JPS60141710A - Polyurethane-acrylic acid ester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention Technical Field Invention 6 Hydrophilic polyurethane-acrylic ester compositions, in particular acrylic esters in the presence of one or more hydrophilic polyurethanes obtainable by reaction of polyalkylene glycols with diisocyanates. The present invention relates to a composition obtained by reacting one or more of the following.

Technical Background Patent Application No. 206, received November 12, 1980.
No. 407 describes polyurethane-diarylate compositions that are nearly insoluble in alcohols such as ethanol or methanol. The hydrophilic polyurethane-acrylic acid ester composition of the present invention forms a hydrogel when immersed in water. ions and nonionic substances with various molecular weights '1f! :To Penetrate. However, unlike the hydrophilic polyurethane-diacrylate compositions, these are soluble in alcohol.

(7) The parent aqueous polyurethane/acrylic ester composition of the present invention is prepared by reacting acrylic ester Y in the presence of one or more hydrophilic polyurethanes. A free radical catalyst may be present to initiate the reaction of the acrylic ester.

To the hydrophilic polyurethane used as one component of the present invention.

(Al　(at diethylene glycol.

(B) one or more diols having a number average molecular weight within the range of about 106 to 20,000 selected from the group consisting of (b) long-chain polyoxyalkylene diols, and (c) dialkanolamines; It is produced by reacting a urethane precursor selected from the group consisting of organic polyisosilinates and nitrile carbonates in the presence of an organotin catalyst. If desired, a polyfunctional lactone represented by the 11th formula (8) and ethers derived from the lactone may be added from 0.1% by weight to 30 parts by weight based on the total reaction mixture. . In the formula R+
f'st(,-〇82N)12.

-8020)13 , -G)[)HGOOH, and -
((3HO)1)nC) A monovalent group selected from the group consisting of 120H; nσ an integer from 0 to 5; R2 and a divalent group -
(CHOH) rn-; rn tj represents an integer from 2 to 10. Polyurethane resins containing such polyfunctional lactones are described in U.S. Pat. No. 4,156,066 and U.S. Pat. No. 4,156,067.

The hydrophilic polyurethane component coexisting with the diacrylic ester during the reaction contains diethylene glycol and long chain diols. The long chain diol is at least about 106. It should preferably have a molecular weight of rs1450 to 7500. Preferred diols are those in which the thick (9) portion consists of an oxyethylene group or an oxypropylene group, but may also contain other oxyalkylene groups in small proportions.

The polyisocytonate used to prepare the V-component of the invention is represented by tjR(Neo)n.

In the formula, ntd1 is thicker (, preferably 2 to 4), and H is an aliphatic group having 4 to 26 carbon atoms.

Alicyclic, aliphatic-alicyclic, aromatic or aliphatic-aromatic hydrocarbon compounds having a carbon number of σ6 to 20, generally 6 to 13, are commonly used. Representative examples of the above-mentioned sardines include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, infron diisocyanate, diethylbenzene diisocyanate, decamethylene 1.10-diisocyanate, cyclohexane 1.2-diisocyanate, and Cyclohexylene 1,4-diisocyanate; and aromatic incyanates such as 2,4- and 2
．． 6-) Lylene diisocyanate.

(10) 4.4-diphenylmethane diisocylene), 1.5-
Naphthalene diisocyanate, dianisidine diisocyanate, toridine diisocyanate; polymeric polyisocyanates such as neopentyl tetraisocyanate, m
-xylylene diisocyanate, tetrahydronaphthalene 1,5-diisocyanate, and bis(4-incyanatophenyl)methane.

A preferred isocyanate is methylene di(cyclohexyl incyanate). Other diinsyanates that are slightly less preferred include trimethylhexamethylene diisocyanate and isophorone diisocyanate.

Other compounds that may be used include incyanate equivalents that form urethane bonds, such as carbonate IJ carbonate (II) of the formula:

In preparing the hydrophilic polyurethane resin component of the present invention, low molecular weight glycols such as diethylene glycol, dipropylene glycol or aromatic glycols may be added to the reaction mixture. The preferred low molecular weight aromatic glycols are bisphenol A and 4,4'-sulfonyldiphenol.

The proportions of long chain polyglycols and low molecular weight glycols, i.e. diethylene glycol, present in the hydrophilic polyurethane component of the present invention vary depending on the ILB and H of the final composition.
Determined by LB. The higher the molecular weight of the long-chain polyoxyethylene glycol and/or the amount of the polyol, the more hydrophilic the final product becomes. This effect is counteracted by increasing the proportion of low molecular weight glycols, ie diethylene glycol or dipropylene glycol, by 2.

If we understand the fact that what determines the hydrophilicity is the number of polyethylene oxide groups in the polymer molecule, we can understand that upon reaction with the acrylic ester (I2) the hydrophilic polyurecne present will have the desired properties. It is easy to select the reaction mixture as follows.

The hydrophilic polyurethane component can be tailored to satisfy a wide range of properties by selecting the polyethylene glycol molecule 12 or by using two poly57 alkylene glycols with different molecular weights. As used throughout this specification and claims, the term "hydrophilic polyurethanes" refers to polyurethanes that form hydrogels through hydrogen bonding and that when immersed in water have at least 2
Polyurethanes that absorb 0% water by weight.

In addition, the hydrophilic polyurethane-acrylate composition of the present invention, like the hydrophilic polyurethane component, forms a hydrogel when immersed in water and contains at least 20% by weight.
absorbs water.

As mentioned above, the hydrophilic polyurethane component that reacts with the acrylic ester to form the composition of the present invention may contain a polyfunctional lactone. Typical examples of polyfunctional lactones are polysaccharides and monosaccharides such as mannolactone, delta gluconolactone, sorbolactone, and D(13) monoglucuronolactone.

The lactones used have at least 6, preferably 4 or more, hydroxyl groups in the molecule, or at least one more hydroxyl group than is required to form linear polyurethanes. It is desired that Free (unreacted) hydroxyl groups remain in the main chain of the polymer and participate in crosslinking of the polymer. The lactone ring is also reactive and opens upon hydrolysis to form carboxylate or carboxyl groups in the backbone of the polymer.

In making the first component of the invention, the lactone, if present, is mixed with the KH glycol lactone.

A polyisocyanate is reacted with this mixture.

However, there are other methods as well. The reaction takes place catalytically with known catalysts for such reactions, suitable catalysts being tin salts, organotin esters such as dibutyltin dilaurate, triethyldiamine (DABOD).

or N, N, N', N'-tetramethyl-1
, tertiary amines such as 6-butanediamine, and other known (14) catalysts for urethane reactions.The reaction may be carried out with or without the presence of a diluent or solvent. I can do it.

The second component of the composition of the present invention is the σ acrylic ester! The term "acrylic acid ester" is used throughout the present specification and claims to refer to monoacrylic monomethacrylic acid having up to 16 carbon atoms, which is produced by combining 1 mole of σ acrylic acid or methacrylic acid with 1 mole of alcohol. Ester Y. Preferred acrylic esters are hydroxyethyl methacrylate, methyl methacrylate and methyl acrylate, but other acrylic or methacrylic esters may also be used.

When producing the hydrophilic polyurethane acrylic ester composition of the present invention, 100 parts by weight of one or more polyurethanes are mixed with about 1 part of one or more acrylic esters in a solvent such as methanol or 95% thiemenol.
Preferably, a free radical catalyst is added to dissolve and initiate the conjugation of the acrylic ester (15) with 0 to about 50 parts by weight. A film is formed by solution casting of the two components and cured by heating at a temperature within the range of 110°C to 1'55°C, or the film is cured by the action of ultraviolet light. If the insolubilization of the two-component composition is initiated by ultraviolet radiation, no free radical catalyst σ is required. However, it may be desirable to add to the binary mixture an ultraviolet absorber such as Rhodamine B and an azo-type catalyst such as azohizisobutyronitrile.

When it is desired to make molds or tubes from the hydrophilic polyurethane acrylic ester composition of the present invention, a. Remove the solvent under reduced pressure and heat the remaining mixture at 110°C to 165°C.
Cure the hydrophilic polyurethane acrylate composition by molding for about 20 to about 60 minutes at a temperature of .degree.

The hydrophilic polyurethane acrylic ester composition of the present invention absorbs water, and the amount of water absorbed depends on the composition, the nature of the hydrophilic polyurethane present in the composition, the amount of acrylic ester present in the composition, and the amount of water absorbed. (16) Varies depending on model.

The hydrophilic polyurethane acrylic ester resin compositions can also be used in coatings, molding compounds, absorbents, tunable mold release agents, ion-exchange resin dentistry, and dialysis membranes, power 2 lenses, contact lenses, packaging materials. , desalination membrane, burn bandage,
Birthing devices, sutures.

Surgical implants, blood oxygenators, intrauterine devices, canal prostheses, oral feeding devices, battery septa, eye bandages, corneal prostheses, anti-fog paints, sterile surgical cloths, oxygen exchange. Membrane 1 Artificial fingernails, fingernails, adhesives, gas permeable membranes, and belly-retaining paints,
It can be used in the production of chemical-resistant paints.

The practice of the present invention is further illustrated in the examples in the appendix, which are not intended to limit the invention. Parts used in the examples indicate parts by weight unless otherwise specified.

[Example I]

Carbowax 8.000 in a container
x8.000) (Product name: Union Carbid
e Corporation + New York
A polyurethane polymer is prepared by melting together 822.3 parts of polyethylene glycol having a number average molecular weight of 3,000 (manufactured by New York 10017) (17), 23.0 parts of diethylene glycol, and 5.4 parts of water. The mixture becomes clear at about 80°C and is cooled to 75°C. When the temperature reached 75℃, methylenebiscyclohexyl-4゜4'-isocyanate (
Mobay Chemical +Corporati
on + Penn Lincoln Parkway
West+ Pi)Isburgh, Penn5yl
Made by vania 15205, product name DESMODUf (
Add 149.7 parts of the product. Mixture care 5℃
After stirring for 15 minutes and cooling to 50°C, organotin catalyst-dibutyltin dilaurate (Metal and
ThermiteG company of Ftah
Add 2.0 volume parts of T12 (trade name) manufactured by New Jersey, Inc. The catalyst is added and the reaction mixture is exothermed from 50°C to 75°C. #! The molten product Y was poured into a polypropylene pan at 75°C and heated in a furnace to 100°C to complete the reaction and obtain a foamed hydrophilic polyurethane as a product. When you soak it in water,
This raw material (1B) absorbs 100 parts of acid and 470 parts of water (water absorption rate: 4470
%).

When this polyurethane product was cooled to room temperature, taken out from the pan, and dissolved in 95% ethanol, the solid content was 982%.
A solution containing % by weight is obtained.

6.0 parts of methacrylic acid hydroxyethyl ester was added to 305.5 parts of this polyurethane ethanol solution.

Add 0.427 volumes of peroctanoic acid tert-butyl ester with stirring. Evaporation of the solvent under reduced pressure at room temperature yields a product containing 10 parts of hydrophilic polyurethane and 20 ffB of methacrylic acid hydroxyethyl ester. This is then heat treated at 121° C. for 20 minutes. Product salt water after heat treatment 408 to 428
The elongation is 70 inches to 75%.

[Example I]

Contact lenses Y can be manufactured from a solution using the swirling method. A mixture of 1305.5 parts of the polyurethane ethanol solution described in Example I, 6.0 parts of methacrylic acid hydroxyethyl ester and 0.42711 J of perthioctaic acid tert-butyl ester was evaporated under reduced pressure to form a solution. Viscosity is 12 to 15
Poise (solid content until non-volatile content is 11 to 1υ1?
increase.

A concave mold matching the convex side of the desired shape of the contact lens is placed on a vertical axis that can be rotated at a maximum speed of 200 rpm.

Add a 12 to 15 poise solution groove halfway up the cavity of the mold. Rotate the mold slowly at 4 speeds to maximum speed for at least 5 minutes.

After rotating at maximum speed for an additional 5 minutes, the rotating mold is brought to a standstill.

The mold is then placed in a furnace with a nitrogen atmosphere. Next, the temperature was gradually raised to 125°C and left for 20 minutes. When the mold is placed in water after cooling, the polymer becomes hydrated and begins to fall out of the mold.

If necessary, the polyurethane-methacrylic acid hydroxyethyl ester composition described in Example I is mixed with a cross-agent or filled into capsules prior to the heat treatment step. Drugs dispersed in this way are, for example, vitamins, hormones, steroids, (2o) herbal medicines and antituberculous drugs.

The heat-treated polymer gradually releases the drug when placed in an aqueous saline solution or body fluid. Accordingly, the compositions described in this example can be formed into any convenient form, such as tablets for oral administration, implants, intrauterine devices, membranes for controlled slow kK release, and suppositories. If desired, a daughter repellent such as lactic acid is added to the membrane or contraceptive during its manufacture.

[Example Amount]

Hydrophilic polyurethane resin 30 as described in Example I above.
6.0 parts of methyl acrylate and 0.427 parts of tert. Evaporation of the solvent at room temperature under reduced pressure yields a product consisting of 100 parts of hydrophilic polyurethane and 20 parts of methyl acrylate.

This product is heat treated in various forms by heating in an oven under nitrogen at 121 DEG C. for 60 to 60 minutes. Heat-treated polyurethane-acrylic (21) methyl sulfate compound absorbs 716% to 758% of water and has an elongation of about 112%.

In addition, the polyurethane-methyl acrylate composition was heated to 100°C.
The product is heated under pressure in a press, and the temperature is raised to 160° C. for 2 minutes while maintaining the E force to compression mold it into a flat sheet or contact lens shape.

The sheet is used as a membrane for the transmission of water and steam, and has medical uses as a surgical sterile cloth (sometimes coated with an adhesive on the side) and as a membrane for the transmission of water and steam. It is particularly suitable as a burn dressing when it contains a medicinal agent. Polyurethane-acrylic acid ester composition (containing methyl acrylate 1D weight it4 or more)
are useful as dialysis membranes and have applications in the field of separation technology.

[Example　■]

A polyurethane-methyl methacrylate composition is developed from the following mixture by the method described in Example 1 above.

Hydrophilic polyurethane (98% ethanol solution of Example I) 305.5 parts (22) Methyl acrylate 6.0 parts Tert-butyl peroctoate 0.432 parts This solution was evaporated to dryness under reduced pressure at room temperature. By extrusion under heat and pressure, a product is obtained that allows for the production of hydrophilic cannulae with desired physical properties. If necessary, the resin is mixed with a drug before extrusion.

The polyurethane-acrylic acid ester compositions described in the examples (in ethanol solution) can also be used to coat preformed cannulae, which, after evaporation of the solvent, can be heat treated at a temperature of 120 °C. I can do it.

The above composition was heated at 201° C. in an inert atmosphere in a furnace.
After heat treatment for 50 minutes, the resulting product absorbs 726 inches of water and has an elongation of 111 inches.

The resin composition of this example was prepared by adding iodine (23) after heat treating the polyurethane-methylene methacrylate composition to form a cast film that slowly releases iodine and can be used as a wound dressing. be done.

[Example　■]

The hydrophilic polyurethane described in Example ① (solid content 9
．． 3 parts by weight of mercurous acetate and 1 part by weight of honey (resin (relative to solid content). This bath solution can be applied to the hull of a boat and cured by actinic radiation in sunlight to form an insoluble coating.
This coating reduces underwater resistance and mercury is gradually released, inhibiting the growth of marine life.

[Example　■]

The hydrophilic polyurethane described in Example 1 (solid content 9
．． An ethanol solution of 305.5 parts of methacrylic acid and droxyethyl ester, and 0.427 parts of tert-butyl peroctanoate was heated at room temperature under a sacrificial pot to produce ethane! -Remove the key. The resulting white solid is extruded under pressure at a temperature below the heat treatment temperature to form an almost completely cured water and gas permeable tube Z. Such tubing is used in renal dialysis machines.

(25) Continued from page 1 ■Int, CI,' Identification code Internal reference number 0 Inventor Christian Dabri American Congregation I New York Station number 1°1 New Chassis 08853. Neshanin, Amwell Road, R Box 19

Claims (1)

[Claims] 1. A gas comprising about 100 parts by weight of hydrophilic polyurethane and about 10 to 50 parts by weight of acrylic ester, which forms a hydrogel when immersed in water. A hydrophilic polyurethane-acrylic ester composition permeable to ions and non-ionic substances of small molecular weight. 2. The hydrophilic polyurethane-acrylic ester composition according to claim 1, wherein the acrylic ester is hydroxyethyl methacrylate. 6. The hydrophilic polyurethane-acrylic ester composition according to claim 1, wherein the acrylic ester is methyl methacrylate. 4. The hydrophilic polyurethane-acrylic ester composition according to claim 1, wherein the acrylic ester is methyl acrylate. 5. The hydrophilic polyurethane-acrylic ester composition of claim 1, wherein the acrylic ester is about 17% by weight of the composition. 6. The hydrophilic polyurethane-acrylic ester composition according to claim 5, wherein the acrylic ester is hydroxyethyl methacrylate. 1. A hydrophilic polyurethane-acrylate composition according to claim 1, wherein the polyurethane is derived from a mixture of polyols and diisocyanates. 8. The hydrophilic polyurethane-acrylic ester composition according to claim 7, wherein one of the polyols is a polyol having a molecular weight of 8,000. 9. A burn bandage made of the hydrophilic polyurethane/acrylic acid ester (2) according to claim 1 in the form of a film. 10. A burn dressing as claimed in claim 9 containing a medicament in the hydrophilic polyurethane-acrylic ester composition. 11. A burn dressing according to claim 10, wherein the 1 t nuclear F drug is sulfadiazine. 12. An intratissue implant comprising the hydrophilic polyurethane-acrylic acid ester composition described in claim 1 and containing the drug Y. 16. Claim 1, wherein the medicine is an anti-tuberculosis drug.
The tissue implant described in Section 2. 14. Claim 12, wherein the drug is the active drug
Tissue implants as described in Section. 15. Claim 1, wherein the medicine is a hormone.
The tissue implant described in Section 2. 16. The tissue implant according to claim 12, wherein the Yjs drug is a steroid. 17. Claim 1, wherein the medicine is a vitamin.
The tissue implant described in Section 2. 1B. An interstitial implant according to claim 12 in the form of a contraceptive device. 19. A contraceptive device as claimed in claim 18 in the form of a membrane trap. 20. A contraceptive device according to claim 18 in the form of an intrauterine device. 21. The intrauterine device according to claim 20, wherein the anti-eating agent is lactic acid. 22. A cannula whose walls are formed of the hydrophilic polyurethane-acrylic ester composition according to claim 1. 26. The cannula according to claim 22, wherein the hydrophilic polyurethane-acrylic ester composition contains a medicament throughout. 24. Claim 22, wherein the drug is iodine
Cannula described in section. 25. A cannula in which at least one of the walls is coated with a hydrophilic polyurethane-acrylate composition according to claim 1. 26. An orally administered mixture comprising a pharmaceutically active agent and the parent (4) aqueous polyurethane-acrylate composition as claimed in claim 1 as its carrier vehicle. 2Z Gas permeable 1 m formed of the hydrophilic polyurethane-acrylic acid ester composition described in claim 1 above. 28. A corneal prosthesis comprising the hydrophilic polyurethane-acrylic ester composition described in claim 1. 29. A method of imparting moisture to a dry gas, comprising passing the gas through a tube formed of the hydrophilic polyurethane-acrylate composition according to claim 1. 60. A surgical sterilization cloth formed of a membrane of the hydrophilic polyurethane-acrylic ester composition according to claim 1. 61. A dialysis membrane formed from the hydrophilic polyurethane-acrylate composition described in claim 1. 32. A surface liquid oxygen supply device comprising a carbon dioxide-oxygen exchange membrane formed of (5) the hydrophilic polyurethane-acrylic acid ester composition described in claim 1. 63. A contact lens comprising a molded hydrophilic polyurethane-acrylic ester composition according to claim 1. 34. The hydrophilic polyurethane-acrylic ester composition according to claim 1, which is molded into a desired shape. 65° About 10 to about 50 parts by weight of acrylic ester? A method for preparing a hydrophilic polyurethane-acrylic ester composition comprising reacting in the presence of about 100 parts by weight of a hydrophilic polyurethane. 36. A transparent object provided with fog resistance wh by the hydrophilic polyurethane-acrylic ester composition described in claim 1. 3Z A boat whose hull is coated with the hydrophilic polyurethane-acrylic ester composition described in claim 1 to provide underwater resistance suppressing properties. (6)