JPS638998B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to poly(amide-ester) resins. In particular, the present invention relates to poly(amide-ester) resins having a structure in which hydroxyl groups are suspended, and which are useful as vehicles for printing inks and coating compositions. The preparation of polyamide resins from epoxy resins, dibasic acids and polyamines is known. No. 3,308,076 teaches resinous polyamides by (1) esterifying an epoxy resin with a dibasic acid to form a carboxyl-terminated epoxy ester, and then (2) reacting with a polyamine to form an amine-terminated polyamide. I am forced to do so. Such resin products are disclosed in US Pat. No. 3,207,653 as being useful as adhesives in laminating Mylar and polyethylene films. Poly(amide-ester) resins according to the present invention are produced by (1) reacting a dimeric fatty acid with a diamine to form a carboxyl-terminated polyamide resin, and then (2) reacting with an epoxy resin through the terminal epoxy groups to have secondary hydroxyl groups. Manufactured by a process that forms a poly(amide-ester) resin. The dimeric fatty acid is reacted with a polyamine in the presence of a chain terminator to form a carboxyl-suspended polyamide resin (Step 1). The carboxyl group is then reacted with an epoxy resin through the terminal epoxy group in the presence of a catalyst. A second hydroxyl group is generated by opening the epoxy ring (step 2). The general reaction formula is as follows: [In the formula, D is an alkyl-substituted cyclohexenyl ring; R ¹ represents the main skeleton of the epoxy resin structure excluding the glycidyl ether groups at both ends, where the epoxy resin is a bisphenol A-epichlorohydrin type, novolac type and polyglycol type; A is is a repeating unit represented by (where R is an aliphatic chain, aromatic nucleus, alkyl-substituted cyclohexyl ring, or polyoxypropylene structural moiety), and n is 2 to 20
Dimer fatty acids have the general formula HOOC-D-COOH
where D is an alkyl-substituted cyclohexenyl ring. These dimer acids are commercially available from various manufacturers and have approximately the following composition. Weight % Monomer Acid Trace - 15 Dimer Acid 60 - 98 Trimer Acid Trace - 25 Typical dimer fatty acids are as follows, but are not necessarily limited thereto.

[Table] Manufactured by)
T-18 (product name) 3 79 18

[Table] Manufactured by)
1014 (product name) 1 95 4

1018 (Product name) Trace 83 17
Unidyme 18 (manufactured by Union Camp) 3 79 18

Generally the dimeric fatty acids are between about 40% and 88% based on the total charge weight of the reaction materials, preferably about
Used in amounts between 70% and 75%. The polyamine component has the general formula H ₂ NR--NH ₂ , where R is an aliphatic chain, an aromatic nucleus, an alkyl-substituted cyclohexyl ring, or a polyoxypropylene structural moiety. A typical example is ethylenediamine,
propylene diamine, hexamethylene diamine,
isophorone diamine and polyglycol diamine. Depending on the functional group of the acid component, in addition to the diamine, small amounts of triamines such as diethylenetriamine or polyamines such as ethylenetetramine or tetraethylenepentamine may also be used. This is approximately 5% based on the total weight of reaction materials.
and 10%, preferably between about 6% and 9%. The epoxy resin component has the general formula [Here, R ¹ represents the main core of the epoxy resin structure excluding the glycidyl ether groups at both ends (However, the epoxy resin may be any of the bisphenol A-epichlorohydrin type, novolak type, and polyglycol type) )]. For example, in terms of product names, Epons by Ciel Corporation, namely Epon 812 (epoxy equivalent 150 to 170),
Epon 828 (epoxy equivalent 180 to 195), Epon
1001 (epoxy equivalent 425 to 550) and Epon
1004 (epoxy equivalent weight 875 to 1025) and bisphenol A-epichlorostohydrin resins such as Dow's DER331 (epoxy equivalent weight 182 to 190) and DER383 (epoxy equivalent weight 178 to 186);
Dow DEN431 (epoxy equivalent 172 to 179)
and novolak-type epoxy resins such as DEN438 (epoxy equivalent weight 176 to 181) or Dow
DER732 (epoxy equivalent weight 305 to 335) and
It can be a polyglycol type epoxy resin such as DER736 (epoxy equivalent weight 175 to 205). Generally, the epoxy resin is about 5% to 50%, preferably about 10% to 50%, based on the total charge weight of reactant materials.
Used in an amount of 20%. Additional small amounts of C ₈ - _{C 14}
Monoepoxides such as aliphatic glycidyl ethers containing alkyl groups may also be used. In the first step, ethanol, n-
Improves the solubility of the product in alcohols such as propanol or isopropanol. Preferred terminators are monobasic acids such as acetic acid, propionic acid and acids having about 3 to 18 carbon atoms in the chain. The terminator is used in an amount of between about 2% and 10%, preferably between about 4% and 6%, based on the total charge weight of reaction materials. In the second step, a catalyst is used to increase the esterification rate. Typical catalysts are tertiary amines such as N,N-dimethylbenzylamine or tri-n-butylamine, rare earth metal oxides such as cerium oxide, lanthanum oxide, and transition metal salts such as chromium acetate or zirconium octoate. It is. The temperature used in the first step is approximately 150℃ to 225℃
℃, preferably in the range of about 175°C to 200°C. The second step is generally between about 100°C and 150°C, preferably between about 115°C and 140°C. The resulting poly(amide-ester) resins are hard but pliable. These have an acid value of about 0 to
30, preferably about 0 to 15 mg. KOH/gm. resin, amine value about 0 to 5, preferably about 0 to 3 mg. KOH/gm. resin and a softening point between about 85°C and 160°C, preferably between about 95°C and 135°C. These are soluble in higher alcohols and mixtures of hydrocarbon or ester solvents and alcohols, and have excellent compatibility with nitrocellulose. By adding these poly(amide-ester) resins to the composition, printing inks with excellent adhesion to various plastic and metal surfaces, high heat resistance and latent crosslinking properties are obtained. For example, when used as a vehicle for flexographic or gravure inks, the resinous products of the invention improve gloss, adhesion, scratch resistance and heat resistance. When these are reacted with lime rosin for use in gravure publishing inks, excellent gloss and high scratch resistance are obtained. Because these resinous products contain secondary hydroxyl groups (formed by ring opening of epoxy groups), they can be transesterified with other suitable resins such as alkyds or polyesters to form the final product. Increases adhesion, gloss and scratch resistance. They also have potential as vehicles for water-based inks. When the hydroxyl group is reacted with an anhydride, the product becomes water-soluble or water-dispersible depending on the salt formed by neutralizing the free carboxyl group (formed by ring opening of the anhydride) with an organic base. become. Organic oxides such as ethylene oxide may also be added to achieve water solubility. The poly(amide-ester) resins according to this invention are also useful as UV curing vehicles or additive resins in UV applications. These hydroxyl groups react with polyisocyanates and hydroxyl acrylates to form urethanized-acrylated amide-esters. The invention is illustrated by the following examples, in which all categories and percentages are by weight unless otherwise indicated. Example 1 (A) Dimer fatty acids (trade name
Crodym T-18, manufactured by Crosby Chemicals)
395.5 parts, propionic acid (99% purity) 24.8 parts and antifoaming agent (trade name DC-200 silicone liquid,
Add 3 drops (manufactured by Dow Corning). The reaction was heated to 50° C. under a blanket of nitrogen, then 25.3 parts of ethylenediamine (99% purity) was added. The temperature reached 100℃ due to heat generation, but it was kept at 110-120℃ for 1 hour. The generated polymer salt is dehydrated and 140-
Water was distilled off at 200°C. Acid value 100-110,
An acid-terminated polyamide resin having an amine value of 0.1 was obtained. (B) The product of (A) was cooled to 120-130°C and bisphenol A-epichlorohydrin resin (trade name)
155.0 parts of Epon828 (manufactured by Shell) and 0.6 parts of N,N-dimethyl-benzylamine were added. The temperature was maintained at 120-140°C until the acid number of the product was below 10. The product is an amber, hard poly(amide-ester) resin with some elasticity at room temperature.
It has the following physical properties: Acid value: 7.3 Amine value: 0 Softening point (Duran), °C. 98 Gardner Viscosity (25°C, @40% solids in n-propanol) G Example 2 (A) 1 volume four-neck Pyrex flask equipped with stirrer, moisture trap, nitrogen inlet and water-cooled condenser. Dimer fatty acid (product name)
Crodym T-18) 472.0 parts, propionic acid (99% purity) 29.6 parts and antifoaming agent (trade name DC-
200) Add 5 drops. The reaction material was heated to 50° C. under a nitrogen blanket and then 42.2 parts of ethylenediamine (99% purity) was added. 90- due to fever
It showed 100℃, but it was heated to 115℃ and kept for 1 hour. The produced polymer salt was dehydrated and water was distilled off at 140-200°C. Acid value 60-65, amine value
An acid-terminated polyamide resin having a value of 0.1 was obtained. (B) The product of (A) was cooled to 130-135℃ and bisphenol A-epichlorohydrin resin (trade name)
Epon828) 110.0 parts and N, n-dimethyl-
0.6 parts of benzylamine was added. The temperature was maintained at 120-135°C until the acid number of the product was approximately 10. The produced poly(amide-ester) resin was poured onto a tray, cooled and solidified, and pulverized. The product was amber in color, slightly harder and less elastic than the product of Example 1, and had the following physical properties: Acid number: 10.9 Amine number: 1.1 Softening point (Duran), °C. 115-116 Gardner viscosity (25℃, @40% solids in n-propanol) D+ Example 3 Unidyme18 (Union
Camp dimer fatty acids) and Emery
Dimer fatty acid manufactured by Industries (product name: Empol)
Example 1 except that 1014 and Empol1018) were used.
The operation was repeated. Similar results were obtained. Example 4 Instead of the bisphenol A-epichlorohydrin type epoxy resin “Epon828”, the same type “Epon812”, “Epon1001”, “Epon1004” (all trade names of Shell), “DER331” and “DER383” were used. (both are Dow product names), novolak type epoxy resins DEN431 and DEN438
The procedure of Example 1 was repeated except that DER732 and DER736 (trade name of Dow Company) and polyglycol type epoxy resins were used. Similar results were obtained. Example 5 The procedure of Example 1 was repeated except that the following polyamines, propylene diamine, hexamethylene diamine, and isophorone diamine were used instead of ethylene diamine. Similar results were obtained. Example 6 Example 1 using acetic acid instead of propionic acid
The operation was repeated. Similar results were obtained. Example 7 A flexographic ink was prepared according to the following formulation. Part Product of Example 1 14.0 Lithol Rubine (trade name)
15.0 Nitrocellulose 5.0 Polyethylene wax 1.0 Ethanol 40.0 n-propyl acetate 15.0 Heptane 10.0 A printed film with high gloss, good adhesion, excellent scratch resistance, and good heat resistance was produced on the corona-treated polyolefin film and on paper. Example 8 A gravure ink was prepared according to the following formulation. Part Product of Example 2 14.0 Lithol Rubine (trade name)
10.0 Nitrocellulose 5.0 Polyethylene wax 1.0 Ethanol 30.0 n-propyl acetate 15.0 Toluene 25.0 Printed films with high gloss, good adhesion, excellent scratch resistance, and good heat resistance were produced on corona-treated polyolefin film and paper.

Claims (1)

[Scope of Claims] 1. A printing ink composition comprising a resin, a solvent, and a pigment, wherein the resin has the following general formula: [In the formula, D is an alkyl-substituted cyclohexenyl ring; R ¹ is the main skeleton of the epoxy resin structure excluding the glycidyl ether groups at both ends, where the epoxy resin is a bisphenol A-epichlorohydrin type, novolac type and polyglycol type; A is is a repeating unit represented by (where R is an aliphatic chain, aromatic nucleus, alkyl-substituted cyclohexyl ring, or polyoxypropylene structural moiety), and n is 2 to 20
is an integer of ], and the resin has an acid value of 0 to 30, an amine value of 0 to 5, and a softening point of 85 to 85.
A printing ink composition such that the temperature is 160°C. 2. The resin undergoes the following step: (a) about 40-88% by weight of the total charge of dimeric fatty acids is reacted with about 5-10% by weight of a polyamine in the presence of about 2-10% by weight of a chain terminator; molecular weight
3000 or less, an acid value of 35 to 200, and an amine value of 0 to 10. [In the formula, R ¹ represents the main bone core of the epoxy resin structure excluding the glycidyl ether groups at both ends,
Here, the epoxy resin is any of the bisphenol A-epichlorohydrin type, novolak type and polyglycol type. ] The printing ink composition according to claim 1, which is synthesized by a step of reacting with an epoxy resin shown in the following. 3 The amount of dimeric fatty acids is approximately 70 to 75 of the total amount of preparation
% by weight, the amount of polyamine is about 6-9% by weight, the amount of chain terminator is about 4-6% by weight, the amount of epoxy resin is about 10-20% by weight, and the chain terminator is a monocarboxylic acid. The printing ink composition according to claim 2, characterized in that: 4 The acid value of the terminal carboxyl group polyamide resin obtained in step (a) is 50 to 125 and the amine value is 0 to 6, and the acid value of the poly(amide-ester) resin obtained in step (b) is 0 to 15. The printing ink composition according to claim 2, having an amine value of 0 to 3 and a softening point of 85 to 135°C. 5. Printing ink according to claim 2, characterized in that the dimeric fatty acids consist of traces to 15% by weight of monomer acids, about 60 to 98% by weight dimer acids and traces to 25% by weight trimer acids. Composition.