JPS59166513A - Ultraviolet ray absorption stabilizer - 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 The invention relates to monomeric UV absorption stabilizers preferably containing resorcinol monobenzoate. More particularly the invention relates to the use of such stabilizers in coating compositions.

Many types of organic compositions, including coatings, fibers, films, moldings and dyes, are sensitive to and are degraded by ultraviolet radiation. The usual such radiation is sunlight, but fluorescent lights and nightlights also provide some of it.

Various means have been used to minimize the degrading effects of such degradation. UV absorbing stabilizers absorb UV radiation and ultimately convert it to heat at a sufficiently low level that it is much less degrading than C radiation.

In practice heat is usually not measured, but this is done by excluding other potential pathways for energy dissipation such as fluorescence and irreversible chemical changes. Organic phosphor materials generally have less chemical stability than UV stabilizers and this is not well suited for outdoor applications. UV sensitizers also absorb UV radiation, but generally use that radiation to generate free radicals. Although this can be useful for initiating cross-linking in certain systems, it is usually considered degradative or degradative in most organic compositions. Radical quenchers act as traps for the free radicals generated by ultraviolet light decomposition during the decomposition process, and this therefore prevents the spread of undesired effects.
It tends to slow down or stop. Antioxidants retard the oxidation of organic compositions and thereby minimize the secondary effects of oxidation in which ultraviolet light degradation does most of the damage.

Both UV absorption stabilizers and sensitizers can be referred to as UV absorbers. However, the former is better at preserving the integrity of the organic composition, while the interface promotes changes through free radical formation, and the free radicals can cause some degradative polymer degradation at the same time. Cross-linking can be usefully produced. free radical quencher
Antioxidants and antioxidants act at the secondary level to minimize damage from free radicals and other effects caused by ultraviolet radiation, heat, ozone, or other sources.

UV-absorbing stabilizers are generally monomeric, however they are sometimes provided as oligomers or with an amount of linkage that increases the molecular weight. The increased molecular weight and presence of reactive groups can minimize problems caused by the mobility of unmodified stabilizers. When used in coatings, films, and other organic objects, intact stabilizers tend to leach out of the body and bloom on surfaces, and even evaporate at undesirable rates.

The use of dihydroxybenzophenone in coating compositions bound into acrylic co-10-polymers by glycidyl methacrylate and optionally blended with other polymers is described in U.S. Pat. No. 3,328,
No. 491, No. 3,340,231, No. 3,341
, No. 493, No. 3,288,880, No. 3.36
No. 5,421 and No. 3,445,566. rtrltravtolet S
tabili-2ing Monomers and
Polymers It, 5ynthesisanc
l Polymerization of Acryl
ate and Metha-cr5Q, ate De
rivatives of 2.4-dihydrox
ybenzo-phenone j (J, Ferti
gOthers), r Journal ofApplied
Polymer 5science J Vol. 10 No. 663
See also pages 672-672 (1966). Benefits mentioned include reduced migration of UV stabilizers and improved compatibility and stability.

Dihydroxybenzophenone or its derivatives are first reacted with glycidyl methacrylate or its derivatives, and the reaction product is homopolymerized or copolymerized with other acrylic monomers. Other polymers taught for blending into paints include polystyrene, polypropylene, polyvinyl fluoride and chloride, vinyl chloride/vinylidene chloride copolymers, polymethyl methacrylate, isoprene, vinyl acetate and celluloses. .

Also, US Pat. No. 3,418,397 describes the in-situ preparation of hydroxybenzophenone suspended in a styrene polymer. U.S. Patent No. 3,595,60
No. 2 discloses an absorption stabilizer comprising hydroxybenzophenone and benzylidene malonate bound to an esterified methylolated melamine.

The urethane polymer contains 4-amino- or 4-(3-aminopropyl)amino-2,2,6,
6-thitramethylbi is a derivative of West German Patent Publication Nos. 2,642,374 and 2.642,386.
As disclosed in each specification of the No.
It is photostabilized by the inclusion of tetramethyl-4-bixridinyl) sepacate as disclosed in German Patent Publication No. 2.820,419. According to U.S. Pat. No. 3,445,423, 0.1-2%, preferably 0.4-0.8%, is added to automobile windshields.
resorcinol monobenzoate bound to a urethane adhesive at low concentrations.

The effectiveness of 2,2,6,6-thitraalkylbioIJ lysine as a UV stabilizer has also been described in the art in West German Patent Publication No. 2.748,362 and in ``M
akromo:'l), Chem, J Vol. 181 No. 5
95-633 (1980), in which the stabilizer is included in the free radically polymerizable monomer. Stabilizer-containing monomers such as 2,2,6
．． 6-Tetramethyl 4-piperidyl acrylate can be homopolymerized and copolymerized with suitable free radical copolymerizable monomers to produce polymers with improved photostability. Similar acrylate and methacrylate monomers containing heterocyclic groups and which can be polymerized into photostable polymers are disclosed in U.S. Pat. Nos. 4,210,612 and 4,294,949. is being done.

However, non-UV-absorbing stabilizers, such as piperidine derivatives, whether bound to a polymer or not, are generally highly polar and may not be able to impart water resistance to the coating. Furthermore, because they act on the indirect effects of UV degradation, they can be effective throughout the entire thickness of the coating, rather than concentrating their effects at the surface, as sorbent stabilizers can. .

Patent No. 4,308,362
Copolymers having repeat units of maleic or fumaric acid esters or amides containing a gin moiety are disclosed. The alkyl biOIJ moiety imparts photostability to the polymer. The light-stabilizing portion of the polymer is characterized by low volatility, good migration stability and good compatibility with the base polymer to which the light-stabilizing properties are to be imparted. 'Azo and /ξmi-oxy leaving group initiators containing ultraviolet light stabilizing groups and their use in the preparation of free radical initiated polymers exhibiting ultraviolet light stability are disclosed in Patent No. 5,956,269. ing. A large number of types of ultraviolet light stabilizing compounds are disclosed for inclusion in free radical initiators, such as phenyl salicylate, 0-hydroxybenzophenone, cyanoacrylate, benztriazole and resorcinol monobenzoate.

One problem with incorporating UV absorbing stabilizers into polymers by linking them to polymerization initiators such as azo and peroxy initiators is that this method usefully does not involve the use of stabilizers that can be incorporated at high molecular weights. This essentially means limiting. This patent does not mention stabilizers at levels above 10 weight plates in coatings, and does not use more than 2 monomer units (mar) of stabilizers in the polymer molecule.

U.S. Pat. No. 3,429,852 teaches ethylenically unsaturated benzophenone sensitized acrylic copolymers that can be used to provide cross-linking in paint films.

U.S. Pat. No. 2,970,066 contains UV stabilizers containing dihydroxybenzophenone and aryl analogs of methyl β-resolucrate, and reacts the stabilizers with incyanate prepolymers and possibly in the reacted polymer. discloses urethane polymers that retain some reactive incyanate groups.

U.S. Pat. No. 3,441,545 discloses reacting UV stabilizers containing stabilizer precursors including dihydroxybenzophenone and resorcinol monobenzoate with various prepolymers via acid-ride groups. ing. On the other hand, residual chlorides, which are useful for a variety of purposes, including certain coatings, may pose some difficulties in end use.

U.S. Patent No. 4.3510.650 and U.S. Patent No. 4,36
No. 2,895 discloses an acrylic resin having residual double bonds and no cross-linking agent, and having a safety time of up to 5% and copolymerized in a single step.
Benzophenone stabilizer copolymers are disclosed. (Department,
Weights and ratios are by weight unless otherwise specified. ) U.S. Patent Nos. 4,208,465 and 4. ．． 35
5.071 each specification also has a paint solids content of 1 to 20.
European Patent Publication No. 29595 (19a1) discloses glycidyl acrylic polymers with melamine crosslinkers and UV stabilizers; The stabilizer is not bound to the polymer.

U.S. Patent No. 3,372,835 (U.S. Pat. No. 4
．． No. 528,346 (divisional application) contains ultraviolet stabilizers such as resorcinol monobenjetra, such as 15%
It is copolymerized via silane groups at a high level.

18- U.S. Pat. No. 3,652,492 teaches the preparation of self-crosslinking monomers and polymers containing fluorophores and mixed ultraviolet absorption sensitizers and stabilizers.

GB Patent Application No. 2,036,033A discloses the use of epoxy bridges to attach salicylate UV stabilizers to polymers.

U.S. Pat. No. 3,849,373 discloses attaching ultraviolet absorbers to polymers through acid-base salt bonds.

The patents are incorporated herein by reference.

A common method for UV stabilization is to use a strong absorbing stabilizer such as a hydroxyphenylbenztriazole such as Tinuvin 328, sold by Hachiha Kaigyi Co., Ltd., at low concentrations, e.g. 0.5 to 3 parts of the total composition. be. Higher concentrations are generally considered uneconomical due to the high cost of the stabilizer and unstable due to mobility.

However, the present invention provides for relatively high concentrations of ultraviolet light absorption stabilizers that need not have any significant effect when chemically bound to the polymeric binder as a substantial portion of the composition to be protected. Includes discoveries that can be used.

This makes it possible to produce thin paint layers or thin films that are completely opaque to ultraviolet radiation, but which are effectively transparent to visible light. This concept is useful in many applications, for example, outer transparent layers of paint, some of which can be pigmented and others over other paint layers, coatings on textiles or fabrics that may contain UV-sensitive dyes or other ingredients, through glass, etc. Coatings or films for glass to minimize UV transmission, coatings for wood or plastics, coatings of molded resins used as reflectors or/housings for fluorescent or arc lighting e.g. high pressure mercury arc melting, films. 'ft is a bulk additive, hairspray to minimize solar bleaching or discoloration of hair dyes (U.S. Pat. No. 3,445,5
66), may be advantageously used in color photographic coatings and other potential applications.

The present invention is a top automotive finishing system having one or more colored layers on the primer and overcoated with one or more clear layers to enhance the aesthetics of the vehicle and give it a higher gloss. It appears to be particularly useful for thin, unpigmented transparent coats to be used as layers.

The present invention provides an outer clear coat in a 21-color coat/clear coat finish system that provides strong UV stabilization sufficient to localize degradation to the outer portion of the surface. Intermediate coats that sometimes occur with color coat/clear coat finishes can be slowed down and surface chalking can be reduced. With the refractive index of the appropriately chosen components, the gloss is well maintained and the hollytusch is able to repair this type of aging effect.

The present invention is directed to reacting with a resorcinol monobenzoate or a resorcinol monobenzoate-containing derivative that absorbs ultraviolet radiation and effectively dissipates the resulting energy as heat, bonding to the hydroxyl group on the resorcinol monobenzoate via a linking group. and containing from 12.5 to 8096 resorcinol monobenzoate by weight, the remainder being said moiety, and said linking groups being ether, carbonate and urethane groups and at least one group selected from the group consisting of ester groups containing at least 2 carbon atoms; is an alkyl or alkoxy group containing 14 carbon atoms and has at least one unsubstituted position ortho to the carbonyl group on the a-ring. Provides coalescence.

The present invention also encompasses coating compositions containing a UV stabilizer polymer that absorbs UV radiation and effectively dissipates the resulting energy as heat, but does not contain an effective amount of a UV sensitizer. but the coating composition includes 12.5% to 50% by weight of a first portion that absorbs ultraviolet energy, which first portion is bonded to a polymeric second portion to provide 12.5% to 50% by weight of a first portion that absorbs ultraviolet energy. .5-8
The coating composition also contains a cross-linking material (cross-1) that aids in curing the coating by cross-linking with the stabilizer polymer. ,inki
ngsnecies).

Preferred coating compositions contain about 15-50% resorcinol monobenzoate, more preferably about 20%. Such coating compositions may contain an aqueous or organic solvent-based liquid carrier or they may be dry powder coating compositions.
Preferably it contains at least about 2.1 or 2.5 mar, more preferably about 7.5 mar of resorcinol monobenzoate. The number average molecular weight of the polymer is about 1,500 to 45,000 for some systems, preferably 3.000 to 10,000, more preferably a00
It ranges from 0 to 10,000.

The polymer-bound resorcinol monobenzoate of the present invention can be prepared by reacting the haresorcinol monobenzoate with functional groups on a preformed polymer, or by comonoming, e.g., resorcinol monobenzoate with a suitable methacrylic monomer. and then homopolymerization or copolymerization of this comonomer.

The resorcinol monobenzoate can be attached to an acrylic 13 complex containing an epoxy group provided by a polymer such as glycidyl methacrylate via the hydroxyl group on the resorcinol monobenzoate. When the resulting polymer-bound resorcinol monobenzoate is subjected to ultraviolet radiation, it absorbs a portion of the radiation and undergoes photo-Flys rearrangement.
The polymer-bound dihydroxybenzophenone undergoes a photorearrangement called Fries re-arrangement. This is the structural formula of resorcinol monobenzoate, and it is a dihydroxybenzophenone structure.

As is known, the UV stabilizing effect of dihydroxybenzophenone = 26- involves the interaction of the middle carbonyl of the ring with the hydroxyl group shown at the top of the ring to the right of the position ortho to this carbonyl. do. Since the bonding of resorcinol monobenzoate is via a hydroxyl group, the group remains bound to the polymer in the form of dihydroxybenzophenone generated by phototransfer.

"Derivative containing resorcinol monobenzoate"
The expression resorcinol monobenzoate refers to a compound or reaction product which retains its properties and the effect of performing its functions in the invention as defined below. Although such derivatives may be used in the present invention for maximum cost effectiveness under the present circumstances, resorcinol monobenzoate itself is preferred.

The resorcinol monobenzoate derivative has the structure (wherein R
and P' is hydrogen or an alkyl or alkoxy group containing 1 to 14 carbon atoms). Furthermore, the positions of R and B' must be such as to provide at least one unsubstituted ortho position (2 or 6) on aJJl.

Lerresorcinol monobenzoate bound to a linking group via its hydroxyl group includes, but is not limited to, the following:

29 - X=N or O 3-chloroformoyl-resorcinol monobenzoate In the preparation of the polymers of the invention, prepolymers of various acrylic monomers, including, for example, glycyl-30-cysyl methacrylate, are prepared and then this prepolymer is It has been found that reacting the UV stabilizer is sometimes better than attempting to copolymerize all the monomers containing the UV stabilizer at once.

There are two important differences between lacquer and enamel. Enamels undergo chemical reactions after application, and foreign additives that can inhibit such reactions are generally undesirable. Also, the molecular weight of enamels is generally lower than that of lacquers.

Prescribing enamels can be more difficult than lacquers. Enamel resins do not need to be synthesized under conditions that can decompose the UV stabilizer. For example, for high solids enamels low molecular weights are required and polymerization at relatively high temperatures must be used. Therefore,
In the context of the present invention, the post-reaction of the stabilizer with the prepolymer in the enamel is difficult, if possible - when using a stabilizer pre-reacted with the enamel monomers prior to polymerization. It has been discovered that polymer attachment of stabilizers is possible.

Dihydroxybenzophenone and resorcinol monobenzoate b and their derivatives, although many types of UV stabilizers can be used in the enamels of the invention, including both more and less efficient stabilizers. In addition, the following stabilizers are particularly useful in the coating compositions of the present invention.

2-hydroxy-4-hydroxyethoxybenzophenone (R=OH) 2-hydroxy-4-amine ethoxybenzophenone (
R=NH2) R=OH or NH2 Phenylsalicylate 4-aminophenylsalicylate 2-(2,4-4; hydroxyphenyl)-benztriazollo'n Reported coatings stabilized with dihydroxybenzophenone It is believed that some of the yellowing of the composition is due to metal ions or 33-complex cleavage or chelating agents reacting with the stabilizer.

However, if resorcinol monobenzoate is used as an absorption stabilizer precursor, for example in a film or dry coating, it will not rearrange to dihydroxybenzophenone until irradiated with ultraviolet light. Metal ions or other color-forming substances incorporated into the matrix of a solidified film or coating as compared to in the liquid state.
A decrease in the mobility of cj, es) is thought to reduce color prohibition.

It is also believed that commercially available resorcinol monobenzoates are purer than the available dihydroxybenzophenones.

Although some yellowing can result from different mechanisms, including byproducts of incomplete polymerization of resorcinol monobenzoate and byproducts of photorearrangement of resorcinol monobenzoate to dihydrobenzophenone, melamine cross-linking Using higher concentrations of the stabilizer of the invention compared to the upper limits suggested in the literature, even more so when using more aggressive amine crosslinkers than when using binders. I might be able to do it.

Furthermore, certain chemical cures, such as air oxidation, are inhibited by phenol. Large amounts of dihydroxynzophenone inhibit such chemical curing. However, when resorcinol monobenzoate is used, no such effect exists if the conversion to dihydroxybenzophenone is not carried out until after the film or coating has been cured.

2-) - Lacquers generally tolerate higher amounts of plasticizers and other additives than enamels because they have more swelling properties than mels. Unable to tolerate high levels of additives. Therefore, it is not highly anticipated that enamels can use higher levels of the UV stabilizers of the present invention than if lacquers were included.

In films, the first is cohsrent.
) the use of cross-linking in at least two steps, the second to produce the film itself and the second to change the properties of the film being used after it wraps around the object, e.g. to harden or shrink the film; be able to.

Other adjuvants can be used in the compositions of the invention provided they do not impair the basic and novel characteristics of the invention. Supplementary UV-active ingredients such as hindered amine light stabilizers or quenchers and phenolic antioxidants can be used as is often practiced in conventional paints. Pigments, particularly light-transmitting pigments of desired refractive index, aid in chalking and abrasive properties. Coating compositions can be formulated with additional resins to achieve the desired effect.

The polymers used in the invention containing glycidyl methacrylate can be produced by methods described in the literature. 1500-45,0 for norisolid enamel
Such polymers having a number average molecular weight of 0.00, preferably from 3,000 to 10,000, can then be reacted with a UV stabilizer containing reactive functional groups such as amine, hydroxysweet or acid groups. Cyamine, via the epoxy group of glycidyl methacrylate, to the starting functional group
The desired amount of UV stabilizer can be incorporated into the polymer backbone through ether or ester linkages. The amount of UV stabilizer can be varied depending on (1) the desired level of UV protection and (2) the amount of residual epoxy desired for cross-linking. The amount of UV stabilizer included is from 12.5 to 12.5, based on total polymer solids.
50 weight division can be changed hereditary, but the desired range is 20-5
It is between 0%. This inclusion reaction occurs at temperatures between 80° and 130°C, with the preferred range being between 100 and 110°C. The reaction time is 1-12 hours, the optimum range is 6
~8 hours. Generally, the incorporation of stabilizers into the polymer is incomplete. Some unreacted stabilizer then remains in the composition.

Optionally, the modified acrylic copolymers of the present invention may be mixed with conventional cross-linking agents such as monomeric or polymeric melamines, isocyanates, phenols, alkyds and other air drying systems or preferably various 2-13-14- and Cross-linking can be achieved using polyfunctional amines. A particularly suitable amine is methylenedicyclohexyl 4,4'
- diamines and other cycloaliphatic or aromatic diamines such as Ancamine 1618.1,5-hexane diamine, hexamethoxymethyl melamine or polyamine resins, e.g. weight ratio 40/48/ 12/4.3
Solid content with (P engineering stoichiometry with respect to MAA) 4
Mention may be made of methyl methacrylate/lauryl methacrylate/methacrylic acid/propylene imine with 1.39 milliequivalents of amine per 1'y of 3% solid polymer. Alternatively, the crosslinking can also be carried out by incyanates, which may be monomers such as Desmodur N from Mobay or polymers such as styrene/butyl methacrylate in a weight ratio of 42.2/10/4610.08. /isocyanate ethyl methacrylate)/N-dodecyl mercaptan.

The molar ratio of crosslinker to acrylic was adjusted to 1.0.
°1~4. Gives a stoichiometric ratio of D:1. A desirable range is between to:1 and 3.0:1.

Such films cure at room temperature or above with a cross-linking agent system to give a high gloss of 80 to 115 at a 20° angle and 4 ~20
Gives a film with Knoop hardness and good toughness.

Lower hardness is also desirable and can be obtained for certain purposes. Furthermore, these coatings exhibit outstanding UV stability lasting from more than 2,000 hours to more than 19,000 hours in the QUV test, with gloss retention of 70-93% depending on the coating system. These coatings can be applied to a variety of substrates including painted surfaces, wood, plastic, glass, metal and organic films.

Example 1 Acrylic prepolymer with epoxy groups 49/4/
The following components in a weight ratio of 37: butyl acrylate/
Manufactured from hydroxyethyl acrylate/glycidyl methacrylate.

The prepolymer is made by standard vinyl polymerization techniques. That is, the monomers are combined with 0.5-7% free radical initiator. This mixture is fed into a solvent (e.g. 2-heptanone) maintained at a controlled temperature to form a solution polymer.

The prepolymers are then combined and sufficient 2,4-dihydroxybenzophenone tyc is reacted with resorcinol monobenzoate to form a polymer containing 20-50% UV stabilizer. This reaction can be catalyzed. However, the preferred method is without catalyst. The reaction is maintained at a temperature in the range of 41-100°C to 175°C to avoid excessively long reaction times and degradative side reactions.

A typical enamel can be made by blending the following ingredients:

Acrylic ultraviolet stable resin 50-80 parts Hexamethoxymethyl melamine 20-50 parts
20 to 400 parts of these enamels are applied by conventional methods such as air tin spraying and fired for 30 minutes at 120 DEG C. to produce a hard gloss finish.

Example 2 Acrylic prepolymer 1237.2F in refluxing methyl amyl ketone (MAK) 834, II glycidyl methacrylate, 1100
．． 02 n-butyl acrylate, 300. A solution of 125.21f of human 42-oxyethyl acrylate, 125.21f of methyl amyl ketone, and 62.69 of Luzol 70 (a 75% solution of tertiary butyl peracetate sold by Hanwald) was added over 225 minutes. After this feed, a solution of 62.62 Luzurzol 70 in 8.01 MAK was added over 15 minutes. After an additional 30 minutes of reflux, the resin was allowed to cool, producing a 62% solids prepolymer.

Example 3A Resorcinol Monobenzoate Resin 32.2
11.26 f (0,05
26 mol) of resorcinol monobenjetra was added. This mixture was refluxed for about 3 hours. This resulted in a 72% solid resin containing 36.1% resorcinol monobenzoate on resin solids.

Example 3B Dihydroxybenzophenone Resin The method described above for resorcinol monobenzoate was followed exactly, except that 11°269 2,4-dihydroxybenzophenone was substituted for the resorcinol monobenzoate.

This reaction yielded a 72% solid resin containing 36.1% dihydroxybenzophenone on the resin solids.

Example 4 Clear enamel 9831 resorcinol monobenzoate or dihydroxybenzophenone resin, 3. Ot's cash register 7y (
Resimene) 755, (completely alkylated melamine formaldehyde resin sold by Monosand), 0.0
69 50% p-toluenesulfone powder in methanol
A clear enamel was formulated by mixing hydrate and 3.84 f xylene. This enamel was applied to a metal substrate primed with a conventional silver metallic automotive enamel. This transparent enamel is heated in an oven at 121°C for 30 minutes.
Cured for 0 minutes.

Example 5 Accelerated exposure
ering) A Q, LIV weathering tester manufactured by Q Panel Company was subjected to a light cycle at 70°C for 8 hours and a light cycle at 50°C for 4 hours.
It was used in a humid cycle at °C. The formulations tested were:

A, resorcinol monobenzoate as described in Example 4 Suzu, Meru B, dihydroxybenzophenone enamel as described in Example 4, Ru C0 transparent enamel similar to A and B above but without UV stabilizer D, Ciba. Enamel C containing 3% of Teinuvin 328, a UV stabilizer sold by Geigy. Results are reported at 20° gloss. A result with 100 is the best.

45- 5ov time AB CD o 100 100 80
B6550 87 96 84
881100 89 95 7
7 B21261:l 87
95 52(1) 811730
1 321880
1
12780 79 815460
57 73 (1) Cracks occurred on the enamel surface.

Example 6 Preparation of copolymerizable resorcinol monobenzoate comonomer Resorcinol monobenzoate 214.2f? (1 mol), triethylamine 106f (1.05 mol) and 1t of reagent grade acetone were added under nitrogen atmosphere. The mixture was stirred until dissolved, then cooled to 0°C. Then methacryloyl chloride 11
(1 (0.05 mol)) was added at such a rate that the temperature was kept at or below 10 °C. A white precipitate formed during the addition process. After the addition was complete, the cooling bath was removed and the reaction mixture was The mixture was stirred for a minute.

The reaction mixture was filtered and the precipitate was washed with acetone.

The filtrate was slowly added to twice the volume of vigorously stirred water. As stirring continued, a solidified oil separated. The solid was filtered and dried to yield 2652 3-methacryloxyphenylbenzoate.

Example 7 Preparation of Acrylic Epoxy Preformer 120 O
The toluene of f was processed.

The solvent was brought to reflux temperature and the monomer and initiator feeds were started. Methyl methacrylate 500 F, butyl methacrylate 6002 and glycidyl methacrylate 600? of monomer feed was added over 3 hours. During this time, DuPont sold Noazobisisobutyronitrile 1-polymer initiator, VAZO-6730? and toluene 15
A 0-initiator feed was added over 5.5 hours. After the addition was complete, the polymer solution was kept at reflux for an additional hour and then allowed to cool at room temperature. The final resin solution contained 54% polymer solids. Gel permeation chromatography revealed that this resin has a number average molecular weight (M9) of 8800 and a
It was shown to have a weight average molecular weight ("w) of 0.000.

Example 8 This example is an example of a series of post-reactions for the attachment of UV stabilizers to acrylic polymers.

In a 1 ton 4 diameter round bottom flask equipped with a reflux condenser, mechanical stirrer, temperature monitor and nitrogen inlet, 300 g of the acrylic polymer described in Example 7, 667 resorcinol monobenzoate or 2,4-dihydroxybenzophenone or half of each, 56 g of tetrahydrofuran and 0.12 g of Irganox 101, a hindered phenol antioxidant sold by Ciba Geigy.
I loaded 0. The reaction mixture was heated to reflux for 6 hours,
Then it was allowed to cool to room temperature. The resin containing the 25 inferior UV stabilizer, resorcinol monobenzoate or 2,4-dihydroxybenzophenone, was a clear, slightly yellow resin solution. Acrylic polymers containing higher or lower UV stabilizers can be prepared in a similar manner by adjusting the amount of stabilizer added to the prepolymer.

It also has a blend of UV stabilizers! It can be added in a similar manner. For example, for a resin containing a 20% stable 49-agent, either 31.5r' or half the amount of each can be used in place of the 662 stabilizer.

Example 9 The acrylic resin described in Example 7 of 6002 was placed in a mechanical stirrer, reflux condenser, temperature control, and nitrogen inlet.
into a 4 diameter round bottom flask.

The resin was brought to reflux temperature and treated with 100.3 f of either resorcinol monobenzoate or 2,4-dihydroxybenzophenone or a blend of both in tetrahydrofuran. The reaction mixture was heated to reflux for 6 hours and then allowed to cool. This acrylic polymer containing a hereditary external light stabilizer of 37 weight polymer solids was a clear, slightly yellow solution.

Example 1050 - This example demonstrates a method for cross-linking with the acrylic polymer described in Example 8 and its transparent film/two-tie/g preparation.

Ancamine 1618” (cycloaliphatic amine crosslinker sold by Pacific Anchor),
The acrylic polymer described in Example 8 can be cross-linked and a transparent film or coating produced by blending 1 to 1.79 of the acrylic polymer described in Example 8 with the acrylic polymer 152 described in Example 8. For application, the blend is combined with a solvent mixture of toluene/xylene/cellosolve acetate (ethylene glycol monoethyl ether acetate, sold by Union Carbide) and 0.1 f Irganox '1010 (a hindered phenol antioxidant, sold by Ciba-Geigy). ) to the desired viscosity. The finish is then applied to the desired surface by spraying or brushing and can be cured at ambient temperature or baked at 82°C for 60 minutes. The cold cure system gives a solvent resistant film after 3 days and the fired system after cooling at room temperature. Both the baked and cold cured films provide outstanding durability as demonstrated by 90% 20° gloss retention after over 1700 hours in the QUv test.

Example 11 This example demonstrates a method for cross-linking the acrylic polymer described in Example 9 and producing transparent films/coatings.

The UV-stable acrylic polymer described in Example 9 was cross-linked by blending Desmotowool N (a multifunctional isocyanate cross-linker sold by Mobay) 4.2-51 with the acrylic polymer 101 described in Example 9. A transparent film/coating can then be produced. For application, a mixture of acrylic polymer and isocyanate cross-linking agent is used in toluene/xylene/cellosolve acetate (sold by Union Carbide) (50/40/10).
and dibutyltin dilaurate to the desired viscosity and applied to the substrate by spraying or brushing. The coating can then be baked at 82° C. for 30 minutes or can be cured at ambient temperature. The cold cured film becomes solvent resistant after 5 days and the fired system after cooling. Both the fired and cold cured films exhibit good durability in the Q, UV test, retaining 90% gloss after 100 hours.

Example 12 1 part acrylic polymer to 2 parts polymeric isocyanate,
For example, methyl methacrylate/butyl methacrylate/with 54% solids content of 2000 Mn
The acrylic resin of Example 9 can also be cross-linked and produce transparent films or coatings by blending with isocyanate ethyl methacrylate/n-dodecyl mercaptan (42,210,8/4 B/10). Application is accomplished in a similar manner to Example 11. 1% dibutyltin dilaurate was added as a catalyst.

Example 13 This example demonstrates the production and molding of a transparent UV-absorbing coating that is oxidatively cured using a linoleic acid ester.

300f of the prepolymer of Example 7 was charged to a 1 ton 4 diameter round bottom flask equipped with a mechanical stirrer, reflux condenser, nitrogen inlet and addition funnel. The resin solution was heated to reflux and 66.55' of a UV stabilizer (resorcinol monobenzony hl or 2,454-dihydroxybenzophenone 9 was added in 502 m of tetrahydrofuran. The reaction was allowed to proceed for 6 hours at the reflux point. 50 g of linoleic acid was then added dropwise over 1 hour. After the addition was complete, the reaction mixture was refluxed for an additional hour, and the cooled polymer was cooled with 1% cobalt naphthinate to induce cross-linking. A transparent film/coating can be produced by diluting with a suitable solvent blend.The resin can be applied to the substrate by spraying or brushing.

earth and company 55- 119-

Claims (1)

[Claims] 1) Reacting resorcinol monobenzoate or resorcinol monobenzoate with a sul derivative containing it,
comprising a polymeric moiety attached to a hydroxyl group on the resorcinol monobenzoate by a linking group and containing from 12.5 to 80% by weight of resorcinol monobenzoate, the remainder being said polymeric moiety;
and said bonding group includes at least one group selected from the group consisting of ether, carbonate and urethane groups and ester groups containing at least two carbon atoms, and said derivative has the structural formula (wherein R and R' are hydrogen or an alkyl or alkoxy group containing 1 to 14 carbon atoms, and there is at least one unsubstituted position 1 m above ortho to the carbonyl group) Polymers with 2) Claims in which the moiety includes one or more acrylic monomers comprising glycidyl methacrylate, and the hydroxyl group on the resorcinol monobenzoate is bonded to the epoxy group on the glycidyl methacrylate. The polymer according to item 1. 6) The polymer according to claim 1, having a weight ratio of 20 to 50 (resorcinol monobenzony). 4) The polymer of claim 1 having a number average molecular weight in the range of about 1,500 to 45,000. 5) The polymer of claim 1, containing on average at least about 2.1 mer of resorcinol monobenzoate per molecule. 6) Approximately 1500~45. resorcinol monobenzoate having a number average molecular weight in the range of ODD from about 15 to 8
Contains 0% by weight, and has a diameter of about 2.1m per molecule.
A polymer according to claim 1 containing resorcinol monobenzoate of ar. 7) reacting a monomer precursor of the polymer moiety with resorcinol monobenzoate or a monomer derivative containing resorcinol monobenzoate to form a comonomer;
A method for producing a polymer according to claim 1, which comprises then polymerizing the polymer. 8) A process for producing a polymer according to claim 1, wherein resorcinol monobenzoate or a derivative containing resorcinol monobenzoate is reacted with the polymer moiety to bond them together via the linking group. 9) The hydroxyl group on the resorcinol monobenzoate is attached to the epoxy group on the glycidyl methacrylate in the monomer precursor or the polymeric part. Method. 10) First part 12.5~ that absorbs ultraviolet energy
50% by weight and said first portion comprises a polymer second portion.
to form the UV stabilizer polymer containing 12.5 to 80% by weight of the first portion;
It contains an ultraviolet stabilizer polymer that absorbs ultraviolet radiation and effectively dissipates the resulting energy as heat, which also contains a cross-linking material that aids in the curing of the coating by cross-linking with said stabilizer polymer. , but does not contain an effective amount of a UV sensitizer. 11) the second portion contains the first portion, and the first portion is bonded to the first portion by means including a bonding group that does not substantially inhibit ultraviolet absorption stability; 11. A composition according to claim 10, wherein the composition comprises at least one group selected from the group consisting of ether, carbonate and urethane groups and ester groups having at least 2 carbon atoms. 12) The coating composition according to claims 5 to 10, wherein the first moiety is dihydroxybenzophenone having a hydroxyl group ortho to the carbonyl. 13) The structural formula in which the first portion contains resorcinol monobenzoate (where P and R' are hydrogen or an alkyl or alkoxy group having 1 to 14 carbon atoms, a carbonyl group, 11. The coating composition according to claim 10, wherein the coating composition is a derivative having at least one unsubstituted position in the apical ortho position. 14) Said patent, wherein said second portion is an acrylic prepolymer containing glycidyl methacrylate, and the hydroxyl group on the resorcinol monobenzoate is bonded to the epoxy group on the glycidyl methacrylate to form said bonding group. The coating composition according to claim 16. 15) The resorcinol monobenzoate absorbs the incident UV radiation and photorearranges to form the dihydroxybenzophenone that remains bound to the polymer; and the dihydroxybenzophenone absorbs the incident UV radiation and effectively converts the resulting energy into heat. 14. A coating composition according to claim 13 which is dissipated.