JPH04502777A - UV-curable formulations of vinyl ether polyurethane and unsaturated elastomers and coatings containing the same - 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] UV-curable formulations of vinyl ether polyurethanes and unsaturated elastomers and Paint technology field including this The present invention relates to vinyl ether-terminated polyurethane and ethylenically unsaturated elastomer. UV-curable formulations of Stomer and also include coatings containing these formulations. . These formulations contain catalysts that cause cationic vulcanization to occur when exposed to actinic radiation. Therefore, unsaturated elastomers participate in vulcanization and have the effect of softening vulcanized paints. Ru.

Background technology UV-curable paints based on acrylate-terminated polyurethanes is well known. Many fast-curing polyurethanes with terminal acrylate groups are used for optical glass. It is too hard for some purposes, such as a primer for lath PI strips, and It is combined with a liquid substance that has the effect of softening the film formed during vulcanization. be done. Ethylenically unsaturated elastomers, some of which are 1m sulfurized. Since it is a long-chain molecule that softens paint, it has been attempted to be used as a softening agent. It's been coming.

However, these unsaturated elastomers are contained within this elastomer. Ethylenic unsaturation does not participate fully in free radical-initiated vulcanization and is present in the vulcanized product. It was useless because of its residual ethylenic unsaturation. This remaining The tyrenic unsaturation remains reactive, so that the vulcanized film is likely exposed to atmospheric acids. Vulcanized film ages by reacting with the elements and hardens over time. . This hardening leads to embrittlement, especially at low temperatures.

Ethylenically unsaturated elastomers in radiation-curable mixtures terminated with acrylates This unfavorable result obtained with polymers suggests that this type of mixture softens UV-curable compositions. was not considered as a suitable substance for conversion.

Summary of the invention In the present invention, in the presence of a cationic photoinitiator that actually has hydroxyl functionality, the ultraviolet Curable by actinic radiation at or near the line. Vinyl ether as a terminal group A liquid mixture consisting of polyurethane and an ethylenically unsaturated liquid polymer elastomer. The present invention provides a compound that undergoes cationic vulcanization when exposed to actinic radiation. These as a mixture with one quantity of a cationic photoinitiator having an initiating action. Surprisingly, unsaturated elastomers, including formulation-containing paints, Although it does not participate in conventional free radical polymerization, it participates in cationic vulcanization. In the paint of the present invention, the unsaturated elastomer has the effect of softening the vulcanized paint. have a purpose.

Polyurethane whose polyol polyvinyl ether has vinyl ether as a terminal group It is noted that it is a useful diluent for the Should be. However, these polyfunctional reactive diluents are generally used in vulcanized compositions. It has the effect of hardening. Monovinyl ethers are usually somewhat volatile and therefore This can be used in UV-curable paints that are desirably free of volatile components. is undesirable, this reduces the slight chance of increasing the softness of the vulcanized paint and therefore In order to reduce or at least compensate for the proportion of reactive diluent in the lever, It is desirable to reduce the hardening effect by introducing the softening effect of Ru.

Despite these difficulties, vinyl ethers can be used to produce softer coatings. It would be desirable to be able to use polyurethanes terminated with . That's because Vinyl ethers are more toxic and troublesome than the corresponding acrylate-terminated materials. No. 1: In some cases, cationic vulcanization is extremely fast. It is. These paints benefit from the increased softness provided by the unsaturated elastomers. This allows the paint to maintain its optical properties without introducing low temperatures, which pose a slight challenge. Optical glass fibers that need to be allowed to contact the glass surface of the fiberglass. Particularly suitable for coaching purposes.

Vinyl ether-terminated polyurethanes are known per se and are vulcanizable. Processed materials tend to harden and become brittle, and those with relatively low molecular weights have a tendency to become hard and brittle. It is harder and more brittle than its molecular weight counterpart. For the purpose of the species In this case, the hardness of the vulcanized polyurethane is not a problem, and it is desirable to soften it. . In this case, softness is measured by reduced tensile strength and reduced elastic modulus. workman Ethylenically unsaturated liquid polymer elastomer based on the total weight of lastomer and polyurethane The mixture contains from about 0.1% to about 40%, advantageously from 0.5% to 20%, of stomers. It has been found that the desired softness is produced when this is vulcanized by cationic vulcanization. this The effect is particularly important when the polyurethane is of higher molecular weight. Because this These polyurethanes have a higher viscosity and are more reactive to obtain a coating viscosity. The liquid unsaturated high molecular weight elastomer used here requires a diluent. - increases the softness as well as the proportion of reactive diluent needed to apply the composition. can be lowered.

Saturated elastomers are not useful in this case because the saturated elastomer prevents vulcanization. This is also because it slows down this process. The higher the proportion of saturated elastomer, the more the desired Cationic vulcanization is increasingly hindered.

In comparison, ethylenically unsaturated elastomers participate in cationic vulcanization and remain The unsaturation is largely removed by its vulcanization, and the vulcanized film is tested for heat aging. No difficulties were encountered during this process.

Detailed description of the invention As pointed out earlier, the paint according to the present invention is made of vinyl ether-terminated polyurethane. It consists of a blend of tan and an ethylenically unsaturated liquid polymeric elastomer.

Vinyl ether terminated polyurethanes are well known. These polyurethane The compound is prepared by conventional methods from aliphatic vinyl ethers, which are known and available compounds. It will be done. These -valent vinyl ethers can be prepared in various ways, e.g. by polyhydric alcohols, usually By reacting diol with acetylene in the presence of potassium hydroxide as a catalyst Therefore, it is formed. Therefore any liquid diol such as 1,4-butanediol is partially reacted to form a monovinyl ether, and this monovinyl ether is It can be separated and obtained as such. Other aliphatic vinyl ethers can also be produced in the same way or in other ways. These -valent vinyl ethers produces polyurethanes in which -valent acrylates terminate in vinyl ethers. It is used as a capping cutter for as well as inocyanate end groups and It can be used as an unsaturated capping agent for oligomers.

The present invention is characterized in that monovinyl ether of 1,4-butanediol is used as vinyl ether. Although the explanation will be based on the following examples, it is also possible to substitute the aliphatic-valent vinyl ether of ponds. You should understand that it is possible. These other vinyl ethers are, for example, 1.4 -Cyclohexane dimetatool, 1,6-hexanediol, ethylene glycol monovinyl ether of triethylene glycol or triethylene glycol. −valent vinyl ether The higher functionality polyols used to make the polyolefins are e.g. divinyl ether of propane or glycerin.

More specifically, vinyl ether-terminated polyurethanes are aliphatic-valent vinyl ether and incyanate-terminated oligomers (which are organic diisocyanate-terminated oligomers) Anate and incyanate The stoichiometry of a substance that has a large number of reactive hydrogen atoms, usually two. is a reaction product with a theoretically insufficient amount of vinyl ether Polyurethanes with terminal groups include Bishop (B15-hop), Pasta-Nut Paternack and Cutter, U.S. Pat. No. 4, No. 472.019 and Lapin TIL and House ) in U.S. Pat. No. 4,751.273. these statements In each of these, the vinyl ether-terminated polyurethane is an aliphatic vinyl Formed by reacting an ether with a diisocyanate. many organic Diincyanates are described in the Rabin and House patent specifications, which include Preferable ones are also included in the present invention.

Incyanates - Substances with a large number of reactive hydrogen atoms are usually polyols or and if they are used in insufficient stoichiometric amounts, incyanate Oligomers with terminal groups are formed. Polyols are advantageously diols, especially polyols. Ether diols, such as polyoxyethylene glycol, polyoxypropylene glycol or polytetrahydrofuran, but diol and caprolactone Also useful are polyester diols, such as reaction products with. These diols may have a molecular weight of from about 60 to about 3,000, preferably from 300 to 2,000. Corresponding diamines are also useful, in which case isocyanine is used instead of polyurethane. A nate-terminated polyurea is produced. Substances with higher functionality are e.g. Tyrolpropane and its use with alkylene oxides such as propylene oxide It is an adduct. The terminal hydroxy groups in these polyols are amine groups, advantageously can be replaced by a primary amine group, in which case for use in the present invention A polyamine that can be dissolved is produced.

These incyanate-terminated oligomers are used in the present invention to form monovinyl ethers. or polyvinyl ether. capped by After capping with -valent vinyl ether, the top All of the above incyanate-terminated polyurethanes or polyureas are This is a polyurethane with a polyether as a terminal group, and this is also a polyurethane in the present invention. Include as.

Capped polyurethane is multi-step, i.e. incyanate-terminated. monomers that form oligomers that are then later reacted with polyols or polyamines. The capping agent is pre-reacted with the diisocyanate to form the soocyanate. or by reacting all of each reactant together simultaneously. It should be noted that it can be manufactured by All of these variants is an aliphatic-valent vinyl ether isocyanate-reactive polyol or polyamine and and inocyanate-reactive functionality. Permissible in connection with reaction products of isocyanates (preferably diisocyanates) It is possible and will be adopted.

Urethane and urea forming reactions are well known and advantageously include dibutyltin dilaurate. easily carried out by heating to a moderate temperature in the presence of a suitable catalyst such as 9 The reaction is usually carried out at a temperature of 40 to 80°C to ensure completion. Promote it. This example is a good illustration of the urethane reaction and involves the reaction with urea. The reaction can be carried out similarly, except that no catalyst is required.

Additionally, certain aromatic diinsyanates, namely alkylene bisphenyl diisocyanates, It is also preferred to use anates, which compounds are well known in their own right. the Alkylene groups contain 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Examples are 1,2-diphenylethane diisocyanate and 1,3-diphenylethane diisocyanate. Nylpropane diisocyanate. Two phenyl groups are present on the same carbon atom It is preferable to use a compound which is a derivative of methane. It can be regarded as. A preferred diisocyanate is 4.4°-diphenylmeth The present invention, which is a diisocyanate, is particularly suitable for contacting the glass surface of optical glass PJ fibers. The present invention relates to paints that retain sufficient softness upon vulcanization for use as paints. For this is a vinyl ether having an average molecular weight within the range of about 1.50.0 to about 6,000. Presence of elastomeric components, preferably using polyurethane terminated If not, materials with low molecular weights in this range should not be used in contact with optical glass surfaces. is too hard, and optical glass P! has a high molecular weight in this range. Primer on fibers Too hard to use as However, with the present invention, this entire molecular weight range is even more effective. softened.

Therefore, it is more useful in areas where increased softness is desired.

Ethylenically unsaturated liquid polymer elastomers are well known in their own right and can be carbonized. It is a hydrogen or halogen-substituted hydrocarbon. Any diethylenically unsaturated C4 or is a liquid polymer of C9 hydrocarbons or halogen-substituted hydrocarbons, such as butadiene. Ene or chloroprene are suitable. These polymers usually have oily liquid properties. and low viscosity ones have excessive viscosity (higher than desired for applying the coating). ) or optionally terminated with a vinyl ether having solid properties. Polyisoprene is preferred because it reduces the viscosity of polyurethane. A useful ethylenically unsaturated elastomer, liquid polyisoprene is currently available. It is useful and can be used illustratively.

The actinic radiation considered in the present invention is preferably ultraviolet radiation between 200 and 400 nm, but The wavelengths of light that can be used include visible light near ultraviolet rays as well as those within ultraviolet rays. therefore, as used herein, actinic radiation is defined as radiation sufficient to initiate cationic polymerization. Includes and uses rays of energy.

These paints contain cationic photoinitiators that initiate cationic vulcanization when exposed to actinic radiation. , usually promoted with sulfonium compounds. The proportion of this photoinitiator is an effective amount, advantageously is less than about 1.5% based on the weight of unsaturated material present. catalyst A preferable ratio is O01% to L, 4%, fk is also preferable based on the weight of the above substance. is 0.2% to 1.0%.

Cationic photoinitiators are well known per se and are commercially available. Representative of this photoinitiator The common ones are sulfonium compounds, but iodonium compounds are also diazo compounds. It is a known cationic photoinitiator. These compounds are used in the proportions already mentioned. used. An excellent exemplary catalyst is triphenyl hexafluorophosphate. Ruphonium salt, registered name UVE 1016 and General Ele. It is commercially available from Ctric Co., Ltd. Commercially available photoinitiators in propylene carbonate It is provided as a 50% solution of A small amount of this volatile solvent introduced with the catalyst is too small to impair the essentially solvent-free properties of the compositions used herein. . The commercially available catalyst composition used in each example had an activity of 50% (50% of the catalyst composition was charcoal). acid propylene solvent), and therefore half of the commercially available catalysts are actually It is a catalytic substance.

This class of cationic photoinitiators is further described in U.S. Pat. No. 4,156,035. Although it is discussed in detail, the content is written in the form of references. This patent Specifications include Section VIA, which is capable of separating Lewis acids when exposed to radiant energy. We show that radiation-sensitive aromatic onium salts of group elements can be used, and as an example Especially to triphenylsulfonium fluoroborate, triphenylsulfonium Hexafluorophosphate and triphenylsulfonium hexafluoroanti Monet is mentioned. This patent specification describes these onium salts as carbonyl salts. those described as molecule-type photoinitiators, i.e. directly bonded to the carbonyl group. Aldehyde and ketone carbonyl compounds having at least one aromatic nucleus It is used in combination with other things. This type of carbonyl type photoinitiator is used in the present invention. It is also possible to use onium salts which can be functionalized by themselves. Preferred diaryliodonium salts 1 such as those commercially available under the registered name FC509 3M products such as benzophenones are also considered, but these are usually Onium salts that can be considered, used in combination with photoinitiators, are Patent Nos. 4,069.055, 4.069.056 and 4,423. It is described in the specification of No. 136.

Iodonium salts usually require the presence of an aryl ketone, making them difficult to register. 3M products commercially available under the registered name FC50g and registered names UVE 1014 and Products commercially available under UVE 1016 (General Elect It is preferable to use triarylsulfonium salts such as ric Co., Ltd.). desirable, these sulfonium salts do not require the presence of an aryl getone. stomach.

Cationic vulcanization is well known per se. Amine and carboxyl functional compounds are It is known to be harmful and therefore its inclusion in paints is inappropriate.

It is known that small amounts of hydroxy functionality inhibit the vulcanization of vinyl ether systems. There wasn't. By the way, add 0.1% hydroxy functionality to the weight of the composition By the cationic vulcanization in the present invention, no hydroxy functionality was added. It turned out to be about three times slower than the previous version. This is actually hydroxy-free It shows the importance of composition.

Thickness is an important factor in this invention, 1 to 10 mils for vulcanized paints and 2.5 mils for thickness. Optical glass fibers as contemplated herein, preferably having a thickness of ~6 mils In a typical glass coating, the coating applied to the glass is approximately 3.0 mil thick. , which requires that its entire thickness be rapidly vulcanized, thereby making it difficult to fracture. Good physical properties including not enough elongation resistance and waterproofing (including both absorption and extraction) A clear coating of very light color with characteristic properties is obtained.

Rapid vulcanization of these relatively thick coatings requires at least about 0.5 J/sqcm and This is usually achieved by projecting ultraviolet radiation at slightly higher doses. here The paint evaluated had a thickness of approximately 3 mils and was first exposed to 0.75 J/sqcm. Next, it is vulcanized by irradiation of Q, 5 J/sqcm.

The proportion of cationic photoinitiator used in the present invention is extremely important. 351g of cationic photo #IM agent along with ether-terminated polyurethane When used in typical amounts of ~4%, the vulcanized film has an f! Fades at the edges and prevents vulcanization and therefore does not span the entire length of the film, where advantageously the sulfonyl Outstanding vulcanization rates are obtained when using 0.5-0.9% photoinitiator. . In other words, just by irradiating 0.5 to 0.7 J/sqcm, the entire film is exposed. Complete vulcanization occurs and the vulcanized paint is clear and has a light color as described above.

When using acrylate-terminated polyurethane compositions, many Requires much more irradiation than 0.5J/5qctn when using a radical photoinitiator and the vulcanizations provided here are those obtained with conventional acrylate functional compositions. at least approximately the same speed.

Vinyl ether-terminated polyurethanes, unsaturated elastomers and photoinitiators may be the best substance present, but other ethylene series saturated substances, especially inbutyl vinyl ether, vinyl ether such as octyl vinyl ether, or 1.4 -butanediol, 1°4-cyclohexanediol or 1,6-hexanediol Even in the presence of polyvinyl ether represented by divinyl ether of Good, these substances are reactive diluents, and they affect the reactivity and viscosity of liquid paints. as well as modifying the hardness of the vulcanized product. Polyvinyl ether thins the paint. Depending on the degree of hardness, the elastomer component has a corresponding hardness. let

Reactive diluent is not an essential requirement of the invention, 5i, if a reactive diluent is used, The vinyl ether-terminated polyurethane is about 20% polyurethane in a mixture with a reactive diluent. % to 99%, advantageously 30% to 80%. Lastomer components, some of which are reactive and liquid, belong to that category. Despite this, there are many preferred reactive diluents that are not considered reactive diluents. These diluents, which are polyvinyl ethers of polyvalent compounds, have lower viscosities and lA It provides only limited additional hardness to the composition.

As highlighted above, the urethane-forming reaction actually depletes all of the hydroxy functionality present. promote the exhaustion of all things. In this case the hydroxy functionality is actually Not present in the composition means that the hydroxyl content is less than 0.11% by weight of the composition. Additionally, hydroxy-functional vinyl ethers are non-polyurethane vinyl ethers. When tel is used as a reactive diluent, it is not actually present in the composition, so Hydroxybutyl vinyl ether is used to increase the hydroxy content of the composition. In the present invention, it can be used as a diluent because it increases the amount beyond the limit value. Vulcanization is also inhibited by small amounts of hydroxyl functionality in the composition to be vulcanized. , therefore the composition that also vulcanizes rapidly is the one containing the least hydroxyl functionality. .

Paints according to the present invention are vulcanized in an atmosphere with relatively low relative humidity, e.g., less than about 45%. The preferred range is 30% to obtain lower relative humidity. Usually it is at least about 15% because it is difficult to do so. Preferably 25 % relative humidity and all results obtained are at 25% relative humidity. It was obtained from a film vulcanized in the atmosphere.

These coatings are compatible with typical vinyl coatings to enable or enhance this type of utility. A more rapid vulcanization rate than that obtained from ester-terminated polyurethanes. Particularly suitable for obtaining coatings for optical glass fibers where increased flexibility and softness are required. . Primers and single coatings for optical glass fibers and ribo coated optical fibers. The ribbon paint that collects in a ribbon shape provides the excellent appearance of the present invention9. Also contemplated herein are actinically vulcanized paints having the utility of Useful in areas where great softness is desired.

Other advantages and features of the invention will be apparent to those skilled in the art from each side listed below. All "r parts" in "r" are parts by weight.

Vinyl ether terminal group Polyurethane Oligomer” 87.9 98.5 Isolene 40" 9.8 - UVE 1016 (50% active)"" 1.8 1.5D C57!　0.25 DC190!　0.25 ! Silicone flow control agent manufactured by Dot-Corning.

8 Triethylene as a 50% solution in triethylene glycol divinyl ether Glycol monovinyl ether 3 mol, 4,4°-diphenylmethane diisocy A vinyl ester made from 3 moles of anate and 1 mole of trimethylolpropane. A polyurethane oligomer with terminal groups.

”Hardman Incorporated (Belesville, Liquid cis-1,4 polyyne with an average molecular weight of 40,000 provided by Prene rubber (viscosity ranging from 36,000 to 55,000 cps at 100F).

"" UVE1016 G, E, company mnoli ion optical fiM agent r (carbonic acid pro Triphenyl sulfonate of hexafluorophosphate as a 50% solution in pyrene salts).

All films were deposited by drawing down onto glass to obtain a nominal thickness of 3 mils. Manufactured. The wet film was irradiated with 11 D-runs and 1 H-lamp until 0. ．． A dose of 75 J/sqcm was delivered. Both vulcanized films turn pale yellow. The 161C film was clear while the 162 film was cloudy. H - and D- lamps are each 12 inches long, approximately 300 l/in. They are the same in that they emit 11. D-lamp radiation penetrates the film better and also contain more of the longer wavelengths, which is preferable for curing thicker films. To be more specific, the D-lamp is 25.6W/in at 200-300nm, 30CI -63.8W/in at 400nw and 26.91' at 400-470nm radiates l/in. H-lung is 2Q (44.8W/in+ at 1-300n* 300-400n va 31.01117in and 400-47On+ 17.711 in n! /in.

Water absorption” 12.3 8.9 Extracted content (%)” 4.2 3.1 Tensile force, i4 P a 24 35 Elongation rate (%) 5 Elastic modulus, 14Pa 650 925 E' (100C! JPa, 100MPa) 'C4g, 66 52.6 7 Tan Delta, Max, 'C6667 DMA curve single type single type 1. Showing the results of a test conducted by immersing free paint in water at 25°C for 24 hours. It is. f4Pa indicates megapascals.

Eo, tan delta and DMA curves are the results of dynamic mechanical analysis. This is mechanical Stiffness and energy dissipation are determined by imposing vibrational strain on a material and measuring the resulting strain. Therefore, this is a known method of measurement. Eo is the elastic modulus. Tan delta is the viscoelastic modulus vs. is the ratio of the elastic modulus, and the DMA curve is calculated by plotting various factors. can get. If pro-soto shows greater than the maximum value, this indicates phase separation. It is reported here that f:, jl-form pro soto (unia+odal pl ot) indicates that the material under test is a Hayabusa-continuous phase.

This data shows that polyisoprene is blended with vinyl ether polyurethane oligomers. By doing so, the elastic modulus and tensile strength can be improved without affecting its glass transition temperature. Tests on percentage elongation have been carried out to ensure accuracy, showing that the The results reported here are the only Since the test results have only been reported, they cannot be considered definitive. , no significant changes in dynamic mechanical properties were observed between 0 and 100 °C, and the properties with temperature changes were A high aI rate allows the composition to retain strength at elevated temperatures.

The water sensitivity of both the formulation and the control is high, which is due to the origin containing a high percentage of ether linkages. Depends on the nature of the sesame/diluent mixture.

The apparent increase in water sensitivity of vinyl ether-terminated polyurethane rubber formulations is due to expected since polyisoprene is more hydrophobic than the polyether urethane backbone. It is contrary to the effect of This observed anomaly is due to this test on sample thickness. This seems to be due to the sensitivity of the person. The reported results therefore indicate that the test is accurate. It cannot be considered definitive unless it has been repeated many times to ensure that this is done. There wasn't.

Infrared analysis to determine the fate of polyisoprene unsaturation during vulcanization is definitive. However, as shown by the experiment below, liquid polyisoprene It is clear that it is actually co-vulcanized with polyurethane with a nyl ether terminal group. Proven: Vulcanized film of 4017-162A was cured with methyl ethyl ketone (M Reflux in EK) for 8 hours, followed by soaking in MEK for 72 hours. The film was then dried in a vacuum desiccator for 2 hours before being rescaled. Dry in air for 24 hours. No change in weight was observed after MEK extraction as described above. Ta. This is a polyurethane terminated with an elastomer and vinyl ether during vulcanization. It can be concluded that the thermal stability of the formulation indicates complete co-reaction with The effect of polyisoprene on films of formulated materials and controls heated at 200°C Investigated by aging. The results are shown below.

LL 0 pots at 200℃ Time (hours) Loss Weight Sample (9.8% Boliisolune) Control %# S, D, %# S, D.

P, 21.4 0.95 20.4 2.7032 32.5 1.73 3 0.3 3. ．． 5364 35.4 3.64 3g, 2 1.93128 4 3.0 2.65 39.9 3.76200 45.6 2.89 44.7 3.42# indicates the weight loss (%) when exposed to the temperature for the indicated time, S, D , represents the standard S deviation.

- Statistical analysis using the distribution test shows that with greater than 95% confidence that the two substances This test statistically shows that two samples have the same heat aging properties. By comparing the standard deviations obtained from the whether the average value is the same as the specified level of desired reliability (95% in this case). Determine whether they are the same.

Thermoplasticity of saturated thermoplastic rubber, i.e. poly(ethylene-butylene)-styrene When rubber-like copolymers are used in place of unsaturated elastomers , vulcanization of the formulation is completely prevented and the prescribed radiation dose does not result in detectable vulcanization. It was.

Additives to provide coatings useful as primers and single coatings for optical glass fibers A test was conducted. These tests may require a stronger or harder coach than desired. Adding 5 parts and 10 parts of polyisoprene to the vulcanized control to obtain It was carried out by The addition of polyylene does not significantly change the viscosity of the paint. However, a slightly larger amount of catalyst was required. The results are shown below.

Oligomer solution” 67.4 63.8 72.0T E G D V E 2 5.7 24.3 27.5 UVE 1016 1.0 1.0 0.5 wait-1 gender one Dose (J/sqcm>0.5 0.5 0.5 Elongation rate (%) 33 31 3 8 Tensile strength, MPa 2.7 2.7 12 Modulus of elasticity, MPa 14 13 60 1 The oligomer solution used was prepared using a stirrer, dry nitrogen sparger, and 250+β addition. 500 with funnel, reflux condenser, thermometer and thermostatically controlled heating mantle was prepared using an apparatus consisting of a 4-mg round-necked round-bottom flask. 4゜4'-diphenylene 20.91 parts of rumethane diisocyanate was charged into a flask and heated to 60°C. 0 and then 22.74 parts of 1,4-butanediol divinyl ether as a diluent. Add to the flask and add 7.45 parts of 4-hydroxybutyl vinyl ether to the addition funnel. The reaction mixture was added over 10 minutes and kept at 60°C for an additional 2 hours. The NGO content was then analyzed and diethylene glycol with an average molecular weight of about t, ooo Caprolactone adducts with Union Carbide Corprat: Uses Tone 220 manufactured by on company (Chrcago, IL) ) was charged into an addition funnel (to react with unreacted incyanate). 0.06 parts of dibutyltin dilaurate catalyst was then added to the flask and the contents of the addition funnel The mixture was kept at 60°C and added over 10 minutes. Then heat the flask to 70℃ , this temperature was maintained until the NGO content was less than 0.1%. Calculated on average The molecular weight was determined to be 2400. TEGDVE is triethylene glycol It is ludivinyl ether.

As can be seen from the table, the tensile strength and elastic modulus decreased significantly, and polyisoprene 1 Adding 0% does not result in a greater reduction than adding 5%. It was. It is concluded that even smaller modifications can be obtained if significantly lower loadings are used. can be used. Either of the two additives will add a thick layer to the newly drawn fiber. A 3 mil coating is applied and this is then UV vulcanized as previously described. Primer or coating material useful for coating optical glass fibers. yielding test compositions suitable for both.

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Claims (1)

[Claims] 1.　Actualization without actual hydroxyl functionality and promoted by cationic photoinitiators In a liquid mixture that can be cured by radiation, this terminates the vinyl ether. Consisting of base polyurethane and ethylenically unsaturated liquid polymer elastomer, 0.1 of the elastomer based on the total weight of its mixture with the polyurethane. % to 40%. 2. The mixture contains a cationic photoinitiator that is effective and present to initiate vulcanization. 2. The composition according to claim 1, comprising less than 1.5% based on the weight of the unsaturated material. blend. 3. 3. A mixture according to claim 2, wherein the photoinitiator is a sulfonium compound. 4. A mixture according to claim 3, wherein the photoinitiator is present in an amount of 0.1% to 1.4%. . 5. A mixture according to claim 2, wherein the photoinitiator is present in an amount of 0.2% to 1.0%. . 6. The vinyl ether-terminated polyurethane is an aliphatic monovalent vinyl ether ether, isocyanate-reactive polyols or polyamines, and isocyanates The reaction product of the organic polyisocyanate is sufficient to react with all of the reactive functionalities. A mixture according to claim 1, which is a composition of the present invention. 7. The polyisocyanate is a diisocyanate, and the isocyanate is diamines and diamines in which the reactive materials have an average molecular weight of about 60 to about 3,000; 7. The mixture according to claim 6, wherein the mixture is selected from the following. 8. Vinyl ether having a molecular weight within the range of about 1,500 to about 6,000 In order to obtain polyurethane with terminal groups, the diisocyanate is phenyl diisocyanate, and the isocyanate-reactive substance is 300 8. The mixture of claim 7, which is a diol having a molecular weight of ~2,000. 9. Claim 1 wherein a polyvinyl ether of a polyol is present as a reactive diluent. Mixture as described. 10. The vinyl ether-terminated polyurethane is combined with the reactive diluent. 10. The mixture of claim 9, comprising about 20% to 99% of the mixture. 11. The vinyl ether-terminated polyurethane is combined with the reactive diluent. 10. A mixture according to claim 9, comprising from 30% to 80% of the mixture. 12. The elastomer is a liquid hydrocarbon polymer or a liquid halogen-substituted hydrocarbon. 2. The mixture of claim 1, which is a polymer. 12. a diethylenically unsaturated hydrocarbon in which the elastomer contains 4 or 5 carbon atoms; Claim 1, wherein the polymer is a pure liquid polymer or a liquid polymer of a halogen-substituted hydrocarbon. A mixture of ingredients. 13. The mixture of claim 1, wherein the elastomer is a polyisoarene. 14. Claim wherein the composition contains hydroxy groups in an amount less than 0.1% by weight. 1. The mixture according to 1. 15. A virtually hydroxy-free paint that can be cured when exposed to actinic radiation. This is a cationic photoinitiator and vinyl ether-terminated polyurethane. This is an aliphatic monovalent vinyl ether, an isocyanate-reactive polyol or a polyamide. sufficient organic dihydrogen to react with all of the isocyanate-reactive functionalities. is a reaction product of socyanates) and ethylenically unsaturated liquid polymer elastomers. -(This is a diethylenically unsaturated hydrocarbon containing 4 or 5 carbon atoms or a halogen a polymer of substituted hydrocarbons), said elastomer being a polymer of said polyurethane. characterized in that it is present in an amount of 0.1% to 40% relative to the total weight of the mixture with A paint that actually does not contain hydroxyl. 16. The cationic photoinitiator comprises 0.1% to 1.4% of the weight of unsaturated material present. 16. A paint according to claim 15, wherein the sulfonium compound is present in an amount of %. 17. the diisocyanate is 4,4'-diphenylmethane diisocyanate; 18. The paint according to claim 15, which comprises: Vinyl ether-terminated polyurethane and an ethylenically unsaturated elastomer (this elastomer is present in an amount of 0.1% to 0.4% based on the total weight of the mixture with urethane) and a certain amount of cationic photoinitiator, which opens cationic vulcanization when exposed to ultraviolet light. 1.5% by weight of unsaturated substances present. actually hydroxy-free UV-curable liquid composition consisting of A film having a thickness of 1 to 10 mils of the composition is applied and the film is exposed to ultraviolet light. A method of coating a base material, which is characterized by vulcanizing it by irradiating the base material. 19. The film is exposed to light in an atmosphere having a relative humidity of less than about 45%. 19. The method of claim 18, wherein the method comprises irradiating. 20. The polyurethane has an average molecular weight within the range of 1,500 to about 6,000. 2. The method of claim 1, and wherein said film has a thickness of 2.5 to 6 mils. 21. Specifically, the vulcanized coating is in contact with the glass surface of the optical glass fiber. coated with a vulcanized coating comprising the composition of claim 1, characterized in that Optical glass fiber. 22. The polyurethane has an average molecular weight within the range of about 1,500 to about 6,000. 22. The vulcanized coating has a thickness of 2.5 to 6 mils. coated optical glass fiber.