does not require printing plates or rolls as described above.

A resin composition is prepared by dissolving a lower monoalcohol in an amount of 50 weight φ or more in a solvent containing an aromatic hydrocarbon solvent.

Examples of the lower monoalcohol include methanol, ethanol, imbutanol, n-butanol, secondary butanol, and impropatol, but impropatol is particularly preferred from the viewpoint of toxicity, odor, drying properties, economical efficiency, and the like.

Furthermore, solvents other than aromatic hydrocarbons that can be used in combination include esters such as ethyl acetate, butyl acetate, and amyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene gelicol monomethyl ether. , ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate.

Examples include polyhydric alcohol derivatives such as propylene glycol monomethyl ether acetate, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. Among these.

Propylene glycol derivatives are particularly preferred from the viewpoint of toxicity, drying properties, printability, etc.

The ratio of lower monoalcohol and other solvents other than aromatic hydrocarbons needs to be 50% by weight of lower alcohol, preferably 70/30 to 90/10 (lower alcohol/other solvent). weight ratio). If the lower monoalcohol is less than 50% by weight, the drying properties will be poor.

Furthermore, when the resin composition of the present invention is used as a binder for printing ink for food packaging, etc.

Generally, nitrified cotton and a coloring agent are blended.

As nitrified cotton, about 2 of the 3 hydroxyl groups in cellulose
Nitrated cellulose with a nitrogen content of 10.
7 to 11.5% of the SS type is preferable because it is soluble in alcohol. The amount to be used is appropriately determined in consideration of characteristics such as drying properties.

As the coloring agent, inorganic pigments such as carbon black, titanium dioxide, and red iron oxide, and organic pigments such as azo, phthalocyanine, and isoindoline are used alone or in combination depending on the desired color.

(Example) Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In 9 examples, "parts" means "parts by weight" unless otherwise specified in q#. do.

Example 1 1,710 parts of versatic acid monoepoxy ester (Cardura E, manufactured by Shell Chemical Co., Ltd.) was placed in a 1/4 volume flask equipped with a stirrer, a thermometer, a dehydration trap tube with a rectifying column, a cooling tube, and a nitrogen gas introduction tube.

19LO parts of trimethylolpropane, 1t2 of anhydrous phthalate
51.5 parts and 1.7 parts of maleic anhydride were charged.

160℃ while blowing nitrogen at 100 mj/min
The temperature rose to . The temperature was further increased to 215°C over 3 hours. The reaction proceeded at the same temperature until the acid value (solid content) reached 8.6, and after cooling, diluted with 51.0 parts of propylene glycol monomethyl ether acetate at 150°C or lower and 206 parts of isopropyl alcohol at 80°C or lower to obtain 9 color numbers (Gart). A pale yellow transparent resin composition of No. 1 was obtained.

Table 1 shows the formulation and resin properties of the resin compositions of each example and comparative example.

Example 2 II! with equipment similar to Example 1! Versatic acid monoepoxy ester (Cardura E
), 109.0 parts of trimethylolpropane, 38.0 parts of neopentyl glycol, 154.0 parts of hexahydrophthalic anhydride, 1.35 parts of maleic anhydride, and 128.0 parts of phthalic anhydride. 100 m of nitrogen
The temperature was raised to 160° C. while blowing at Z/min. The temperature was further raised to 230℃ over 4 hours, and at the same temperature the acid value (solid content) was 6.6-! Proceed with the reaction and after cooling, propylene glycol monomethyl ether acetate (8) at 150℃ or below
0.0 part.

The mixture was diluted with 320 parts of isopropyl alcohol at 80° C. or lower to obtain a pale yellow transparent resin composition with 9 color numbers (Gardner) and 2.

Example 3 II! with equipment similar to Example 1! Versatic acid monoepoxy ester (Cardura E
), 106.0 parts of trimethylolpropane, 228.0 parts of isophthalic acid, and 1.0 part of maleic anhydride, and while blowing nitrogen at 100 ml/min,
The temperature was raised to 0°C. The temperature was further increased to 220°C over 4 hours. The reaction proceeded at the same temperature until the acid value (solid content) reached 10, and 18
Dipropylene glycol methyl ether 60 below 5℃
．． 0 copies.

Diluted by adding 60.0 parts of propylene glycol methyl ether acetate at 150°C or below and 210.0 parts of Improvil alcohol at 80°C or below, resulting in 9 colors (Gardner)
A light yellow transparent resin composition of No. 2 was obtained.

Comparative Example 1 11! equipped with the same device as Example 1! The temperature was raised using the same formulation and process as in Example 1, except that maleic anhydride was removed from the 4-tube flask. The reaction proceeded at an acid value (solid content) of 8.3-1, and after cooling, the mixture was diluted in the same manner as in Example 1. A brownish transparent resin composition with a color number (Gardner) of 9 was obtained.

Comparative Example 2 II! equipped with the same equipment as Example 1! The temperature was increased using the same formulation and process as in Example 2, except that maleic anhydride was removed from the 04 Tulo flask. The reaction proceeded when the acid value (solid content) was 7.11, and after cooling, it was diluted in the same manner as in Example 2. A brownish transparent resin composition with a color number (Gardner) of 8 was obtained.

Comparative Example 3 The temperature was raised in the same blending process as in Example 3 except that maleic anhydride was removed in an fc1104 Tulo flask equipped with the same equipment as in Example 1. The reaction proceeded when the acid value (solid content) was 9.61, and after cooling, it was diluted in the same manner as in Example 3. A brownish transparent resin composition with a color number (Gardner) of 7-8 was obtained.

Comparative Example 4 396 parts of coconut oil, 138.6 parts of trimethylolpropane, and 0.01 part of lithium hydroxide were charged into a 1/4 volume flask equipped with the same equipment as in Example 1, and the temperature was raised to 230°C. The transesterification reaction was proceeded with 1, which was dissolved in 3 times the volume of methanol at the same temperature, and the mixture was cooled.

267.3 parts of transesterified oil was taken out, and 128 L of trimethylolpropane, 16 parts of opentyl glycol, 213 parts of phthalic anhydride, and 0.2 part of maleic anhydride were charged and the temperature was raised to 180°C. 21 in 1 hour after keeping warm at the same temperature for 1 hour
The temperature was raised to 0°C. The reaction proceeded in a box with an acid value (solid content) of 8.3 and was cooled.

120 parts of propylene glycol methyl ether acetate at 150℃, 3 parts of Improvil alcohol at 80℃ or less
It was diluted by adding 80 parts. A pale yellow transparent resin composition with a color number (Gardner) of 2-3 was obtained.

Example 4 In 11 four-tube flasks equipped with the same equipment as in Example 1, p-tert-butylbenzoic acid monoepoxy ester (
PES-10, manufactured by Buyeo Chemical Industry ■) 180.0 parts, trimethylolpropane 91.3 parts.

Neopentyl glycol 59.1 parts, phthalic anhydride 12
0.0 part, hexahydrophthalic anhydride 168.1 parts,
Charge 1.35 parts of maleic anhydride and 100 roe of nitrogen.
The temperature was raised to 160°C while blowing / min-.

Further, the temperature was raised at 230'C4 for 4 hours, the reaction proceeded at the same temperature when the acid value (solid content) was 9.3, and after cooling, the propylene glycol monomethyl ether acetate s was heated to 150°C or less.
o, o parts, mesopropyl alcohol 320 below 80°C
．． A pale yellow transparent resin composition having a color number of 1 to 2 (Gardner) was obtained by diluting with 0 parts.

Comparative Example 5 9.0 parts of maleic anhydride was placed in an IJ 4-tube flask equipped with the same equipment as in Example 1, and the temperature was increased using the same blending and steps as in Example 2 except for maleic anhydride. The reaction proceeded when the acid value (solid content) was 11.81.

After cooling, it was diluted in the same manner as in the example. Number of colors (Gardner) 4
A light brown transparent resin composition was obtained.

Comparative Example 6 Versatic acid monoepoxy ester (Cardura E) was added to a 4-I solo flask equipped with the same equipment as in Example.
379 parts of trimethylolpropane, 4.5 g of trimethylolpropane, 212.6 parts of phthalic anhydride, and 2.84 parts of ffthureic anhydride were charged, and the temperature was raised to 160° C. while blowing nitrogen at 100 ml/min. The temperature was further raised to 240°C over 4 hours, the reaction proceeded at the same temperature with an acid value (solid content) of 11.81, and after cooling, 80.0 parts of propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate) was added to 80°C or less. Dilute with 320.0 parts of inpropyl alcohol and make 2 to 3 colors (
Gardner) was obtained as a pale yellow transparent resin composition.

Comparative Example 7 Versatic acid monoepoxy ester (Cardura E) was added to 11 four-tube flasks equipped with the same equipment as in Example 1.
60 parts of trimethylolpropane, 121.6 parts of neopentyl glycol, 120 parts of phthalic anhydride, 199.7 parts of hexahydrophthalic anhydride, and 0.45 parts of maleic anhydride, and nitrogen was charged at 100 i/min. The temperature was raised to 180° C. while blowing. Further 230℃1
The temperature was raised over 4 hours at the same temperature, and the reaction proceeded until the acid value (solid content) reached 9.1. After cooling, the mixture was diluted with 80 parts of propylene glycol monomethyl ether acetate at 150°C and 320.0 parts of isopropyl alcohol at 80°C or below. A pale yellow transparent resin composition with a color number of 2 (Gardner) was obtained.

<Painting and test plate preparation method> (1) Examples 1 to 4. 12 of the resin compositions of Comparative Examples 1 to 4
．． 5 parts (solid content) and 12.5 parts (solid content) of nitrified cotton S S 1/15'' (solid content 40% product diluted with Inopropatool/ethyl acetate-50150 weight),
A paint was obtained by diluting with ingbanol to reach a solid content of 30% and further diluting with ethyl acetate to a solid content of 25%.

(2+ (11 paints were applied to a glass plate and a hiding rate test paper specified in JIS K 5400 6.3 using a bar coater φ12, and dried at 50°C for 20 minutes to prepare a test plate.

(Effects of the Invention) As is clear from the above, if the resin composition of the present invention is used, it will have excellent sterilizing liquid resistance and acid resistance, which were problems of conventional alkyd resins, and will also have excellent water resistance and drying resistance. Produces a coating film with good properties.

Furthermore, the resin composition of the present invention can be obtained by a solvent-free method with almost no coloration.

The resin composition of the present invention is most suitable for printing ink for food packaging.

Claims (1)

[Claims] 1. 20 to 60% by weight of a monoepoxy ester compound, polyhydric alcohol, and 0.1 to 3.0% by weight of maleic anhydride relative to the monoepoxy ester compound, based on the total amount of the ingredients. and other polybasic acids as essential components, and the number average molecular weight obtained by reacting the mixture is 1,000 to 8,0.
00, a resin composition containing an alkyd resin having a hydroxyl value of 50 to 300. 2. The resin composition according to claim 1, which contains a solvent containing 50% by weight or more of a lower monoalcohol and no aromatic hydrocarbon solvent.