CN1246476A - Polyester containing benzotriazolyl, method for preparation thereof, ultraviolet absorption agent containing the polyester and synthetic resin composite - Google Patents
Polyester containing benzotriazolyl, method for preparation thereof, ultraviolet absorption agent containing the polyester and synthetic resin composite Download PDFInfo
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- CN1246476A CN1246476A CN 98118816 CN98118816A CN1246476A CN 1246476 A CN1246476 A CN 1246476A CN 98118816 CN98118816 CN 98118816 CN 98118816 A CN98118816 A CN 98118816A CN 1246476 A CN1246476 A CN 1246476A
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Abstract
The present invention relates to a new polyester containing benzotriazole icsed as ultraviolet absorbent. It is prepared by the open-loop addition polymerization of lactones with the alcoholhydroxyl in 3-(5-chloro-2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyl-phenylpropanol, 3-(2H-benzotriazole-2-yl)-4-hydroxyl-phenylethanol, 3-(5-methyl-2H-benzotriazole-2-yl)-5-(1-methyethyl)-4-hydroxyl-phenylpropanol or bis [3-(2H-benzotriazole-2-yl)-4-hydroxyl-phenylethanol] methane. Mixing it with thermoplastic resin can generate a resin composition with better light and medicine resistance.
Description
The present invention relates to the novel polyester that contains the benzotriazole base, its preparation method, contain the UV light absorber of this polyester and be used the photostabilization and the good resin combination of resistance of this UV light absorber.
The synthetic resins that possesses high strength, high-durability and good forming process is for example, production fields such as automobile, electric and electronic, building are widely used, if contain under the ultraviolet light but be exposed to daylight etc., just exist because of the uviolizing deterioration, variable color appears, cause that molecular weight reduces, and then cause defective such as intensity reduction.
In order to improve synthetic resins, by adopting the method for adding UV light absorber to ultraviolet weather resistance (photostabilization).These UV light absorber comprise 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 5-chloro-2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole category such as benzotriazole and 2,4 dihydroxyl benzophenone, 2-hydroxyl-benzophenones such as 4-octyloxy benzophenone.
But, because above-mentioned known UV light absorber is low-molecular-weight low-boiling compound, so, if they are added in the synthetic resins, variety of problems can appear.For example, if the heavy addition UV light absorber will cause to be separated, the transparency of synthetic resins and physical strength are reduced.So, can only add the UV light absorber of minute quantity, but in this case, the degree that improves the synthetic resins photostabilization can't obtain satisfactory.In addition, loose or thermolysis, or be exuded to moulding product surface, so just can not give synthetic resins for a long time with stable photostabilization because UV light absorber can be waved when molding synthetic resin.
In order to eliminate above-mentioned defective, done following trial, promptly in above-mentioned UV light absorber, added the group of two keys such as the polymerizability that has vinyl, make its polymerization, polymer quantizes, to improve the intermiscibility with resin, prevent that waving of UV light absorber is diffusing, thermolysis and ooze out etc. (open the clear 60-38411 of communique number of Japanese Patent, open the clear 62-181360 of communique number of Japanese Patent, open the flat 3-281685 of communique number of Japanese Patent etc.).
But also there are various defectives shown below in these ultraviolet-absorbing polymers, also have the improved place of needs.That is,, and then the physical strength of synthetic resins is reduced because the kind of synthetic resins can not obtain sufficient intermiscibility.This tendency shows obviously especially in thermoplastic resins such as polyolefine, polyvinyl chloride, polyvinylidene chloride.In addition, on long-term this aspect of photostabilization, also be difficult to satisfy.
Because thermoplastic resins such as polyvinyl chloride, polyvinylidene chloride, polycarbonate, polymeric amide, polyester, TPU(Thermoplastic polyurethanes) have high physical strength, so, be widely used as various molding materials, but polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyester and TPU(Thermoplastic polyurethanes) can be decomposed by alkaline components, cause physical strength to reduce such defective, and, polyamide resin can be dissolved in the common solvent such as methyl alcohol, therefore, above-mentioned any resin all haves much room for improvement on resistances such as alkali resistance, solvent resistance.
Present inventors are for solving the problem that exists in the above-mentioned conventional art, having carried out conscientiously, the result of research is, the polymerizable compound and a lot of synthetic resins that are obtained as raw material by known various UV light absorber have good intermiscibility, can not destroy the characteristic preferably of synthetic resins, can give good photostabilization, and, when molding synthetic resin, can not wave and loose and thermolysis, and can not be exuded to moulding product surface, so, can give synthetic resins for a long time with stable photostabilization.In addition, also find to give the not good synthetic resins of alkali resistance and solvent resistance with good alkali resistance and anti-solvent resistance with the UV light absorber that above-mentioned specific aggregation compound is an effective constituent.The present invention finishes on the basis of above-mentioned result of study.
That is the 1st polyester that contains the benzotriazole base that has provided formula (1) or (1 ') expression of the present invention.
(R
1Expression H, halogen atom or carbonatoms are 1～10 alkyl, R
2Expression H or carbonatoms are 1～10 alkyl, R
3The expression carbonatoms is 1～10 alkylidene group, R
4And R
5Expression H or carbonatoms are 1～10 alkyl, and n represents 4～8 integer, and m represents 1～20)
The 2nd compound that has provided through type (2) or (2 ') expression of the present invention makes the lactone of formula (3) expression carry out the ring opening polyaddition reaction, obtains the 1st the described preparation method who contains the polyester of benzotriazole base of the present invention.
(R
1Expression H, halogen atom or carbonatoms are 1～10 alkyl, R
2Expression H or carbonatoms are 1～10 alkyl, R
3The expression carbonatoms is 1～10 alkylidene group, R
4And R
5Expression H or carbonatoms are 1～10 alkyl, and n represents 4～8 integer, and m represents 1～20)
The 3rd of the present invention has provided the UV light absorber that comprises the polyester that contains the benzotriazole base.
The 4th of the present invention has provided synthetic resins and the 3rd the described resin combination that contains UV light absorber of the present invention.
The 5th of the present invention to have provided synthetic resins be at least a the 4th the described resin combination of the present invention that is selected from polyvinyl chloride, polyvinylidene chloride, polyolefine, polycarbonate, polystyrene, acrylic resin, methacrylic resin, polymeric amide, polyester, acrylonitrile-butadiene-styrene resin and thermoplastic polyurethane.
Can provide high-content by the present invention, and have photostabilization and chemical sproof resin combination steady in a long-term.
Fig. 1 represents the present invention's product (embodiment 1) and the tensile strength characteristic of product (comparative example 1) in the past after the exposure test.
Fig. 2 represents the present invention's product (embodiment 4) and aberration (the Δ Eab of product (comparative example 4) in the past after the exposure test
*).
Fig. 3 represents the present invention's product (embodiment 5) and aberration (the Δ Eab of product (comparative example 5) in the past after the exposure test
*).
Fig. 4 represents the present invention's product (embodiment 6) and aberration (the Δ Eab of product (comparative example 6) in the past after the exposure test
*).
Fig. 5 represents the infrared absorption spectrum of the compound (3) of synthesis example 3 gained.
Fig. 6 represents the NMR (Nuclear Magnetic Resonance) spectrum of the compound (3) of synthesis example 3 gained.
Fig. 7 represents the ultraviolet-visible absorption spectroscopy of the compound (3) of synthesis example 3 gained.
Fig. 8 represents the ultraviolet-visible absorption spectroscopy of the compound (4) of synthesis example 4 gained.
Fig. 9 represents the present invention's product (embodiment 10) and the tensile properties of product (comparative example 10) in the past after the exposure test.
Figure 10 represents the present invention's product (embodiment 13) and aberration (the Δ Eab of product (comparative example 13) in the past after the exposure test
*).
Figure 11 represents the present invention's product (embodiment 14) and aberration (the Δ Eab of product (comparative example 14) in the past after the exposure test
*).
Figure 12 represents the present invention's product (embodiment 15) and aberration (the Δ Eab of product (comparative example 15) in the past after the exposure test
*).
The petchem that contains the BTA base of aforementioned formula of the present invention (1) or (1 ') expression is a kind of material of novelty, and the ultra-violet absorber that can be used as synthetic resin uses.
The preparation method of the polyester that contains the BTA base of aforementioned formula (1) or (1 ') expression makes the lactone of aforementioned formula (3) expression carry out the ring opening polyaddition reaction by the alcohol that aforementioned formula (2) or (2 ') represent.
In formula (1) or (1 '), m is integer to each polymer molecule, but whole polymer integers not necessarily. If all m or the m ' less than 1 of polymer then have the tendency that is exuded to the products formed surface, on the contrary, if m or m ' surpass 20, may cause that then ultraviolet-absorbing is abundant not, so above-mentioned any situation is all bad. As the ultraviolet-absorbing compound of formula (1) or (1 ') expression, the value of m or m ' gets final product in above-mentioned scope, and there is no particular limitation to it.
Alcohol as aforementioned formula (2) expression, specifically comprise 3-(5-chloro-2H-BTA-2-yl)-5-(1,1-dimethyl ethyl)-4-hydroxyl-phenylpropanol, 3-(2H-BTA-2-yl)-4-hydroxyl-benzyl carbinol, 3-(5-methyl-2H-BTA-2-yl)-5-(1-Methylethyl)-4-hydroxyl-phenylpropanol etc.
The alcohols of aforementioned formula (2 ') expression has two [3-(2H-BTA-2-yl)-4-hydroxyl-benzyl carbinol] methane etc. In addition, can be with the substituent R of aforementioned formula (2) on 2 BTA rings of formula (2 ')1, the substituent R of 2 BTA rings1Can be identical, can be not identical yet.
In aforementioned formula (2) and (2 '), make the lactone open loop and the alcohols such as ethanol, propyl alcohol that carries out on the benzene nucleus of addition polymerization can be terminal alcohol or branched-chain alcoho.
These alcohol except can using synthetics or commercially available product, the commercially available benzotriazole that also can use reduction such as lithium aluminium hydride to have ester group be UV light absorber and alcohol.
As the lactone of aforementioned formula (3) expression, can use 6-caprolactone, trimethylammonium-6-caprolactone, monomethyl-6-caprolactone, gamma-butyrolactone, δ-Wu Neizhi etc.
Used catalyzer comprised organic titanium compounds such as tetraethyl titanate, tetrabutyl titanate, metatitanic acid orthocarbonate when the alcohol by aforementioned formula (2) or (2 ') expression made the lactone ring opening polyaddition of aforementioned formula (3) expression, organo-tin compounds such as stannous octoate, dibutyl tin oxide, dibutyl tin dilaurate, lipid acid one normal-butyl tin, the inferior tin of halogenations such as tin protochloride, tin protobromide, tin protoiodide.
Catalyst consumption is generally 0.1～10 corresponding to used raw alcohol, and 000ppm is preferably 1～5,000ppm.If the not enough 0.1ppm of catalyst consumption, then the ring-opening reaction of lactone is significantly slack-off, and is uneconomical.On the contrary, if surpass 10,000ppm, then ring-opening reaction is too fast, rerum natura variation such as the weather resistance of the synthetic resins that gets with the polyester with benzotriazole base of gained and water tolerance, so, no matter above-mentioned any situation is all bad.
Temperature of reaction is generally 90～240 ℃, is preferably 100～220 ℃.
If 90 ℃ of temperature of reaction less thaies, then the ring-opening reaction of lactone is significantly slack-off, and is uneconomical.On the contrary, if temperature is more than 240 ℃, because the depolymerization reaction of the polylactone that ring opening polyaddition forms can take place, so no matter above-mentioned any situation is all bad.In addition, be reflected in the atmosphere of inert gases such as nitrogen and carry out, so the form and aspect of synthetic product etc. are all good.Like this, just synthesized the polyester that contains the benzotriazole base of the present invention.
There is no particular limitation to the synthetic resins that added the polyester that contains the benzotriazole base (being also referred to as ultraviolet-absorbing compound or ultraviolet-absorbing polymkeric substance) as UV light absorber in the present invention, can be extensive use of known in the past resin, consider from the interpolation complexity that contains the polyester of benzotriazole base of the present invention, be preferably the use thermoplastic resin.
As thermoplastic resin, can use polyvinyl chloride, polyvinylidene chloride, polyolefine, polycarbonate, polystyrene, acrylic resin, methacrylic resin, polymeric amide, polyester, acrylonitrile-butadiene-styrene (ABS) (ABS resin), TPU(Thermoplastic polyurethanes), vinylchlorid-vinylidene chloride-acrylonitrile copolymer, acrylonitrile-styrene (AS) resin, VINYL ACETATE MONOMER (VAM), polydiphenyl ether, polysulfones, polyethersulfone, polyetherketone, liquid crystal plastics etc.Wherein, be preferably use polyvinyl chloride, polyvinylidene chloride, polyolefine, polycarbonate, polystyrene, acrylic resin, methacrylic resin, urethane, polyester, ABS resin, TPU(Thermoplastic polyurethanes) etc.The good especially relatively poor thermoplastic resins of solvent resistance such as relatively poor thermoplastic resin of alkali resistances such as polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyester, TPU(Thermoplastic polyurethanes) and urethane that are to use.Among the present invention, these synthetic resins can use separately, also can mix use more than 2 kinds.
There is no particular limitation to the blending ratio of the ultraviolet-absorbing compound of aforementioned synthetic resins and formula (1) and/or (1 ') in the composition of the present invention, can suitably select in the broader context, usually, the weight ratio of synthetic resins and ultraviolet-absorbing compound is 80～99.995: 20～0.005, is preferably 90～99.9: 10～0.1.
If necessary, also can in composition of the present invention, add in the known additives such as antioxidant, photostabilizer, processing stabilizers, protective agent, compatilizer at least a kind.
As antioxidant, can use 1, [3-(3 for 6-hexylene glycol-two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 3, steric hindrance phenol antioxidant such as 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, 3,3 '-organosulfur class antioxidants such as dithio dipropyl acid two lauryls, phosphorus antioxidants such as tricresyl phosphate alkyl phenyl ester etc.
As photostabilizer, can use steric hindrance amine photostabilizers such as two (2,2,6,6-tetramethyl--4-piperidyl) sebates, nickel salt class photostabilizers such as nickel dibutyl dithiocarbamate etc.
As processing stabilizers, can use phosphorus processing stabilizers such as tricresyl phosphate (2, the 4-di-tert-butyl-phenyl) ester etc.As protective agent, can use 1, two (4-hydroxy phenyl) tetrahydrobenzene of 1-, N, N '-phenylbenzene-Ursol D etc.
As compatilizer, can use thermoplastic elastomers such as styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene-styrene segmented copolymer.
There is no particular limitation to the consumption of above-mentioned additive, generally corresponding to synthetic resins, is 0.01～20 weight %.
Composition of the present invention can be used for all purposes of all use synthetic resins, particularly suitable be possible be exposed to daylight or comprise situation under the ultraviolet light.
Object lesson is as follows; glass replacement and its surface be coated with material; dwelling house; facility; the window glass of transmission machine etc.; daylighting glass and Bright Source Protection glass are with being coated with material; dwelling house; facility; the inside/outside decorative material and the exterior and interior packing material of transmission machine etc.; luminescent lamp; mercuryvapour lamps etc. send ultraviolet light source part; precision instrument; electric instrument component; cover the material of hertzian wave that various indicating meters send etc.; food; chemical; the container of medicine etc. or wrapping material; industrial or agricultural is with sheet material or film; printed matter; dyeing; the anti-fading agent of dyestuff etc.; sunscreen; shampoo; shampoo; makeup such as agent for permanent hair waving, sweater; stockings; the dress material of cap etc. fibre product and fiber, curtain; carpet; family's upholster product such as wallpaper; glass lens; contact lens; medical apparatus such as artificial eye; filter coating; bevelled mirror; mirror; optics articles for use such as photographic apparatus, adhesive tape; stationery such as ink, display panel; indicating meter etc. and surperficial Tu Cai etc. thereof.
Below, by synthesis example (the preparation embodiment of ultraviolet-absorbing compound), embodiment (the preparation embodiment of compound resin composition) and comparative example, further the present invention will be described, but the present invention is not limited to this." % " all represents " weight % " except specializing.
(i) exposure test
Use machine: two circulation sunlight weather tester WEL-SUN-DC, ス ガ test apparatus Co., Ltd. system, light source: carbon arc, the rainfall circulation: 120 minutes are once, each rainfall 18 minutes, temperature: 80 ℃ on blackboard.
The (ii) elongation at failure of tensile strength test
Use machine: Tianjin, island omnipotent precise materials trier DSC, Shimadzu Seisakusho Ltd.'s system, condition: 200kg/FS, pinblock speed (Network ロ ス ヘ ッ De ス ピ-De) 50mm/ branch, GL=30mm.
At first, the UV light absorber to formula (1) expression describes.
(synthesis example 1)
In being housed, the glass flask of prolong, nitrogen ingress pipe, thermometer and stirrer adds 134.5g3-(2H-benzotriazole-2-yl)-4-hydroxyl-phenylethyl alcohol (trade(brand)name " JF-269 ", north of the city KCC system), then, add 342g 6-caprolactone and 50ppm one normal-butyl tin soap (trade(brand)name " SCAT-24 ", the synthetic Co., Ltd. of three total machines system) again.Temperature of reaction is remained on 150 ℃, and with the 6-caprolactone concentration in the gas chromatograph for determination reaction solution, when this concentration was 0.45%, the expression reaction finished after 6 hours.The acid number of this reactant (mgKOH/g) is 1.9, is to be the solid compound under the room temperature.
The measurement result of the infrared absorption spectrum (IR) of gained compound (1) is, at the characteristic absorption wavelength 1460,1257,1217,870 and the 748cm of 3-(2H-benzotriazole-2-yl)-4-hydroxyl-phenylethyl alcohol
-1There is absorption at the place, and the while is at characteristic absorption wavelength 2941,2864, the 1257cm of polycaprolactone
-1Also there is absorption at the place.
The measurement result of proton N MR is, by ownership for the 2.3ppm signal (NMR spectrographic integrated value B) of the methene proton adjacent with the carbonyl carbon of polycaprolactone be 3 by ownership for the 7.5ppm signal (NMR spectrographic integrated value A1) of the aromatic nucleus proton of benzotriazole ring and the ratio (B/ (A1+A2)) of 7.9ppm signal (NMR spectrographic integrated value A2), confirmed the structure of compound (1) thus.
Then, 10mg compound (1) is dissolved in the 50ml chloroform, uses the quartzy cuvette of optical path length, measure ultra-violet absorption spectrum (UV) as 1mm.Consequently, at 220nm (absorbancy is 0.98), 300nm (absorbancy is 0.51), 350nm (absorbancy is 0.58) characteristic absorption is arranged, in addition, the size of absorbancy has shown in the ultraviolet radiation absorption field has fully big UV to absorb.
(synthesis example 2)
Use the device same with synthesis example 1.In 134.5g 3-(2H-benzotriazole-2-yl)-4-hydroxyl-phenylethyl alcohol (trade(brand)name " JF-269 ", north of the city KCC system) adds 570g 6-caprolactone and 50ppm one normal-butyl tin soap (trade(brand)name " SCAT-24 ", the synthetic Co., Ltd. of three total machines system) in.Temperature of reaction is remained on 150 ℃, and with the 6-caprolactone concentration in the gas chromatograph for determination reaction solution, when this concentration was 0.30%, the expression reaction finished after 8 hours.The acid number of this reactant (mgKOH/g) is 2.05, is to be the solid compound under the room temperature.
The IR measurement result of gained compound (2) is, with the same absorption position of compound (1) on, at the characteristic absorption wavelength and the polycaprolactone characteristic absorption wavelength place of 3-(2H-benzotriazole-2-yl)-4-hydroxyl-phenylethyl alcohol absorption is arranged.
In addition, the measurement result of proton N MR is also identical with compound (1), have the aromatic nucleus proton of benzotriazole ring and the methene proton adjacent with the carbonyl carbon of polycaprolactone, their integrated value is 5 than (B/ (A1+A2)), has confirmed the structure of compound (2) thus.
The UV measurement result of compound (2) is also identical with compound (1), at 220nm (absorbancy is 0.82), 300nm (absorbancy is 0.39), 350nm (absorbancy is 0.42) characteristic absorption is arranged, in addition, the size of absorbancy has shown in the ultraviolet radiation absorption field has fully big UV to absorb.
(embodiment 1 and comparative example 1)
Corresponding to 100 weight part polypropylene, be mixed into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past according to the blending ratio shown in the following table-1, then, injection moulding obtains the JIS2 dumbbell-shaped specimen.
Table-1
| The ultraviolet-absorbing compound | | ||
| Embodiment | |||
| 1 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 1 | ????2 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 2 | ????2 | |
| Comparative example 1 | ?No.1 | Trade(brand)name " JF-269 " | ????2 |
| ?No.2 | Do not mix | ????2 |
With sunlight weather tester the gained dumbbell-shaped specimen is carried out exposure test, exposed the specified time after, carry out test for tensile strength, measure the elongation at failure of tensile strength separately.Test conditions is as follows.The test-results of the elongation at failure of tensile strength as shown in Figure 1.As can be seen from Figure 1, use the composition (the present invention's product) of UV light absorber of the present invention to compare, have better photostabilization with the composition (product in the past) that uses UV light absorber in the past.
(embodiment 2 and comparative example 2)
Corresponding to 100 weight part polyvinyl chloride, according to the ultraviolet-absorbing polymkeric substance of the above-mentioned synthesis example gained of mixed shown in the following table-2 or UV light absorber in the past, injection moulding makes the flat board that thickness is 1.6mm.Similarly to Example 1, the gained flat board is carried out exposure test, its result is shown in table-2.
Table-2
| The ultraviolet-absorbing compound | Weight part | | ||
| Embodiment | ||||
| 2 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 1 | ????1 | No change after 2000 hours |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 2 | ????1 | No change after 2000 hours | |
| Comparative example 2 | ?No.1 | Trade(brand)name " JF-269 " | ????1 | 1000 hours poststainings |
| ?No.2 | Do not mix | ????1 | 600 hours poststainings |
(embodiment 3 and comparative example 3)
Corresponding to 100 weight part polyvinylidene chloride, according to the ultraviolet-absorbing polymkeric substance of the above-mentioned synthesis example gained of mixed shown in the following table-3 or UV light absorber in the past, injection moulding makes the flat board that thickness is 1.6mm.Similarly to Example 1, the gained flat board is carried out exposure test, its result is shown in table-3.
Table-3
| The ultraviolet-absorbing compound | Weight part | Exposure test | ||
| Embodiment 3 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 1 | ????1 | No change after 2000 hours |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 2 | ????1 | No change after 2000 hours | |
| Comparative example 3 | ?No.1 | Trade(brand)name " JF-269 " | ????1 | 800 hours poststainings |
| ?No.2 | Do not mix | ????1 | 400 hours poststainings |
(embodiment 4 and comparative example 4)
Corresponding to 100 weight part polystyrene, according to the ultraviolet-absorbing polymkeric substance of the above-mentioned synthesis example gained of mixed shown in the following table-4 or UV light absorber in the past, injection moulding makes the flat board that thickness is 1.6mm.
Table-4
| The ultraviolet-absorbing compound | | ||
| Embodiment | |||
| 4 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 1 | ????1 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 2 | ????1 | |
| Comparative example 4 | ?No.1 | Trade(brand)name " JF-269 " | ????1 |
| ?No.2 | Do not mix | ????1 |
Similarly to Example 1, the gained flat board carried out exposure test after, with colour-difference meter (trade(brand)name: カ ラ-コ Application ピ ュ--SM-2, ス ガ trier Co., Ltd. system) to before exposing and planar surface aberration (the Δ Eab after exposing
*) carry out quantitatively.Its result as shown in Figure 2.As can be seen from Figure 2, the present invention's product have better photostabilization than product in the past.
(embodiment 5 and comparative example 5)
Corresponding to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past according to ratio shown in the following table-5, injection moulding, obtaining thickness is the flat board of 1.6mm.
Table-5
| The ultraviolet-absorbing compound | Weight part | ||
| Embodiment 5 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 1 | ????1 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 2 | ????1 | |
| Comparative example 5 | ?No.1 | Trade(brand)name " JF-269 " | ????1 |
| ?No.2 | Do not mix | ????1 |
Similarly to Example 1, the gained flat board carried out exposure test after, with colour-difference meter (trade(brand)name: カ ラ-コ Application ピ ュ--SM-2, ス ガ trier Co., Ltd. system) to planar surface aberration (Δ Eab
*) carry out quantitatively.Its result as shown in Figure 3.As can be seen from Figure 3, the present invention's product have better photostabilization than product in the past.
(embodiment 6 and comparative example 6)
Corresponding to 100 weight part polycarbonates, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past according to ratio shown in the following table-6, injection moulding, obtaining thickness is the flat board of 1.6mm.
Table-6
| The ultraviolet-absorbing compound | | ||
| Embodiment | |||
| 6 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 1 | ????1 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 2 | ????1 | |
| Comparative example 6 | ?No.1 | Trade(brand)name " JF-269 " | ????1 |
| ?No.2 | Do not mix | ????1 |
Similarly to Example 1, the gained flat board carried out exposure test after, with colour-difference meter (trade(brand)name: カ ラ-コ Application ピ ュ--SM-2, ス ガ trier Co., Ltd. system) to planar surface aberration (Δ Eab
*) carry out quantitatively.Its result as shown in Figure 4.As can be seen from Figure 4, the present invention's product have better photostabilization than product in the past.
(embodiment 7 and comparative example 7)
According to the ratio shown in the following table-7, in tetrachloroethane, sneak into ultraviolet-absorbing polymkeric substance or the UV light absorber in the past and the polystyrene of above-mentioned synthesis example gained, make uniform solution.Is that 30mm, thickness are to drip this solution on the silica glass system plate of 1mm with the rotary coating machine at diameter, and making thickness is the homogeneous film of 0.9～1.0 μ m.This plate is placed in 70 ℃ the warm water, measured the absorbancy of this film in per 2 hours at 340nm.
The trial target that uses UV light absorber (comparative example 7) in the past is because the stripping of used UV light absorber, and its absorbancy almost linearly reduces.Corresponding to this, use the trial target of the polymkeric substance (embodiment 7, UV light absorber of the present invention) of synthesis example 1 stripping not occur or ooze out phenomenon, absorbancy and initial stage keep same degree.Initial stage absorbancy (the A of each comfortable 340nm place film
0) and the absorbancy (A after 10 hours
10) and absorbancy conservation rate (%, A
10/ A
0) all be recorded in table-7.
Table-7
| The ultraviolet-absorbing compound | Combined amount (mg) | Epimere: A 0Epimere: A 10 | Absorbancy conservation rate (%) | |
| | The ultraviolet-absorbing compound polystyrene of synthesis example 1 | ????100 ????900 | ????0.320 ????0.318 | ????99.3 |
| Comparative example 7 | Trade(brand)name ＂ JF-269 ＂ polystyrene | ????100 ????900 | ????0.325 ????0.205 | ????63.1 |
In addition, utilize the sunlight weather tester identical that plate after 10 hours is carried out exposure test with embodiment 1, plate corresponding to embodiment 7 gained did not have the visual variation that recognizes yet after 500 hours, yellow has just appearred in the plate of comparative example 7 gained after 200 hours.So, can confirm that composition of the present invention has stable photostabilization.
(embodiment 8 and comparative example 8)
According to the ratio shown in the following table-8, in tetrachloroethane, sneak into ultraviolet-absorbing polymkeric substance or the UV light absorber in the past and the polymethylmethacrylate (PMMA) of above-mentioned synthesis example 2 gained, make uniform solution, use this solution, by making the uniform film that thickness is about 1 μ m with method identical shown in the embodiment 7.This plate is placed in 70 ℃ the warm water, measured the absorbancy of this film at 340nm in per 2 hours, its result is shown in table-8.
Table-8
| The ultraviolet-absorbing compound | Combined amount (mg) | Epimere: A 0Epimere: A 10 | Absorbancy conservation rate (%) | |
| | The ultraviolet-absorbing Compound P MMA of synthesis example 1 | ??150 ??850 | ??0.468 ??0.458 | ????97.9 |
| Comparative example 8 | Trade(brand)name ＂ JF-269 ＂ PMMA | ??100 ??900 | ??0.430 ??0.055 | ????12.8 |
Can find out that from the result of table-8 in the composition of the present invention, the ultraviolet-absorbing polymkeric substance is present in the resin matrix fully, the phenomenon appearance that does not have stripping fully or ooze out.
(embodiment 9 and comparative example 9)
Similarly to Example 7, with in the past UV light absorber of the ultraviolet-absorbing polymkeric substance of 15mg synthesis example 2 gained and 85mg polyethylene terephthalate (embodiment 9) or 5mg (2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-benzotriazole) and 95mg polyethylene terephthalate (comparative example 9) make film respectively.The gained film is placed in 70 ℃ 2% aqueous sodium hydroxide solution.Measured the absorbancy (At) of this film at 340nm or 231nm place in per 2 hours, conservation rate is represented with At/Ao.Measure the UV absorbing properties after 10 hours and the conservation rate of film, comprise the polyethylene terephthalate film of UV light absorber in the past or have only the film of polyethylene terephthalate except the stripping (decrement of the conservation rate at 340nm place is 85%) of UV light absorber, the polyethylene terephthalate film is significantly dissolving (decrement of the conservation rate at 231nm place is 50%) also, relative with it, above-mentioned any conservation rate of embodiment 9 all is almost 100%.
Then, the UV light absorber to formula (1 ') expression describes.
(synthesis example 3)
In being housed, the glass flask of prolong, nitrogen ingress pipe, thermometer and agitator adds two [3-(2H-benzotriazole-2-the yl)-4-hydroxyl-phenylethyl alcohol] methane (trade(brand)name ＂ MBEP ＂ Otsuka Chemical Co., Ltd system) of 129.3g, 170.3g 6-caprolactone and 50ppm one normal-butyl tin soap (trade(brand)name ＂ SCAT-24 ＂, the synthetic Co., Ltd. of three total machines system).Temperature of reaction is remained on 150 ℃, and after 6 hours, with the concentration of 6-caprolactone in the gas chromatograph for determination reaction solution, when concentration was 0.43%, the expression reaction finished.The number-average molecular weight (MN) that this reactant is that acid number (mgKOH/g) is 1.8, concentration is 2645cP/60 ℃, obtain by gpc analysis is 1391, weight-average molecular weight (MW) is 1688, MW/MN is aqueous compound under 1.213 the room temperature.
The IR spectrum of gained compound (3) as shown in Figure 5, NMR spectrum is as shown in Figure 6.
In addition, 10mg compound (3) being dissolved in the 50ml chloroform, is the quartz cell mensuration ultra-violet absorption spectrum of 1mm with optical path length.Its result as shown in Figure 7.Can confirm that from Fig. 7 compound (3) demonstrates fully big absorption in ultraviolet field.
(synthesis example 4)
Use the device same with synthesis example 3, add two [3-(2H-benzotriazole-2-the yl)-4-hydroxyl-phenylethyl alcohol] methane (trade(brand)name ＂ MBEP ＂ Otsuka Chemical Co., Ltd system) of 93.7g, 206.3g 6-caprolactone and 50ppm one normal-butyl tin soap (trade(brand)name ＂ SCAT-24 ＂, the synthetic Co., Ltd. of three total machines system).Temperature of reaction is remained on 150 ℃, and after 6 hours, with the concentration of 6-caprolactone in the gas chromatograph for determination reaction solution, when concentration was 0.55%, the expression reaction finished.The MN that this reactant is that acid number (mgKOH/g) is 2.5, concentration is 987cP/60 ℃, obtain by gpc analysis is 2017, MW is 2465, MW/MN is the solid compound under 1.222 the room temperature.
The IR measurement result of gained compound (4) is, at characteristic absorption wavelength 1460,1257,1217,870, the 748cm of two-[3-(2H-benzotriazole-2-yl)-4-hydroxyl-phenylethyl alcohol] methane
-1The place has absorption, and the while is at characteristic absorption wavelength 2941,2864, the 1257cm of polycaprolactone
-1The place has absorption.
In addition, the measurement result of proton N MR is, by ownership for the 2.3ppm signal (NMR spectrographic integrated value B) of the methene proton adjacent with the carbonyl carbon of polycaprolactone be 5 by ownership for the 7.5ppm signal (NMR spectrographic integrated value A1) of the aromatic nucleus proton of benzotriazole ring and the ratio (B/ (A1+A2)) of 7.9ppm signal (NMR spectrographic integrated value A2), confirmed the structure of compound (4) thus.
Then, 10mg compound (4) is dissolved in the 50ml chloroform, uses the quartz cell of optical path length, measure ultra-violet absorption spectrum (UV) as 1mm.Its result as shown in Figure 8.Can confirm that from Fig. 8 in ultraviolet field, compound (4) shows fully big absorption.
(embodiment 10 comparative examples 10)
Corresponding to 100 weight part polypropylene, according to ratio shown in the following table-9, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past, injection moulding obtains the JIS2 dumbbell-shaped specimen.
Table-9
| The ultraviolet-absorbing compound | | ||
| Embodiment | |||
| 10 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 3 | ????2 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 4 | ????2 | |
| Comparative example 10 | ?No.1 | Trade(brand)name " MBEP " | ????2 |
| ?No.2 | Do not mix | ????2 |
With sunlight weather tester the gained dumbbell-shaped specimen is carried out exposure test, carry out test for tensile strength after the exposure specified time, measure the elongation at failure of tensile strength separately, test conditions is as follows, and test-results as shown in Figure 9.Can confirm that from Fig. 9 the present invention's product have better photostabilization than product in the past.
(embodiment 11 and comparative example 11)
Corresponding to 100 weight part polyvinyl chloride, according to ratio shown in the following table-10, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past, injection moulding, obtaining thickness is the flat board of 1.6mm, similarly to Example 10, the gained flat board is carried out exposure test, its result is shown in table-10.
Table-10
| The ultraviolet-absorbing compound | Weight part | Exposure test | ||
| Embodiment 11 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 3 | ????1 | No change after 2000 hours |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 4 | ????1 | No change after 2000 hours | |
| Comparative example 11 | ?No.1 | Trade(brand)name " MBEP " | ????1 | 1200 hours poststainings |
| ?No.2 | Do not mix | ????1 | 600 hours poststainings |
(embodiment 12 and comparative example 12)
Corresponding to 100 weight part polyvinylidene chloride, according to ratio shown in the following table-11, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past, injection moulding, obtaining thickness is the flat board of 1.6mm, similarly to Example 10, the gained flat board is carried out exposure test, its result is shown in table-11.
Table-11
| The ultraviolet-absorbing compound | Weight part | | ||
| Embodiment | ||||
| 12 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 3 | ????1 | No change after 2000 hours |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 4 | ????1 | No change after 2000 hours | |
| Comparative example 12 | ?No.1 | Trade(brand)name " MBEP " | ????1 | 950 hours poststainings |
| ?No.2 | Do not mix | ????1 | 400 hours poststainings |
(embodiment 13 and comparative example 13)
Corresponding to 100 weight part polystyrene, according to ratio shown in the following table-12, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past, injection moulding, obtaining thickness is the flat board of 1.6mm.
Table-12
| The ultraviolet-absorbing compound | | ||
| Embodiment | |||
| 13 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 3 | ????1 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 4 | ????1 | |
| Comparative example 13 | ?No.1 | Trade(brand)name " MBEP " | ????1 |
| ?No.2 | Do not mix | ????1 |
Similarly to Example 10, the gained flat board carried out exposure test after, carry out quantitatively with the aberration (Δ Eab*) of colour-difference meter (trade(brand)name: カ ラ-コ Application ピ ュ--SM-2, ス ガ trier Co., Ltd. system) planar surface.Its result as shown in figure 10.Can confirm that from Figure 10 the present invention's product have better photostabilization than product in the past.
(embodiment 14 and comparative example 14)
Corresponding to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, according to ratio shown in the following table-13, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past, injection moulding, obtaining thickness is the flat board of 1.6mm.
Table-13
| The ultraviolet-absorbing compound | Weight part | ||
| Embodiment 14 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 3 | ????1 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 4 | ????1 | |
| Comparative example 14 | ?No.1 | Trade(brand)name " MBEP " | ????1 |
| ?No.2 | Do not mix | ????1 |
Similarly to Example 10, the gained flat board carried out exposure test after, with aberration (the Δ Eab of colour-difference meter (trade(brand)name: カ ラ-コ Application ピ ュ--SM-2, ス ガ trier Co., Ltd. system) to planar surface
*) carry out quantitatively.Its result as shown in figure 11.Can confirm that from Figure 11 the present invention's product have better photostabilization than product in the past.
(embodiment 15 and comparative example 15)
Corresponding to 100 weight part polycarbonates, according to ratio shown in the following table-14, sneak into the ultraviolet-absorbing polymkeric substance of above-mentioned synthesis example gained or UV light absorber in the past, injection moulding, obtaining thickness is the flat board of 1.6mm.
Table-14
| The ultraviolet-absorbing compound | Weight part | ||
| Embodiment 15 | ?No.1 | The ultraviolet-absorbing compound of synthesis example 3 | ????1 |
| ?No.2 | The ultraviolet-absorbing compound of synthesis example 4 | ????1 | |
| Comparative example 15 | ?No.1 | Trade(brand)name " MBEP " | ????1 |
| ?No.2 | Do not mix | ????1 |
Similarly to Example 10, the gained flat board carried out exposure test after, with aberration (the Δ Eab of colour-difference meter (trade(brand)name: カ ラ-コ Application ピ ュ--SM-2, ス ガ trier Co., Ltd. system) to planar surface
*) carry out quantitatively.Its result as shown in figure 12.Can confirm from Figure 12, use the composition (the present invention's product) of UV light absorber of the present invention to have better photostabilization than the composition (product in the past) that uses UV light absorber in the past.
(embodiment 16 and comparative example 16)
According to the ratio shown in the following table-15, in tetrachloroethane, sneak into ultraviolet-absorbing polymkeric substance or the UV light absorber in the past and the polystyrene of above-mentioned synthesis example gained, make uniform solution.Is that 30mm, thickness are to drip this solution on the silica glass system plate of 1mm with the rotary coating machine at diameter, and making thickness is the homogeneous film of 0.9～1.0 μ m.This plate is placed in 70 ℃ the warm water, measured the absorbancy of this film in per 2 hours at 340nm.
The trial target that uses UV light absorber (comparative example 16) in the past is because the stripping of used UV light absorber, and its absorbancy almost linearly reduces.Corresponding to this, use the trial target of the polymkeric substance (embodiment 16, UV light absorber of the present invention) of synthesis example 3 stripping not occur or ooze out phenomenon, absorbancy and initial stage keep same degree.Initial stage absorbancy (the A of each comfortable 340nm place film
0) and the absorbancy (A after 10 hours
10) and absorbancy conservation rate (%, A
10/ A
0) all be recorded in table-15.
Table-15
| The ultraviolet-absorbing compound | Combined amount (mg) | Epimere: A 0Epimere: A 10 | Absorbancy conservation rate (%) | |
| | The ultraviolet-absorbing compound polystyrene of synthesis example 3 | ????100 ????900 | ????0.320 ????0.318 | ????99.3 |
| Comparative example 16 | Trade(brand)name ＂ MBEP ＂ polystyrene | ????100 ????900 | ????0.325 ????0.243 | ????74.8 |
In addition, utilize the sunlight weather tester identical that plate after 10 hours is carried out exposure test with embodiment 10, plate corresponding to embodiment 16 gained did not have the visual variation that recognizes yet after 500 hours, yellow has just appearred in the plate of comparative example 17 gained after 200 hours.So, can confirm that composition of the present invention has stable photostabilization.
(embodiment 17 and comparative example 17)
According to the ratio shown in the following table-16, in tetrachloroethane, sneak into ultraviolet-absorbing polymkeric substance or the UV light absorber in the past and the polymethylmethacrylate (PMMA) of above-mentioned synthesis example 4 gained, make uniform solution, use this solution, by making the uniform film that thickness is about 1 μ m with method identical shown in the embodiment 16.This plate is placed in 70 ℃ the warm water, measured the absorbancy of this film at the 340nm place in per 2 hours, its result is shown in table-16.
Table-16
| The ultraviolet-absorbing compound | Combined amount (mg) | Epimere: A 0Epimere: A 10 | Absorbancy conservation rate (%) | |
| Embodiment 17 | The ultraviolet-absorbing Compound P MMA of synthesis example 3 | ????150 ????850 | ????0.468 ????0.458 | ????97.9 |
| Comparative example 17 | Trade(brand)name ＂ MBEP ＂ PMMA | ????100 ????900 | ????0.430 ????0.079 | ????18.4 |
Can find out that from the result of table-16 in the composition of the present invention, the ultraviolet-absorbing polymkeric substance is present in the resin matrix fully, the phenomenon appearance that does not have stripping fully or ooze out.
(embodiment 18 and comparative example 18)
Similarly to Example 16, with in the past UV light absorber of the ultraviolet-absorbing polymkeric substance of 15mg synthesis example 4 gained and 85mg polyethylene terephthalate (embodiment 18) or 5mg (2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-benzotriazole) and 95mg polyethylene terephthalate (comparative example 18) make film respectively.The gained film is placed in 70 ℃ 2% aqueous sodium hydroxide solution.Measured the absorbancy (At) of this film at 340nm or 231nm place in per 2 hours, conservation rate is represented with At/Ao.Measure the UV absorbing properties after 10 hours and the conservation rate of film, comprise the polyethylene terephthalate film of UV light absorber in the past or have only the film of polyethylene terephthalate except the stripping (decrement of the conservation rate at 340nm place is 85%) of UV light absorber, the polyethylene terephthalate film is significantly dissolving (decrement of the conservation rate at 231nm place is 50%) also, relative with it, above-mentioned any conservation rate of embodiment 18 all is almost 100%.
Claims (5)
1. contain the polyester of benzotriazole base, it is characterized in that, by formula (1) or formula (1 ') expression,
In the formula, R
1Expression H, halogen atom or carbonatoms are 1～10 alkyl, R
2Expression H or carbonatoms are 1～10 alkyl, R
3The expression carbonatoms is 1～10 alkylidene group, R
4～R
5Expression H or carbonatoms are 1～10 alkyl, and n represents 4～8 integer, and m represents 1～20.
2. the described preparation method who contains the polyester of benzotriazole base of claim 1 is characterized in that, the compound of through type (2) or formula (2 ') expression makes the lactone of formula (3) expression carry out the ring opening polyaddition reaction,
In the formula, R
1Expression H, halogen atom or carbonatoms are 1～10 alkyl, R
2Expression H or carbonatoms are 1～10 alkyl, R
3The expression carbonatoms is 1～10 alkylidene group, R
4～R
5Expression H or carbonatoms are 1～10 alkyl, and n represents 4～8 integer, and m represents 1～20.
3. comprise the described UV light absorber that contains the polyester of benzotriazole base of claim 1.
4. the resin combination that comprises the described UV light absorber of synthetic resins and claim 3.
5. resin combination as claimed in claim 4, synthetic resins wherein are to be selected from least a in polyvinyl chloride, polyvinylidene chloride, polyolefine, polycarbonate, polystyrene, acrylic resin, methacrylic resin, polymeric amide, polyester, acrylonitrile-butadiene-styrene resin and the TPU(Thermoplastic polyurethanes).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98118816 CN1125820C (en) | 1998-08-27 | 1998-08-27 | Polyester containing benzotriazolyl, method for preparation thereof, ultraviolet absorption agent containing the polyester and synthetic resin composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98118816 CN1125820C (en) | 1998-08-27 | 1998-08-27 | Polyester containing benzotriazolyl, method for preparation thereof, ultraviolet absorption agent containing the polyester and synthetic resin composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1246476A true CN1246476A (en) | 2000-03-08 |
| CN1125820C CN1125820C (en) | 2003-10-29 |
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ID=5226120
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| CN (1) | CN1125820C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712744A (en) * | 2009-11-02 | 2012-10-03 | 伊诺莱克斯投资公司 | Uv absorbing complex polyester polymers, compositions containing uv absorbing complex polyester polymers, and related methods |
| CN110494425A (en) * | 2017-03-29 | 2019-11-22 | 希普洛化成股份有限公司 | Benzotriazole derivatives compound and application thereof |
-
1998
- 1998-08-27 CN CN 98118816 patent/CN1125820C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712744A (en) * | 2009-11-02 | 2012-10-03 | 伊诺莱克斯投资公司 | Uv absorbing complex polyester polymers, compositions containing uv absorbing complex polyester polymers, and related methods |
| CN110494425A (en) * | 2017-03-29 | 2019-11-22 | 希普洛化成股份有限公司 | Benzotriazole derivatives compound and application thereof |
| CN110494425B (en) * | 2017-03-29 | 2022-08-16 | 希普洛化成股份有限公司 | Benzotriazole derivative compound and use thereof |
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| Publication number | Publication date |
|---|---|
| CN1125820C (en) | 2003-10-29 |
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