前苏联专利SU805962A3 Photlpolymerized composition for coatings

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专利摘要:
1536378 Radiation-polymerizable monomers BAYER AG 31 Oct 1977 [11 Nov 1976] 45179/77 Heading C3P [Also in Division C2] A radiation - crosslinkable diluent for radiation - hardenable compositions comprises a mixture of triacrylates of a reaction product of trimethylol propane and ethylene oxide with an average degree of ethoxylation of from 2À5 to 4, the ethoxylated trimethylol propane being substantially free from trimethylol propane and having the following distribution: 4 to 5% by weight of monoethoxylation product; 14 to 16% by weight of diethylation product; 20 to 30% by weight of triethoxylation product; 20 to 30% by weight of tetraethoxylation product; 16 to 18% by weight of pentaethoxylation product; and 6 to 7% by weight of hexaethoxylation product. Mixtures having average degrees of ethoxylation 2, 6 and 12 are used for comparison. The compositions may comprise a binder with radiation-polymerizable double bonds, e.g. an epoxy acrylate, a polyester containing cocondensed fumaric acid and styrene, or a urethane acrylate.
公开号:SU805962A3
申请号:SU772541694
申请日:1977-11-10
公开日:1981-02-15
发明作者:Шустер Карл-Эрнст；Юрген Розенкранц Ганс；Фур Карл；Рудольф Ганс
申请人:Байер Аг (Фирма)；
IPC主号:

专利说明:

one
The invention relates to photographic methods, and in particular, to photopolymer-containing compositions that can be used to make coatings on various materials, for example, plastics, wood, etc.
A photopolymerizable coating composition is known, comprising a polymerization-capable compound, for example an epoxy acrylate or an unsaturated ether, a photoinitiator, for example a benzoin ether, and also a diluent, trimethylolpropane triacrylate Ull.
The disadvantage of the composition is that it requires a relatively long curing time, and the coatings obtained from it have low adhesion to the substrate, low resistance to solvents and low hardness.
The purpose of the invention is to reduce the curing time of the composition and improve the quality of the coatings obtained from it.
The goal is achieved by the fact that the composition as a diluent
will get the trif rylate oxyethylenated trimethylpropanol composition, wt.%:
Monooxyethylated
4-5
product
Dioxyethylated
14-16
product
Trioxyethylated
20-30
product
Tetraoxyethylated 20-30 product
Pontaoxyethylated 16-18 Hexoxyethylated Product 6-8
product
At the same time, the components of the proposed composition are taken in the following ratio, wt.%.
Polymerization-able compound
0.1-10 Photoinitiator
5-80 Thinner
The diluent used in the composition contains ethoxylated products, the average degree of oxyethylation of which is from 2.5 to 4. The diluent is obtained in a known manner and it is a technical mixture. The preparation of acrylic acid ester of ethoxylated products is also carried out in a known manner, for example, by direct esterification with acrylic acid or azeotropic esterification using benzene, toluene or gasoline as a water carrier in the presence of suitable catalysts and stabilizers. The preparation can also be carried out by transesterifying acrylic acid esters in the presence of catalysts. Curing of the composition can occur through energy-rich radiation, such as ultraviolet light, electron or gamma rays, preferably ultraviolet light. If the polymerization is carried out with ultraviolet light, the photoinitiators usually are suitable for use with compounds such as benzophenone, as well as aromatic ketra dinenei, benzophenone derivatives (for example, alkyl benzophenones, halogenated or halogenylated benzophenones. Anthraquinone and its numerous derivatives are also active photoinitiators, for example, P) methyl anthraquinone, tert-buti anthraquinone and anthraquino carboxylic acid ester, chlorosulfonated xanthones and thioxanthones. The composition can. Also contain tertiary amines, for example, triethylamine, phosphines or thioether in an amount up to 5 wt.%, In terms of the radiation-curable component, as a result of which the reactivity of the system can be further enhanced. Composition - is suitable for use as a pulp for impregnating and coating wood, paper, cardboard, plastics, leather, metals, textiles and crafts, as well as for coating ceramic products. It can also be used as a binding agent for printing ink, as a photoresist for producing printing forms with mesh patterns, and as a mass for printing with mesh patterns. Example 1. Preparation of polyoxyethylated trimethylolpropane triacrylate - 400 g of oxyethylated trimethylolpropane composition, wt.%: Monooxyethylated product .4 Dioxyethylated product Trioxyethylated product Tetraethoxyethylated. product Pentaoxyethylated product Hexoxyethylated first product .6 (degree of oxyethylation 3.75; viscosity 500 cP at, hydroxyl number 550) in Medium 50 ml of toluene is subjected to azeotropic esterification of 216 g of acrylic acid in the presence of 2.5 g of p-toluenesulfonic acid and 0, 2 g of toluhydroquinone until no more water is released. After the reaction, neutralized with an equivalent amount of Na, in terms of p-toluenesulfonic acid, toluene is distilled off in vacuum (final pressure 1 Torr, final temperature of the reaction product 100 ° C) and the product is filtered. A light-yellow, odorless liquid is obtained with a viscosity of 102 SP (20 ° C, a Geppler viscometer, a refractive index of 0 1.4738, an OH number of 13, and an acid number of 0, 8. EXAMPLE 2. Example 1 is carried out with that difference that 300 g of a xethylated trimethylolpropane composition, wt.%. Monoxyethylated product5 Dioxyethylated product 16 Trioxyethylated product23 Tetroxyethylated product30 Pentox. Ethylated product 18 Hexoxyethylated product 8 (degree of ethoxylated 4.0, 530 cP at 20%, in a dosing rate of 20%) in a dimer with 20, ate, 0% per day, 20 p. 00 g of acrylic acid is esterified, hydroxyethyl trimethyl propane triacrylate is obtained with the following characteristic: viscosity 115 cP (20 ° C, Geppler viscometer), refractive index: P 1,4739, and 13 oxroxy number, acid layer 0,8. e p 3. Conducted as described in example 2 with the difference that 300 g of ethoxylated trimethylolpropane contains the following composition, wt.%; Monooxyethylated product5 Dioxyethylated Product Trioxyethylated product Tetroxyethylated product Pentoxyethylated Hexoxyethylated This product (degree of ethoxylation 3, bone 525 cP at 20 ° C, hydroxyl number 530) is subjected to esterification with 200 g of acrylic acid. Oxyethylated trimethylolpropane triacrylate is obtained with the following characteristic: viscosity 110 cP at refractive index n2jO 1.4737, hydroxyl number 13, acid number 0.8. EXAMPLE 4: 60 g (58/25 wt.%) Of epoxy acrylate with a softening point of about 40 g (38.84 wt.%) Of ethoxylated ethylolpropane triacrylate, prepared according to measure 1 and 3 g of C2 / 91 wt.%) SIMPLE cb-cyanoethoxybenzoic ester (photoinitiator) is mixed at about 60 ° C and cooled to room temperature. The resulting composition has a viscosity of 100 cps at 20 ° C (Goppler viscometer). EXAMPLE 5 Example 4 is repeated, with the difference that 400 g (38.84% by weight) of epoxy acrylate and 60 g (58.25% by weight) of ethoxyethylene trimethylpropane triacrylate with a degree of ethoxylation of 3.75 and 3g (2.91 wt.%) Photoinitiator. The resulting composition has a viscosity of 21 cps and at 20 ° C {Geppler viscometer). EXAMPLE 6 Example 4 is repeated with the difference that 19 wt.% Of urethane acrylate (softening point. 35 ° C) is based on 222 g (1 mol) of isophordiisocyanate, 116 g (1 mol) of hydroxy ethyl acrylate and 200 g of polyether based on phthalic acid and ethylene glycol (hydroxyl number 260) are mixed with 80% by weight of the diluent of Example 2 and 1% by weight of benzyldimethyl ketal. The resulting composition has a viscosity of 300 cP at 20 ° C. EXAMPLE 7 Example 4 is repeated with the difference that 94% by weight of unsaturated polyester is based on 2320% of fumaric acid, 451 parts by weight. propylene glycol -1, 2, 144Q weight.h. diethylene glycol, 940 weight.h. simple dialkyl ether of trimethylolpropane and 430 parts by weight of diethylene glycol monobutyl ether are mixed with 5; wt.% of the diluent of Example 2 and 1 wt.% of benzoin isopropyl ester. The resulting composition has a viscosity of 800 cP at 20 ° C. EXAMPLE 8 Example 7 is repeated with the only difference that 94% by weight of unsaturated polyester is mixed with 5.9% by weight of the diluent of Example 2 and 0.1% by weight of the photoinitiator. The resulting composition has a viscosity of 780. CP at 20 ° C, Example 9. Example 4 is repeated with the difference that 67.5% by weight of epoxy methacrylate is mixed with 22.5% by weight of the diluent of example 2 and 10 wt.% Benzophenone. The resulting composition has a viscosity of 5300 cP at 250 ° C. Example 10. Example 4 is repeated. The difference is that 50% by weight of urethas of methacrylate based on 222 g (1 mol) of isophorone diisocyanate, 130 g (1 mol) of hydroxyethyl methacrylate and 200 g of polyether based on phthalic acid and ethylene glycol have a hydroxy number of 260), mixed with 4. wt.% of the diluent of example 2 and 3 wt.% of the useful oxime ester of phenylpropanedia-1, 2 of the formula; -l O CHt O V j7 Vt - // V, f US-C: H-O-C- V The resulting composition has a viscosity of 2500 SP at 25 s. EXAMPLE 11: 19 wt.% Ureg: anacrylate (softening point) based on 222 g (1 mol) of isophorone diisocyanate, 116 g (1 mol) of hydroxyethyl acrylate and 200 g of phthalic acid-based glyph n ethylene glycol (hydroxyl number 260) mixed with 80% by weight of a diluent of Example 2.0.9% by weight of benzyldimethyl ketal and 0.1% by weight of triethylamine followed by cooling to room temperature. The viscosity of the resulting composition is 380 cP (in the Geppler viscometer at 20 s). Example12. Receiver 6 is repeated with the difference that the diluent of Example 3 is used. The resulting composition has a viscosity of 290 cP at 20 ° C. P r and m r. 13. The compositions of examples 4-12 are applied under: a burner from the material indicated in table 1, followed by hardening of the resulting coating by irradiation with a Philips HTO-5 lamp. The same composition is used as a comparison, which, however, contains a known diluent , trimethylolpropane triacrylate (in the same amount as the proposed diluent), Table 1 summarizes the curing time of the coatings, the thickness is 20 microns (on paper), 50 microns on a polycarbonate plate, a copper sheet and a porcelain plate) and 500 microns ., respectively (on the tree constant plate and a glass plate). Data on the quality of the coatings of table 1 are summarized in table 2. T paper II wood l glass IV polycarbonate V copper N1 porcelain Adhesive strength of coatings is decanted as follows. On the coating with a sharp knife, a scratch is made in the form of a large X, onto which a cellophane film is pressed. Then the cellophane film is removed. Adhesion is considered poor if the coating is almost completely removed; acceptable, if small,
Sha part of the coating is removed, and very good, if the coating is not removed at all.
Solvent resistance is determined as follows. 0.5 ml of acetone is poured onto the coating, and then the acetone is triturated with a finger until completely evaporated. If after this treatment the coatings were not peeled off, then the resistance to
acetone is considered good, and if the coatings are sticky, resistance to acetone is considered poor.
As follows from the table. 2, the proposed composition has a shorter curing time, better adhesive strength and solvent resistance, as well as greater hardness compared to the prototype.
Table
Table 2
Continued table.

权利要求:
Claims (1)
[1]
Claim
A photopolymerizable coating composition 40, comprising a polymerization compound, a photoinitiator and a diluent, characterized in that, in order to reduce the curing time and improve the quality of the resulting coating, it contains, as a diluent, an ethoxylated trimethylolpropane triacrylate composition, weight:
Monoxyethylated Product Dioxylated Product Trioxyethylated Product
14-16
20-30
Tetraoxyethylated Product
Pentaoxyethylated product
Hexaoxyethylated Product
20-30
16-18
6-8, while the components are taken in the following ratio, weight:
Polymerization compound * 19-94
Photo initiator 0.1-10
Thinner 5-80

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同族专利:

公开号 | 公开日

DE2651507A1|1978-05-24|

DE2651507B2|1980-10-16|

GB1536378A|1978-12-20|

DE2651507C3|1981-09-10|

IT1091775B|1985-07-06|

FR2370771B1|1983-05-13|

JPS5360982A|1978-05-31|

BE860710A|1978-05-10|

US4180474A|1979-12-25|

FR2370771A1|1978-06-09|

引用文献:

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US3380831A|1964-05-26|1968-04-30|Du Pont|Photopolymerizable compositions and elements|

US3368900A|1964-06-03|1968-02-13|Du Pont|Polymerizable compositions and elements|

US3457178A|1966-10-19|1969-07-22|Olin Mathieson|Polyhydroxy polyethers stabilized with 1,1,3,3-tetramethoxy propane and polyurethane foams prepared therefrom|

US3725355A|1971-10-21|1973-04-03|Dow Chemical Co|Rapid setting polyurethane elastomer compositions|US4382135A|1981-04-01|1983-05-03|Diamond Shamrock Corporation|Radiation-hardenable diluents|

DE3200907A1|1982-01-14|1983-07-21|Bayer Ag, 5090 Leverkusen|RADIATION-curable aqueous binder emulsions|

US4417023A|1982-01-21|1983-11-22|Diamond Shamrock Corporation|Polysiloxane stabilizers for flatting agents in radiation hardenable compositions|

DE3235610A1|1982-09-25|1984-03-29|Bayer Ag, 5090 Leverkusen|RADIATION-BASED PRIMER AND ITS USE|

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US4533445A|1983-07-06|1985-08-06|Shipley Company Inc.|U.V. Curable composition|

US4592816A|1984-09-26|1986-06-03|Rohm And Haas Company|Electrophoretic deposition process|

US5110889A|1985-11-13|1992-05-05|Diamond Shamrock Chemical Co.|Radiation hardenable compositions containing low viscosity diluents|

US4876384A|1985-04-22|1989-10-24|Diamond Shamrock Chemicals Co.|Radiation-hardenable diluents|

US4885229A|1987-12-22|1989-12-05|501 Daicel Chemical Industries Ltd.|Photopolymerizable compositions|

US5496589A|1993-03-23|1996-03-05|Toagosei Chemical Industry Co., Ltd.|Curing composition and method for impregnating wood|

US5498782A|1993-09-08|1996-03-12|Union Carbide Chemicals & Plastics Technology Corporation|Distortion control additives for ultraviolet-curable compositions|

US5523152A|1993-10-27|1996-06-04|Minnesota Mining And Manufacturing Company|Organic compounds suitable as reactive diluents, and binder precursor compositions including same|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

DE2651507A|DE2651507C3|1976-11-11|1976-11-11|Use of triacrylates of oxethylated trimethylolpropane with a degree of oxethylation of 2.5 to 4 as diluents in radiation-curable compositions|

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