JPS6256172B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing epoxy-urethanes based on copolyesters. US Pat. No. 3,763,079 to Fryd discloses polyester/urethanes used as starting materials for the present invention. His earlier patent, US Pat. No. 3,804,810, discloses cross-linking of polyurethanes.
The disclosures of these two Fryd patents are incorporated herein by reference. The present invention is produced by capping the polyester/urethane described in Fryd U.S. Pat. No. 3,763,079 with a dicarboxylic acid anhydride and chain extending the capped polyester/urethane with an epoxy resin. It consists of an improved adhesive composition and an adhesive solution in an organic solvent. The epoxyurethane of the present invention is manufactured by a four-step process, the first two of which are disclosed in U.S. Pat.
No. 3,763,079 and the last two steps are carried out at least partially simultaneously. The chemical reaction of this method can be summarized by the following scheme.

[Table] Tanblock copolymer copolyester-urethanes Manufactured by steps (1) and (2) above
All of the polyester-urethanes described in Fryd's U.S. Pat. It means that. These copolyester-urethanes are produced in a relatively conventional manner by reacting at least one polyester prepolymer with at least one organic diisocyanate, where the isocyanate contained on the diisocyanate versus the copolyester. The equivalent ratio of hydroxyl contained in is 1 or less. These copolyesters are prepared by (1) an esterification reaction, ie, the reaction of one or more diols or polyether glycols with at least two different dicarboxylic acids or two different dicarboxylic acid anhydrides; 2) Produced by transesterification, ie, reaction of one or more diols or polyether glycols with at least two different dicarboxylic acid esters. Copolyesters are manufactured by well known conventional means. Typically, to produce polyester, the reactants are mixed in a suitable reaction vessel while heating to a temperature of about 150 DEG C. to 250 DEG C. for 1/2 to 8 hours. Diols can be aliphatic or aromatic.
Hydrocarbon groups in diols include, for example, N, O,
It may contain non-interfering groups such as S, halogen, etc., ie it may be substituted or interrupted with these. Examples of suitable diols include, for example, ethylene glycol, propylene-1,2-glycol, propylene-1,3-glycol, butylene-1,3-diol, butylene-1,4-diol, butylene-1,3-diol, 2,3-diol, neopentyl glycol, i.e. 2,2-dimethylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,
3-diol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, thioethylene glycol, N-methyldiethanolamine, monoethyl ether of glycerin, α-allyl ether and β-allyl ether of glycerol, etc. Can be done. Preferably, these diols have about 2 to 8 carbon atoms, and most preferably about 2 to 6 carbon atoms. A more preferred diol is ethylene glycol. If desired, one or more polyether glycols can be used with the diol. Examples of suitable polyether glycols include polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, diethylene glycol, and the like. Such polyether glycols are about 200~
10,000, preferably about 500 to 4,000, most preferably about 1,000. A more preferred polyether glycol is polytetramethylene ether glycol. Dicarboxylic acids can be aliphatic, cycloaliphatic, unsaturated or aromatic. The hydrocarbon groups in the dicarboxylic acids can contain non-interfering groups such as O, S, N, halogen, keto, etc., ie can be substituted or interrupted with these. Examples of suitable dicarboxylic acids include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, maleic acid, fumaric acid, dilinoleic acid, diphenic acid, phthalic acid. , tetrachlorophthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid, cyclohexanedicarboxylic acid, p-phenylene diacetic acid, naphthalene dicarboxylic acid, dihydromuconic acid, β-methyladipic acid, trimethyladipic acid, ethyl ether-2,2'-dicarboxylic acid You can give acids, etc. If desired, anhydrides of the dicarboxylic acids mentioned above can be used, such as phthalic anhydride, tetrahydrophthalic anhydride, and the like. A more preferred dianhydride is phthalic anhydride. Examples of more preferred dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, orthophthalic acid, azelaic acid, adipic acid and mixtures of _C4 - _C6 aliphatic dicarboxylic acids. Preferably, the dicarboxylic acid or dicarboxylic acid anhydride has about 4 to 12 carbon atoms. Diisocyanates for use in urethane synthesis can be aliphatic or aromatic. Examples of suitable isocyanates include, for example, hexane-1,6-diisocyanate, decane-1,10
-diisocyanate, diisocyanate derived from dimerized fatty acids, phenylene-1,4-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, naphthylene-1,5 diisocyanate, diphenylmethane-4,4'- Examples include diisocyanate, diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. More preferred are toluene-2,4-diisocyanate, toluene-2,6-diisocyanate and mixtures thereof. Preferred polyester-urethanes are toluene-2,4-diisocyanate and toluene-2,4-diisocyanate.
A mixture of 6-diisocyanates [Hyren (registered trademark) TM] (A) 28-38 mol% of terephthalic acid, 12% of isophthalic acid
~22 mol% and azelaic acid 40-60 mol%, (B) orthophthalic acid or phthalic anhydride 40-60
mol% and adipic acid 40-60 mol%, (C) terephthalic acid 45-65 mol% and azelaic acid 35-55 mol%, (D) terephthalic acid 35-45 mol%, isophthalic acid 35
~45 mol%, azelaic acid 5-15 mol% and adipic acid 5-15 mol%, (E) terephthalic acid 45-55 mol%, isophthalic acid 15
~25 mol% and azelain 20-40 mol%, (F) orthophthalic acid or phthalic anhydride 40-60
40-60 mol% of a mixture of C4 _{-C6 aliphatic} dicarboxylic acids, or (G) 5-15 mol% of terephthalic acid, 40-60 mol% of orthophthalic acid or phthalic anhydride and 25-55 mol% of adipic acid. It is produced by reacting with a prepolymer prepared from mol %. Whatever copolyester-urethane is selected for further processing, it is reacted with (3) a dicarboxylic acid or anhydride and (4) an epoxide under conditions that are generally standard for organic chemistry. The dicarboxylic acid or anhydride selected for step (3) of the above scheme is the same as the prepolymer polyester preparation step in U.S. Pat. No. 3,763,079.
(1)]. These can be aliphatic, cycloaliphatic, unsaturated or aromatic. The hydrocarbon groups in the dicarboxylic acids can contain non-interfering groups such as O, S, N, halogen, keto, etc., ie can be substituted or interrupted with these. Examples of suitable dicarboxylic acids include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, maleic acid, fumaric acid, dilinoleic acid, diphenic acid, phthalic acid. , tetrachlorophthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid, cyclohexanedicarboxylic acid, p-phenylene diacetic acid, naphthalene dicarboxylic acid, dihydromuconic acid, β-methyladipic acid, trimethyladipic acid, ethyl ether-
Examples include 2,2'-dicarboxylic acid. If desired, anhydrides of the dicarboxylic acids mentioned above can be used, such as phthalic anhydride, tetrahydrophthalic anhydride, and the like. A preferred dianhydride is phthalic anhydride. Also, trimellitic anhydride can be used. The epoxide used in step (4) is epichlorohydrin/bisphenol A resin. Examples thereof are well known in the art and include, for example, the formula with the trade name Epon (registered trademark) [Ciel Chemical Company Bulletin SO71-1 "Epon Resins
(1976)]. Preferred for use in the present invention are compounds having the following properties, where the value of n is such as to give the following epoxide equivalent weight:

Table: Preferred in the present invention is an epoxide equivalent weight of about 950 (Epon 1004 or equivalent). It will be clearly understood that other well known commercially available epoxy resins may be used as well as Epons. The preparation of the products of the invention is relatively simple and can be accomplished in a single vessel (see Examples below). The copolyester-urethane is covered by Fryd's U.S. patent.
No. 3,763,079 and can be reacted with a dicarboxylic acid or its anhydride in a solvent or without a polyester-urethane/dicarboxylic acid molar ratio of 10/1 to 1/1. Epoxide is added to the same vessel in a polyester-urethane/epoxide molar ratio of 1/0.2 to 1/2 and end-capping and/or chain extension is performed. Reaction times and temperatures are not critical, typically e.g. 30-60 minutes for reactions with acids or anhydrides and 2 minutes for reactions with epoxides until the reaction is complete as shown in the examples. Refluxing for an hour or more may be used. The final products of this invention are generally organic solids and readily dissolve in common organic solvents. These solvents are in fact the solvents used to carry out the synthetic reactions. The product is useful as an adhesive when dissolved. Examples of suitable solvents include aromatic hydrocarbons such as toluene, xylene, tetrahydronaphthalene, decahydronaphthalene, etc., chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, e.g. diisopropyl ether, tetrahydrofuran, Ethers such as dioxane, ethylene glycol dimethyl ether, etc., esters such as ethyl acetate, butyl acetate, etc.
For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. may be mentioned. The solubility of polymers is highly dependent on the selection and proportions of acids and diols with which they are prepared. When used as adhesives, the epoxy-urethanes of this invention can be cross-linked. The cross-linking agent (or curing agent) can be an organic compound containing groups that react with the hydroxyl groups on the polyester-urethane-epoxy. Cross-linking agents have an average degree of functionality (functionality is the number of groups (such groups react with the hydroxyl groups on the epoxy-urethane) per molecule of cross-linking agent) of 2 or more, and often they are It has an average functionality of about 3 to 6, preferably about 2 to 6, more preferably 3 to 4. One form of suitable crosslinking agent is an aliphatic or aromatic polyester. Isocyanates, such as 4,4',4''-triisocyanate triphenylmethane, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, etc. , for example the expression Biurets of the above diisocyanates such as trimerization products of hexane-1,6-diisocyanate represented by: tolyl-2,4,6-triisocyanate, naphthalene-1,3,7-triisocyanate, diphenylmethane-2 ,4,
4'-triisocyanate, triphenylmethane triisocyanate, from about 3 to obtain a cross-linking agent with a degree of functionality of 2 or more but not greater than about 8.
one or more polyols having about 6 hydroxyl groups (e.g. propanetriol, 1,
2,6-hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, etc.) with one or more diisocyanates (eg, any of the aforementioned diisocyanates). Preferred polyisocyanates are adducts of aromatic diisocyanates (such as any of the aforementioned diisocyanates) with trimethylolpropane in a molar ratio of 3:1 or 5:2 with a degree of functionality of 3 or 4, such as 5:2. toluene-2,4-diisocyanate in a molar ratio of
Mention may be made of adducts of toluene-2,6-diisocyanate or mixtures thereof with trimethylolpropane. Amino or nitrogen-containing resins such as melamine-formaldehyde resins, urea-formaldehyde resins or benzoguanamine-formaldehyde resins are another form of cross-linking agent. Such resins require the application of heat. When using unsaturated copolyesters (i.e. copolyesters made from at least some unsaturated acids or unsaturated acid anhydrides) for the production of polyester-urethanes, such unsaturated polyester-urethanes can be used, for example, with benzoyl peroxide. Cross-linking can be achieved by mixing with a suitable free radical polymerization catalyst such as. Of course, free radical polymerization catalysts do not have the degree of functionality that the crosslinking agents have. Immediately prior to use, the epoxy-polyester-urethane is mixed with a cross-linking agent. The equivalent ratio of reactive groups (contained on the crosslinker) to hydroxyl groups (contained on the epoxy-urethane) is from about 1.0/1.0 to about 4.
0/1.0, preferably about 1.5/1.0 to about 2.5/1.0. The mixture is obtained by evaporation or addition of the solvent from about 0.5 to about 60% by weight, preferably from about 20 to
It may contain about 60% by weight epoxy-polyester-urethane and cross-linking agent. Cross-linking is carried out at room temperature for about 1/2 hour to 5 days depending on the cross-linker used. Heat and/or pressure may be applied to promote cross-linking and ensure good bonding between the bonded materials. As mentioned above, the cross-linked epoxy-urethanes of this invention are particularly useful as adhesives. Any suitable material such as paper, cellulose, polyester (e.g. polyterephthalate), polypropylene, polyethylene, polyvinyl chloride copolymers of vinylidene chloride and vinyl chloride, vinyl acetate and vinyl acetate and other free radically polymerizable monomers. copolymers of, polyamides, flexible films (e.g. produced from any of the foregoing suitable for the production of flexible films),
Metal foils, rubber, etc. can be bonded with the cross-linked epoxy-urethane of this invention. Of course, the same or different materials can be adhered to each other. Typically, the method for bonding materials is (1) applying a mixture of a cross-linking agent and epoxy-urethane to the surface of the material, (2) removing the solvent by air drying or heating, and (3) bonding the material in (1) above. It consists of placing another substance in contact with the mixture applied to it. Optionally, the fourth step of the method can be the application of heat, pressure, or heat and pressure. The mixture of epoxy-urethane and crosslinker is about 0.5 to 60% by weight, preferably about 20 to about 60% by weight.
can be applied to the material from a solution containing the cross-linking agent and the epoxy-urethane. If desired, a solution of the epoxy-urethane in the reaction medium can be mixed with a cross-linking agent and the product preferably adjusted to percent solids by evaporation of the solvent present or addition of more solvent if desired. It can be used directly after After applying the resulting solution to the substance, the solvent is removed. When the mixture of crosslinker and epoxy-urethane is used as an adhesive, additives of inert high molecular weight compounds, such as polyvinyl chloride, polyvinyl acetate, etc., can be added to the adhesive solution. Next, the present invention will be explained by examples. Example 1 Produced according to the method and composition (terephthalic acid, isophthalic acid, azelaic acid and ethylene glycol in a molar ratio of 33/17/50) as set forth in Example 1 of U.S. Pat. No. 3,763,079 and A prepolymer (553.9 g) having a hydroxyl number of about 50 and an acid number of about 2 was placed in a 2 volume three-necked flask equipped with a shaker, reflux condenser, and thermometer. This prepolymer (molecular weight 2244)
To the solution were added 146.7 g of toluene, 0.16 g of dibutyltin dilaurate, and 34.1 g of Hiren™ (toluene diisocyanate). This mixture (1/0.
8 molar ratio of prepolymer to diisocyanate)
was heated to a reflux temperature of about 127°C and held for 2 hours. At the end of the 2 hour hold period, 14.6 g of phthalic anhydride was added and the polyester-urethane/phthalic anhydride (1/2 molar ratio) mixture was refluxed for 40 minutes. At the end of this time 53g methyl isobutyl ketone (MIBK) and 199.2g Epon
Added 1004. 1/2 polyester-urethane/
This mixture with epoxide ratio was brought to reflux and held for 2 hours. At the end of 2 hours pour the mixture
It was diluted with 778.5 g of methyl ethyl ketone (MEK) and cooled to room temperature. The resulting solution had a viscosity of 145 centipoise (cps). This solution was useful as an adhesive to provide a film-tear bond when applied onto a Mylar film, dried and sealed to a second Mylar film with a Sentinel heat sealer. Example 2 In the apparatus of Example 1, 553.9 g of the prepolymer of Example 1, 146.7 g of MIBK, 0.16 g of dibutyltin dilaurate, and 37.5 g of Hiren™ were refluxed for 1 hour. At completion 20.1g trimellitic anhydride, 188.6g epoxide (Epon 1001,
epoxide equivalent weight 450-550) and 52.3g MIBK
added. The respective molar ratios corresponding to those shown in Example 1 are 33/17/50, 1/0.86, 1/2.5 and 1/4.75. The mixture was heated to reflux and held for 2 hours, then diluted with 597.5 g of MEK and cooled. This product has a viscosity of 185 cps when tested as described in Example 1 and provides tear bonding to Mylar films, indicating its usefulness as an adhesive. Example 3 The prepolymer was 3780 g of ethylene glycol,
Prepared by the method described in Example 1 of US Pat. No. 3,763,079 using 2227 g terephthalic acid, 1147 g isophthalic acid and 2967 g adipic acid in a 12 volume flask. This prepolymer was prepared to have a hydroxyl number of 32.5, an acid number of 2.0 or less, and a molecular weight of about 3452. 442.1 g of this prepolymer was added to the 2 volume flask of Example 1 above containing 91.7 g toluene, 30.5 g MIBK and 0.1 g dibutyltin dilaurate. 18 g of Hiren™ was added to the flask and the mixture was heated to reflux and held for 1 hour. At the end of the hold time 44.4 g of Epon 1007 and 1.5 g of phthalic anhydride were added and the mixture was again heated to reflux and held for 2 hours. The corresponding molar ratios are 33/17/50, 1/0.83, 1/0.5, 1/
It is 0.5. At the end of this time 366.5 g of MEK was added and the solution was cooled. This solution is 2000cps
It has a viscosity of Four 50 g samples of the polymer solution were measured and mixed with a toluene diisocyanate prepolymer adduct (Mongiur (registered trademark) CB-75, manufactured by Maupay Chemical Company). The first sample was 1 g of CB-
75, second sample is 1.7g CB-75, third sample is 2.0
g of CB-75 and a fourth sample were each mixed with 2.2 g of CB-75. All were coated on 0.3 mm thick dry film and tested as in Example 1. Peel strengths of 7.5 lbs/linear inch, 6.8 lbs/linear inch, 7.0 lbs/linear inch, and 7.5 lbs/linear inch were recorded, respectively. A second set of laminates was tested after standing for one week to obtain complete cross-linking. The recorded values were 6.3 lb/linear inch, 6.1 lb/linear inch, and 6.3 lb/linear inch, respectively.
5.4 lbs/lineal inch and 5.6 lbs/lineal inch. These results indicate that the product has excellent strength and is useful as an adhesive. Examples 4 and 5 The table below shows the composition (in grams) and properties of the products prepared and tested as in Example 3. Examples 4 and 5
The corresponding molar ratios of each reaction component used in are 33/17/50, 1/0.83, 1/2, 1/0.7 and 33/17/50, 1/0.83, 1/2, 1/0.5, respectively. be.

【table】

【table】

[Table] Example 6 Using the prepolymer composition of Example 1 and the operation of Example 2, 1077.7 g of MIBK, 1.2 g of dibutyltin dilaurate, 4068.6 g of prepolymer, 273 g
HirenTM, 53.7g phthalic anhydride, 344.5
Using 1004g of Epon and 4202.3g of MEK
A product was produced with a viscosity of 155 cps in a 12 volume flask. The corresponding molar ratio is 33/17/
50, 1/0.87, 1/1.44, 1/0.72. This product was tested as shown in Example 8 and shows excellent results. Examples 7-10 Tests were carried out to compare the properties of the products of the invention and those sold on the market as shown in the table below. The properties of the products of this invention are obvious to those familiar with the products sold commercially as 46960 (solution of saturated copolyester polymer) and 56065 (polyester-urethane solution). Remarkable.

【table】

Table: These compositions were applied onto a Mylar film at a coating weight of 5.0 lb/ream (3000 square feet), dried and sealed to another sheet of Mylar using a Sentinel heat sealer.
These laminates were cut into 1 cm pieces and tested as shown below after aging for one week to ensure complete cross-linking. 1 Immersed in test solutions A to H (table) for one week,
Wipe dry and age for 24 hours. 2 Heated to 100℃. 377〓 and 50% relative humidity for one week (control). Table (Test solution) A Tap water B Vegetable oil C 1% NaOH solution D 10% acetic acid solution E Isopropanol F Ethyl acetate G Toluol H Heptane

【table】

Claims (1)

[Scope of Claims] 1 (a) One or more diols or polyether glycols are combined with at least two different dicarboxylic acids, dicarboxylic anhydrides, or dicarboxylic acid methyl esters (these dicarboxylic acids, dicarboxylic anhydrides, or dicarboxylic acid methyl esters) About 40 to 80 mole percent of the acid methyl esters are aromatic and about 60 mole percent of these dicarboxylic acids, dicarboxylic acid anhydrides, or dicarboxylic acid methyl esters are aromatic.
(~20 mol% is aliphatic) and (b) at least one organic diisocyanate, the isocyanate contained in the diisocyanate versus the hydroxyl contained in the copolyester. in a molar ratio of from about 0.7/1.0 to about 1/1 at a temperature and for a sufficient time to form a copolyester-urethane, and to form a copolyester-urethane end-capped with a dicarboxylic acid or its anhydride. Trimellitic anhydride or malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, maleic acid, fumaric acid, dilinolenic acid, diphenic acid, Phthalic acid, tetrachlorophthalic acid, isophthalic acid, terephthalic acid and orthophthalic acid, cyclohexanedicarboxylic acid, p-phenylene diacetic acid, naphthalene dicarboxylic acid, dihydromuconic acid, β
-Methyl adipic acid, trimethyl adipic acid,
and ethyl ether-2,2'-dicarboxylic acid or its anhydride to the extent of 10 to 100% of the hydroxyl groups and the carboxyl groups of the end-capped copolyester-urethane. 10-100% of structural formula wherein n is an integer sufficient to provide an epoxy resin having an epoxide equivalent weight of at least about 450 and up to about 6000. A method for producing an epoxy-urethane consisting essentially of an epoxy-terminated and chain-extended copolyester-urethane. 2. The aromatic component of the copolyester is selected from the group consisting essentially of terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride and mixtures thereof and the aliphatic component is succinic acid, glutaric acid, adipic acid, azelaic acid. acid, pimelic acid,
The method according to item 1, wherein the method is selected from the group consisting of suberic acid, sebacic acid and mixtures thereof. 3 A copolyester is produced from (a) terephthalic acid, isophthalic acid, azelaic acid and ethylene glycol and (b) toluene diisocyanate, reacted with phthalic anhydride and epichlorohydrin/melting point of 95-105°C and 875°C. 2. Process according to claim 1, obtained by end-capping and/or chain extension with a bisphenol A type epoxy resin having an epoxide equivalent weight of ~1025. 4 A copolyester is produced from (a) terephthalic acid, isophthalic acid, adipic acid and ethylene glycol and (b) toluene diisocyanate, reacted with phthalic anhydride, and epichlorohydrin/a melting point of 95-105°C and 2. Process according to item 1, obtained by end-capping and/or chain extension with a bisphenol A type epoxy resin having an epoxide equivalent weight of 875 to 1025.