Photopolymeric acrylic oligomer-oligomer composition, wear-resistant coating on organic glass for glasing elements of buildings, structures and vehicles based thereon and method of producing wear-resistant coating

FIELD: chemistry.

SUBSTANCE: disclosed is a novel photopolymer acrylic oligomer-oligomer composition consisting of a bifunctional oligomer, an oligomer with functionality higher than 2, a monomer, a methyl methacrylate oligomer with molecular weight 20000-70000 and a polymerisation initiator, with the following ratio of components in pts.wt: acrylic bifunctional oligomer 15-95; acrylic oligomer with functionality higher than 2 15-70; acrylic monomer 0-25; methyl methacrylate oligomer with molecular weight 20000-70000 5-20; photopolymerisation initiator 0.1-1.0. Disclosed is a wear-resistant coating on organic glass, obtained via photochemically initiated three-dimensional radical polymerisation of the disclosed composition. Disclosed is a method of producing a wear-resistant coating on organic glass, involving a step for preparing a photopolymeric acrylic oligomer-oligomer composition and a step for curing thereof. The technical result is endowing resistance to formation of microcracks during ablation (silver resistance), low shrinkage and high adhesion to a coated substrate obtained via photopolymerisation of acrylic oligomer-oligomer compositions.

EFFECT: invention enables to obtain wear-resistant protective coatings on organic glass with surface hardness close to that of sapphire crystals.

7 cl, 6 tbl, 19 ex

 

The invention relates to new types of durable acrylic photopolymer coatings on organic glasses, giving them a hardness higher than the hardness of silicate glasses, resistance to crazing when exposed to ablation (cerebrosterol), low shrinkage and high adhesion to the substrate to obtain products of complex configuration. More specifically, the invention relates to new photopolymerizable acrylic oligomer-oligomer compositions, which when exposed to light of the visible or UV range form a coating with the specified properties. More specifically, the invention relates to acrylic oligomer-oligomer compositions containing oligomers of methyl methacrylate with a molecular weight within 20000-70000.

The level of technology

Organic glass on the basis of polymethylmethacrylate, copolymers, polycarbonate, polymers of allyl ethers and other very promising for the fabrication of glazing elements for various purposes due to their ease compared to silicate glasses and the ability to recycle products in any form is quite simple technological methods. However, wide application of organic glass for glazing prevents their principal shortcoming is the low surface hardness and they are easily scratched by particles from akademiese in the air, and as a consequence lose the transparency. In addition, by prolonged exposure in ordinary atmospheric conditions organic glass get coloring, also reducing their transparency.

For many years conducted research on the protection of the surface of the organic glass, which improves their performance properties, due to the coating of polimerizatsionnyh compositions. Development of wear resistant coatings is carried out in 3 main areas: pure organic polymerizable composition, Organoelement, most often silicon and, in recent years, filled with nanoparticles SiO2or TiO2photopolymer coating. Thus, in U.S. Pat. USA 7375144 proposed radiation-curable composition for protection of thermoplastics consisting of flexible diacrylate, aromatic diacrylate and oligoamenorrhea, forming a wear resistant coating with good chemical stability and resistance to impact. Similar composition used in U.S. Pat. USA 4908230 to get photopolymer coatings with pre-cooling the composition below the dew point.

In Pat. USA 6509398 to obtain coatings proposed composition of hydrolyzable organosilane, acrylic oligomer and polyorganosiloxane and acrylic composition for application of protective coatings for PMMA and poly is arbonate (U.S. Pat. USA 6667047), along with mono - and dimethacrylate may contain trimethoxysilylmethyl and colloidal SiO2.

Use nannapaneni compositions described in U.S. Pat. USA 5214085: the composition consists of mono - and polyfunctional acrylates and particles of SiO2the size of 15-30 nm and as a result of photopolymerization gives abrazivnostoykiye and weatherproof cover.

However, until recently, was not received satisfactory practical results in the protection of large-sized products from organic glass, intended for long-term operation, such as glazing of vehicles, buildings and structures, a photopolymerization method source of liquid compositions. In those industries where weight is a critical factor, for example in aircraft construction, glass with protective coatings of this type are often proposed for use, but development is not implemented because of problems associated with the need to improve wear resistance, resistance to crazing when exposed to ablation of the coating and its resistance.

To increase the surface hardness and wear resistance), as well as impact strength and other properties of the products of acrylate use additives hard vysokopreosv. Already in 1942, the Firm "Kulzer Corp." (Germany) for dental enamels used p is the target of polymethylmethacrylate (PMMA) methyl-methacrylate. In Pat. USA 6486234 to improve impact strength of the coating composition based on acrylic oligomers injected 1-20 wt.% PMMA or other polymers, and in U.S. Pat. USA 6462129 for this purpose use 40-99 M.Ch. PMMA or other high-polymer on 61-120 M.Ch. other components. In Pat. RF 2244335 shown that the microadditives of high molecular weight polymer PMMA (0.2 to 0.8 wt.%) to compositions based on acrylic oligomers dramatically increase the speed of the photopolymerization without substantial changes in macroviscosity composition due to the lower threshold known for acrylic oligomers "gel effect" - the rapid polymerization rate after reaching the point of gelation. At higher content of the polymer greatly increases the viscosity of the composition, which prevents the leakage of fluid to the substrate and reduces the efficiency of the process. The latter, in fact, limits the ability of promising applications of vysokopreosv for modification of protective acrylic coating: additive 2-3% PMMA so increases the viscosity of the acrylic composition that the conventional methods of coating becomes impossible.

The closest analogue of the present invention is U.S. patent No. 7375144, IPC C08F 2/48, B32B 27/38, publ. 20.05.2008. (prototype). This patent pending photopolymerizable acrylic oligomer-oligom the RNA composition to obtain a wear-resistant coatings on organic glasses, including:

- bifunctional oligomer, for example, di(meth)acrylates of aliphatic diols or bis-phenols, in particular, diacrylate of hexandiol or Bis-GMA, oligourethane(meth)acrylates),

- oligomer with functionality greater than 2, for example, triacrylate of trimethylolpropane (TATE),

- photoinitiator, for example, 2-hydroxy-2-methylpropiophenone.

Analysis of the solution of the prototype and the above patent literature shows that the status of this field of polymer science requires serious research to create a new generation of protective coatings for organic glasses, giving the product a complex of new valuable properties during long term operation. Practical experience shows that a satisfactory surface hardness and cerebrosterol protective coatings on organic glasses cannot be achieved without the use of additives to the polymer, such as PMMA. At the same time, the introduction of the polymer increases the viscosity of the composition, which leads to technological problems associated with the application, alignment, removing air bubbles their viscous compositions, especially on substrates of complex shape.

The basic idea of the present invention provides for the introduction of photopolymerizable acrylic composition of oligomers of methyl methacrylate (EMMA) mol. mass 2000-70000 instead of high molecular weight PMMA, usually they say. weight of several million. In this case it is possible to enter into the composition of up to 20% of OMMA while maintaining a technologically acceptable viscosity, and get coverage for the complex properties superior coatings from compositions not containing polymers of MMA.

Although a direct comparison of the properties of the coatings according to the present solution and the prototype is impossible due to different test methods, however, considered the prototype of the coatings obtained from the compositions very close in composition to the compositions according to the "Preliminary examples of the present application, i.e. not containing polymers of methyl methacrylate (EMMA mol. mass 20000-70000). Comparison of hardness of the coatings according to Preliminary examples FG1-PP and coatings in Examples 1-19, derived from the claimed composition (containing OMA), shows that the introduction of OMA allows to increase the surface hardness of 1-2 points on the Mohs scale and significantly reduce the shrinkage of the coating, i.e. the disadvantages of the solutions of the prototype are insufficient surface hardness of the resulting coating and its high shrinkage.

The present invention is the creation of photopolymerizable acrylic oligomer-oligomer composition to obtain a wear-resistant coatings on organic glasses, which when exposed to light of the visible or UV range forms a coating on the organization who technical glass with hardness, significantly greater than the hardness of silicate glasses, high resistance to crazing when exposed to ablation (cerebrosterol), low shrinkage and good adhesion to a substrate made of organic glass.

The invention is also developing a method to obtain oligomers of methyl methacrylate (mol. mass 20000-70000 by photopolymerization method. As is known [Karmelava L.V. and other USP. 1984. T. P.223], synthesis of low molecular weight PMMA is a difficult problem and requires special approaches, such as the use of agents, chain transfer to monomer.

The invention is also developing a method of producing wear resistant acrylic photopolymer coating on organic glasses, which will provide the product listed above for high performance.

The objectives are achieved, we offer:

- photopolymerizable acrylic oligomer-oligomer composition to obtain a wear-resistant coatings on organic glasses, including bifunctional oligomer, the oligomer with functionality greater than 2 and the initiator of polymerization, which further comprises an acrylic monomer and oligomer of methyl methacrylate (mol. mass 20000-70000 in the following ratio of components, parts by weight:

- bifunctional acrylic oligomer15-95
- acrylic oligomer with functionality greater than 215-70
- acrylic monomer0-25
- oligomer of methyl methacrylate (mol. mass 20000-700005-20
the initiator of photopolymerization0.1 to 1.0.

The proposed composition as a bifunctional acrylic oligomer can contain oligoether(meth)acrylate-based diatomic alcohols, glycols, bis-phenols, epoxyacrylate, oligocarbonate-methacrylates or oligourethane(meth)-acrylates.

The proposed composition as acrylic oligomer with functionality greater than 2 may contain tri - and Tetra(meth)acrylates three - and chetyrehtomnik spirits.

The proposed composition as the acrylic monomer may include derivatives of acrylic acids, preferably butyl acrylate, glycidylmethacrylate or methyl methacrylate:

- wear-resistant coating on organic glasses, obtained three-dimensional radical polymerization claimed photopolymerizable acrylic oligomer-oligomer composition by photochemical initiation;

- way of gaining the wear of the claimed coating on organic glasses, including the stage of preparation of the inventive photopolymerizable acrylic oligomer-oligomer composition and stage of curing, consisting of the following operations:

1) preparation of a mixture of acrylic oligomers and photoinitiators at room temperature for 30 min;

2) adding to the resulting solution, fine powder of the oligomer of methyl methacrylate (OMA) under stirring and heating the mixture at 40-50°C for 5-7 hours to obtain a transparent homogeneous solution;

3) coating the surface of the organic glass compositions prepared by spray, brush or by centrifuging;

4) curing the composition by photochemically initiated a three-dimensional free-radical polymerization with the formation of organic glass wear-resistant polymer coating.

A detailed description of the preferred option

Used in the acrylic components of the photopolymerizable oligomer-oligomer compositions and their abbreviations are listed in Table 1.

Table 1.
The components used in photopolymerizable acrylic oligomer-oligomer compositions.
Designation Name
IFWOligourethanes based isophorondiisocyanate and AEG
IFUMOligourethanes based isophorondiisocyanate and MEG
TATETriacrylate of trimethylolpropane
TGM-3Dimethacrylate, triethylene glycol
NpdaNeopentylglycol diacrylate
AAAα,ω-Hexanediamine ethoxylated
Bis-PHABisphenol glycerol diacrylate
Bis-peaBisphenol a ethoxylate diacrylate
MMAThe methyl methacrylate
GcmaGlycidylmethacrylate
BAThe acrylate
PHIPhotoinitiator "Darokar 4265" (a mixture (1:1) diphenyl(2,4,6-trimethylbenzoyl)phosphine and 2-hydroxy-2-methylpropiophenone)

Next photo is polymerizate acrylic oligomer-oligomer composition according to this invention, and then other objects of the invention claimed.

According to the present invention offer a photopolymerizable acrylic oligomer-oligomer composition to obtain a wear-resistant coatings on organic glasses consists of a bifunctional oligomer, the oligomer with functionality >2, monomer, oligomer of methacrylate of EMMA mol. mass 20000-70000 and the polymerization initiator in the following ratio of components, parts by weight:

- bifunctional acrylic oligomer in the number of 15-95 wt. parts;

- acrylic oligomer with functionality>2 in the amount of 15-70 wt. parts;

- acrylic monomer in an amount of 0-25 wt. parts;

- oligomer of methacrylate of EMMA mol. mass 20000-70000 in the amount of 5-20 wt. parts;

the initiator of photopolymerization in an amount of 0.1 to 1.0 wt. parts.

Any oligomer containing two (meth)acrylic group (hereinafter, (meth)acrylic. means that the term is derived as acrylic and methacrylic acids), can be used in this composition, if it meets the following requirements:

- combination with other acrylic compounds and oligomers of EMMA in the liquid composition, in the copolymerization process and in the final cross-linked polymer material;

- transparency in the visible region of the spectrum;

- the achievement of an acceptable magnitude of the surface t is agosti cross-linked polymer.

In this composition as a bifunctional acrylic oligomer can be used oligoether(meth)acrylate-based diatomic alcohols, glycols, bis-phenols, epoxyacrylate - products of (meth)calironia epoxy Dianova oligomers, oligokarbonatmetacrylate, oligourethane(meth)acrylates obtained as isocyanates" method and without the use of isocyanates and di(meth)acrylates other known classes.

The most promising from the point of view of use in these compositions are commercially available triethylene glycol dimethacrylate (TGM-3) and epoxyacrylate based on diphenylolpropane and its ethoxylated and glitserinovoye derivatives (bis-GMA, bis-FAA, bis-PHA), the structure of which is given below:

Another valuable bifunctional acrylic oligomer is oligourethane(meth)acrylate-based isophorondiisocyanate (IFW, IFUM):

According to the present invention as acrylic oligomer with functionality >2 can be used tri - and Tetra(meth)acrylates three - and chetyrehtomnik alcohols and glycerin, meriola, atrial, trimethylolpropane, pentaerythritol, etc. are Most suitable for complex technological properties and runasimi properties in the coating was triacrylate of trimethylolpropane (TATE):

The acrylic monomer is preferably used in the inventive composition to adjust the viscosity, as polyfunctional (meth)acrylate and MMA oligomers are highly viscous compounds. The use of low viscosity polyarizatsionnogo monomer allows not only dramatically improve the process of obtaining the claimed composition, but also gives an additional possibility to control the mesh density crosslinked material.

In principle, any capable of radical polymerization and/or copolymerization connection can be used in this composition, if it contains such a group as (meth)acryloyl-, vinyl, allyl or styrene. From the viewpoint of the reaction rate of polymerization is most preferred derivatives of acrylic acid, of which the proposed composition, it is preferable to use butyl acrylate (BA), glycidylmethacrylate (Gcma) or methyl methacrylate (MMA).

Preferred variants of the proposed technical solutions provide an introduction to the composition specially synthesized low molecular weight polymer of poly - oligomerizate with a molecular mass of 20000-70000 (OMMA). OMMA produced by the method of photopolymerization of methyl methacrylate in the presence of 1-10 wt.% photoinitiator with subsequent thermo is the processing at 80-100°C for 20 minutes In the case of EMMA cannot enter into the composition of up to 20% of the polymer while maintaining technologically acceptable viscosity, and get coverage for the complex properties superior coatings from compositions not containing polymers of MMA.

To obtain coverage of a three-dimensional radical polymerization specified acrylic composition has no significant restrictions, and can be used most effective for this purpose a method of photochemically initiated polymerization. As initiator may be used photoinitiator for polymerization in UV and visible regions of the spectrum, high-energy radiation, and any combinations of these effects.

When carrying out the polymerization under conditions of UV irradiation as photoinitiators are benzoin derivatives, such as benzoylbutyric ether, ketals, such as benzylmethylamine, hydroxyketone, for example hidroxizina-hexylaniline. Photoinitiator can also be used in combination of two or more components, as well as in mixtures with heat curing initiators.

For the photopolymerization of the claimed composition, the UV irradiation-the most preferred initiator is a mixture (1:1) diphenyl(2,4,6-trimethylbenzoyl)phosphine and 2-hydroxy-2-methylpropiophenone (PHI).

In the majority of these developments is OK for photochemical initiation was used mercury lamp high pressure output of 1000 watts.

In General, the content of components in photopolymerizable acrylic oligomer-oligomer composition to obtain a wear-resistant coatings on organic glasses can vary within wide limits:

- bifunctional acrylic oligomer in the number of 15-95 wt. parts;

- acrylic oligomer with functionality >2 in the amount of 15-70 wt. parts;

- acrylic monomer in an amount of 0-25 wt. parts;

- oligomer of methacrylate of EMMA mol. mass 20000-70000 in the amount of 5-20 wt. parts;

the initiator of photopolymerization in an amount of 0.1 to 1.0 wt. parts.

A more preferred composition of the following composition:

- bifunctional acrylic oligomer in an amount of 20-70 wt. parts;

- acrylic oligomer with functionality >2 in the amount of 15-60 wt. parts;

- acrylic monomer in the amount of 5-20 wt. parts;

- oligomer of methacrylate of EMMA mol. mass 20000-70000 in the amount of 5-20 wt. parts;

the initiator of photopolymerization in quantities of 0.5-1.0 wt. parts.

A method of obtaining a wear-resistant coatings on organic glass of the above polimerizacionnye monomer-oligomer acrylic composition includes the following stages:

1) preparation of a mixture of acrylic oligomers and photoinitiators using a magnetic stirrer at room temperature for 30 min;

2) adding to the resulting solution, fine powder of the oligomer of methacrylate of OMMA under stirring and heating the mixture at 40-50°C for 5-7 hours to obtain a transparent homogeneous solution;

3) coating the surface of the substrate (organic glass) compositions prepared by spray, brush or by centrifuging ("spin-coating");

4) curing the resulting composition by photochemically initsiirovannoi three-dimensional free-radical polymerization with the formation of durable acrylic photopolymer coating on organic glasses.

As the substrate for the proposed wear-resistant coatings tested organic glass, polymethyl methacrylate (PMMA) various industrial brands, such as oriented AO-120 or undirected CO-120C, industrial polycarbonate glass type CCM-4 and the most common spectacle lens on the basis of diallylmalonate type CR-39.

There is solid experimental investigations on the development of the most promising acrylic compositions not containing polymers of MMA, but can serve as a basis for the proposed photopolymerizable acrylic oligomer-oligomer compositions. The result (table 2) developed a number of songs on technological properties (viscosity, viability / min net the ü and depth of photopolymerization, fluidity, transparency) it is acceptable to create a photopolymer coatings. Especially it should be noted that the surface hardness of the coating of these base compositions already significantly exceed the figure for conventional silicate glasses: 6-6,5 points on the Mohs scale against 4-5, respectively.

Table 3 shows comparative data on the composition of songs, filled with industrial samples of high molecular weight PMMA, and the properties of coatings obtained by photopolymerization. It should be noted that the obtained coatings on surface hardness significantly surpass all known analogs of songs filled with PMMA (no higher than 6 points on the Mohs scale). However, in the case of PMMA coatings with the highest surface hardness have a very high viscosity (>1000 CP), and for their application need to use complex techniques (heating of the substrate, the use of "inert" atmosphere, the use of the applicator, and the like), which often makes it impossible to obtain thin coatings and achieving reproducible properties.

It is found experimentally that the photopolymerization of methyl methacrylate (MMA) in the presence of significant concentrations of photoinitiator, several times exceeding the commonly used number of initiator leads to the formation of oligomer the MMA (OMA) with a molecular mass of 20000-70000. From table 4 provides the data suggest that the use of the photopolymerization at high concentrations of photoinitiator leads to a sharp decrease mol. mass of product compared with commercial samples of PMMA. Table 4 shows data on the molecular masses of AMMA obtained using universal calibration Mwfrom the amount of retention on polystyrene, as well as with the use of the detector scattering, directly determining the molecular weight. The last method is very informative for the analysis of vysokopreosv, but in the case of oligomers gives overestimated results. Therefore, in the text of the application and the claims are used the values of Mwobtained using universal calibration with polystyrene.

The drawing shows a gel chromatogram of EMMA (detector response in Rel. units of volume retention VRin ml). Designation of chromatograms in Table 4.

Table 4.
Mol. weight OMMA obtained by photopolymerization of MMA in the presence of photoinitiator "Darokar" 4265". (Hg-lamp Jack Russell 1000 W, a layer thickness of 1 mm, 10 min)
Synthetic example The concentration of the initiator, %The light diffusingThe polystyrene
MwMw/MnMwMw/Mn
NW-110,0334002,70244004,43
Sz-27,0390002,41296003,50
Sz-35,0270002,20202503,25
Sz-43,0348002,8031900the 3.65
Sz-51,0940003,66752705,01
PMMA-1 (AO-120)the industry is config sample 57000002,01to 2 700 0003,03
PMMA-2 (- 120C)industrial design49600001,6432000001,52

Gel chromatography (Waters, THF, 1 ml/min, temperature 35°C, 2 connected in series columns Plgel 5 mm MIXED-C detectors: the scattering or Refractometer with calibration by polystyrene).

Received OMMA were ground and dissolved in photopolymerizable acrylic oligomer-oligomer compositions. The process of dissolution of EMMA in oligomers terminated for 5-7 hours, while for translation in the solution of industrial designs PMMA requires several days.

It was expected that the use of OMA will increase the polymer component of the composition without the sharp increase in viscosity in comparison with the use of PMMA, and on the other hand, to reduce shrinkage during curing and to increase the surface hardness of the coating in comparison with not containing polymers MMA structures.

Indeed, the data of Tables 5 and 6 show that the introduction of EMMA reduces shrinkage by 3-4% and to increase the hardness on the Mohs scale by 1-2 points. When this composition is technology the automatic acceptable viscosity for coating irrigation, brush or by centrifuging ("spin-coating"), and the coatings have good adhesion to the substrate and excellent glossy surface.

Table 5.
The dependence of the shrinkage of the oligomeric composition composition PP-4 (TGM-3, 70 M.Ch., TATE, 29 M.Ch., PHI, 1 M.Ch.) and hardness of the coating from the content of AMMA for example W-3 (Hg-lamp Jack Russell 1000 W, 10 min).
When
measures
The content of AMMA, M.Ch.Viscosity, SPShrinkage, %The Mohs hardness
PP-4030-3512,156,0
12,2160-20011,497,0
25,0328011,447,5
310,54009,867,8
4 15,1-9,528,0
521,0-8,167,5

The following examples are provided to further disclosure of this invention.

A preliminary example of PP-1. In a flask with a flat bottom are weighed amounts of liquid components of the composition: 5,72 g IFW, 4,13 g TATE and 0.15 g PHI. Included magnetic stirrer, and the system stirred at room temperature for 30 minutes. For fixing the thickness of the coating on the plexiglass was used chemically inert strip of polyamide or polyterephthalate film of a given thickness, for example DT-4910-3006-0 or 4918F. Then the Assembly was closed silicate cover glass. For bonding Plexiglas and glass cover (Assembly) used the clamps-clamps. Next, the Assembly was placed in an installation for the photopolymerization, equipped with a mercury lamp high pressure tank is 1000 watts. The distance from the lamp to the sample 20 cm, the exposure time to 5 minutes on each side. Annealing the polymer coating was performed in a heating Cabinet with forced air circulation at 80-100°C for 20 minutes, the Composition and properties of the coating are shown in Table 2.

Preliminary at the minimum level PP-2 PP-12. According to the method of the Preliminary sample PP-1 from the music composition is shown in Tables 2 and 6, the obtained composition, a photopolymerization which the coating with the properties given in Tables 2 and 6.

Comparative example SP-1. In a flask with a flat bottom are weighed amounts of liquid components of the composition: 1,99 g Bis-FAA, 1,99 g MMA, 5,72 g TATE and 0.1 g PHI. Pre-weighed powdered PMMA in the amount of 0.2 g gradually entered into the flask with a mixture of liquid components with constant stirring. Stirring is continued for 50-70 hours to obtain a homogeneous solution. Further according to the method of the Preliminary sample PP-1 is produced coating whose properties are given in Table 3.

Comparative examples of the SP-2 SP-6. According to the method of Comparative example SP-1 from the music composition is shown in Table 3, the obtained composition, a photopolymerization which the coating with a surface hardness shown in Table 3.

Synthetic example W-1. To 10 g of MMA was added 1 g of PHI under stirring for 10-15 min to obtain a homogeneous solution. The resulting mixture was poured on a substrate of the silicate glass layer thickness of ~1 mm and covered with cover glass. Irradiation was carried out Hg-lamp Jack Russell 1000 watts for 5 minutes on each side. Mol. by weight of the product was determined by gel-permeation chromatography on a Waters instrument, THF, 1 ml/min, temperature 35°C, 2 connected in series columns Plgel 5 mm MIXED-C, detectors for svetorasseyanie or Refractometer with calibration by polystyrene. The results are shown in Table 4 and in the drawing.

Synthetic examples NW-2-Sz-5. According to the method of Synthetic example NW-1 when using the initiator concentration, are shown in Table 4, the samples of EMMA mol. masses are given in Table 4 and in the drawing.

Example 1. To 10 g (100 machine hours) composition obtained in example PP-4, was added to 0.22 g (2,2 M.Ch.) OMMA obtained by example W-3, and stirred with a magnetic stirrer at 40-50°C for 5.5 hours to obtain a homogeneous solution. Further according to the method of example PP-1 was obtained coating on the glass, the properties of which are given in Table 5.

Examples 2-5. According to the method of example 1, the obtained composition composition is shown in Table 5, and a photopolymerization - coating whose properties are given in Table 5.

Examples 6-8. According to the method of example 1 from the composition obtained in example PP-7, and shown in Table 6 number of OMMA obtained coating whose properties are shown in Table 6.

Examples 9-11. According to the method of example 1 from the composition obtained in example PP-8, and specified in Table 6 number of OMMA obtained coating whose properties are shown in Table 6.

Examples 12-14. According to the method of example 1 from HDMI is tion, obtained according to example PP-9, and shown in Table 6 number of OMMA obtained coating whose properties are shown in Table 6.

Examples 15-17. According to the method of example 1 from the composition obtained in example PP-10, and shown in Table 6 number of OMMA obtained coating whose properties are shown in Table 6.

Example 18. According to the method of example 1 from the composition obtained in example PP-11, and are specified in Table 6 number of OMMA obtained coating whose properties are shown in Table 6.

Example 19. According to the method of example 1 from the composition obtained in example PP-12, and are specified in Table 6 number of OMMA obtained coating whose properties are shown in Table 6.

Thus, the proposed solution allows to obtain a wear-resistant protective coating on an organic glass with surface hardness close to that of sapphire crystals (7-8 points on the Mohs scale). The proposed compositions are technologically acceptable viscosity for coating by spray, brush or by centrifuging ("spin-coating"), and the coatings have good adhesion to the substrate and excellent glossy surface. Moreover, the introduction of oligomers of methyl methacrylate reduces shrinkage during photopolymerization 3-4% and, thereby, to reduce internal stresses in the coating material.

1. Photopolymerizable acrylourethane-oligomeric composition to obtain a wear-resistant coatings on organic glasses, including bifunctional oligomer, the oligomer with functionality greater than 2 and a polymerization initiator, characterized in that it further contains an acrylic monomer and oligomer of methyl methacrylate (mol. mass 20000-70000 in the following ratio of components, parts by weight:

acrylic bifunctional oligomer15-95
acrylic oligomer with functionality greater than 215-70
acrylic monomer0-25
the oligomer of methyl methacrylate (mol. mass 20000-700005-20
the initiator of photopolymerization0,1-1,0

2. The composition according to claim 1, characterized in that as a bifunctional acrylic oligomer it contains oligoether(meth)acrylate-based diatomic alcohols, glycols, bis-phenols, epoxyacrylate, oligocarbonate-methacrylates or oligourethane(meth)acrylates.

3. The composition according to claim 1, characterized in that as acrylic oligomer with functionality greater than 2, it contains tri - and Tetra(meth)acrylates three - and chetyrehtomnik spirits.

4. The composition according to claim 1, characterized in that as cryovolcanoes it contains derivatives of acrylic acid, preferably butyl acrylate, glycidylmethacrylate or methacrylate.

5. Wear-resistant coating on the organic glass obtained three-dimensional radical polymerization photopolymerizable acrylic oligomer-oligomer composition according to any one of claims 1 to 4 when photochemical initiation.

6. A method of obtaining a wear-resistant coatings on organic glass according to claim 5, comprising a stage of preparation photopolymerizable acrylic oligomer-oligomer composition according to any one of claims 1 to 4 and the stage of curing, consisting of the following operations:
- preparation of a mixture of acrylic oligomers and photoinitiators at room temperature for 30 min;
- adding to the obtained solution, fine powder of the oligomer of methyl methacrylate with stirring and heating the mixture at 40-50°C for 5-7 hours to obtain a transparent homogeneous solution;
- coating the surface of the organic glass compositions prepared by spray, brush or by centrifuging;
curing of the composition by photochemically initiated a three-dimensional free-radical polymerization with the formation of organic glass wear-resistant polymer coating.



 

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1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to water-base lacquer coating materials, meant for depositing on metallic and non-metallic structures in construction, aviation technology and other industries. Description is given of the lacquer coating composition, which contains water-base aryl copolymer "ОЛД-04С" - a product of cohydrolysis of acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate and calcium (meth)acrylate in quantity of 100 wt %, pigments 50-205.1 wt %, silicone fluid 0.3-0.7 wt %, water 450-550 wt %. The pigments used in the proposed composition are in form of titanium dioxide, blue phthalocyanine pigments, blue anthraquinone, green phthalocyanine, yellow light resistant, red iron oxide, coloured refractory pigments, carbon black and or their mixture. The composition can also contain filler in form of talc, kaolin, modified nano-silicate and or their mixture in quantity of 7-93 wt %, and melamine phosphate in quantity of 1-5 wt % as a fire retarding agent.

EFFECT: proposed lacquer coating composition provides for good rheological properties, in particular good opaqueness, high water resistance and freeze resistance with retention of adhesive and physical and mechanical properties.

FIELD: transportation.

SUBSTANCE: proposed coating includes a lower layer of an aluminum alloy anodic oxide coating and an upper layer representing a thermo regulating paint coat comprising acrylate holmium-containing vanish "АКГ-1,2" (42-38 percent by weight) and oxide-modified zirconium (IV), 7-4 (58-62 percent by weight). The coating features low solar radiation absorption factor values (As ≤ 0,10-0,11) and high radiation factors (ε≥0,92-0,94). This allows reducing the radiator-emitter area which is particularly important in development of promising spacecrafts. Availability of two thermoregulating coatings, i.e. the anodic oxide and paint coatings allows a notable increase in service life of the said radiators and producing the said coatings on the surface of products made from aluminum or its alloys with lower As/ε parameter values and without drawbacks inherent in silicate coatings.

EFFECT: antirust protection of complicated-design structures and provision of preset thermal-and-radiation characteristics.

2 tbl

FIELD: paint and varnish materials.

SUBSTANCE: invention describes a composition used in decorative finishing and comprising the following components, wt.-%: 20% solution of polymethylmethacrylate in dichloroethane as a film-forming agent, 20.5-23.25; aromatic solvent, 70.5-74.5, and aluminum powder modified with an organic dye by grinding, 4.25-5.0, taken in the ratio = 1:(0.005-0.008). The proposed composition provides decorative effect of cover mimic to mother-of-pearl with good adhesion of the composition on plastics of different chemical nature. Invention can be used in coloring plastics with imitation of mother-of-pearl, in particular, for national consumption goods.

EFFECT: improved and valuable properties of composition.

2 tbl, 2 ex

FIELD: chemical industry; polygraphy; methods of the stencil printing.

SUBSTANCE: the invention is pertaining to the paint suitable for the stencil printing inside the pressurized castings. The invention describes the paint suitable for the printing films made out of the transparent thermoplastic, consisting predominantly of: a) one or several pigments; b) the binding in the solution in c) the organic solvent or in the mixture of the organic solvents, d) the routine auxiliary materials, if it is desirable, at that as the binding use the copolymer of the poly-(metha)-acrylate containing (м1) from 50 up to 90 % to the mass of alkylmethacrtlate having from 1 up to 6 atoms of carbon in the ethereal radical; (м2) from 5 up to 25 % to the mass, at least, one vinylaromatic compound; (м3) from 1 up to 25 % to the mass of maleic anhydride, and if it is desirable, (м4) from 0 up to 5 % to the mass of the alkylacrylate having from 1 up to 6 atoms of carbon in the ethereal radical or the copolymer of the poly-(metha)-acrylamide containing polymethylmethacrylate with the degree of imidization from 65 up to 80 %, to 1 up to 15 mass % of methacrylic acid and from 1 up to 15 mass % of methacrylic anhydrade. At that the indicated copolymer has the softening temperature by VIKA (ISO 306 B) at least of 115°С. As the dissolvents use aliphatic, cycloaliphatic and aromatic hydrocarbons, ketones, esters, ethers, alcohols, phenoles or their mixtures. The invention also describes the film made out of the thermoplastic printed by the above described paint; the pressurized casting consisting of the film made out of the thermoplastic printed on the opposite side with the above described paint and supplied on this side with the layer of the thermoplastic coating. At that the indicated layer is applied by the operation of pressure die casting on the inside and at that the film and-or the plastic material for operation of the pressure die casting on the inside represents the copolymer of polymethylmethacrylate; and the method of production of the pressurized castings includes the following stages: a) stencil printing of the thermoplastic films by the above described method, b) the film molding, c) the pressurized castings on the inside on the stencil printed film side in the casting mould with the thermoplastic, and d) removal of the pressurized casting from the casting mould. The technical result of the invention: the paint is resistant to the action of the high pressures and temperatures during the operation of the pressurized casting on the inside, the image stencil printed by the paint has the stable color after long-term action of the atmospheric conditions.

EFFECT: the invention ensures, that the paint is resistant to the action of the high pressures and temperatures during the operation of the pressurized casting on the inside, the image stencil printed by the paint has the stable color after the long-term action of the atmospheric conditions.

6 cl, 1 tbl

FIELD: building industry.

SUBSTANCE: invention relates to manufacturing acryl resins-base building composition materials used in internal and external finishing of compartments of industrial and civil designation, in particular, in making pouring flooring covers, protective and finishing materials and pouring compounds. Acryl composition for finishing works comprising a binding agent, quarts sand as a filling agent, plasticizing agent, hardening agent and water involves 40-60% aqueous dispersion of copolymer of butylacrylate, methylmethacrylate and methacrylic acid as a binding agent, tributyl phosphate as a plasticing agent, Portland cement M400 as a hardening agent and, additionally, it comprises acryl-urethane thickening agent of associative type "Polifob TR-117" wherein components are taken in the following ratio, wt.-%: 40-60% dispersion of copolymer of butylacrylate, methylmethacrylate and methacrylic acid, 15.0-30.0; acryl-urethane thickening agent of associative type "Polifob TR-117", 0.1-0.2; quartz sand, 35.0-50.0; tributyl phosphate, 0.15-0.25; Portland cement M400, 8-12, and water, the balance. The composition can comprise additionally pigment in the amount up to 11 wt.-%. Invention provides enhancing mechanical strength of cover, its adhesion to surface and decreasing water absorption.

EFFECT: improved and valuable technical properties of composition.

2 cl, 2 tbl

Parquet lacquer // 2234523
The invention relates to a process of manufacturing water-soluble acrylic lacquer for wood, which can be used as parquet

The invention relates to a paint and varnish materials, namely water-based paint designed for painting interior and exterior surfaces of concrete, derevobrobnij wood particle Board, asbestos-cement plasters and other materials, both new and previously painted

FIELD: chemistry.

SUBSTANCE: additives are used in compositions which are applied on transparent panel bases, e.g., used in windows. The coating composition additive contains an agent for improving functioning of the coating composition, containing a Michael reaction siloxane product, also containing one or more active hydrogen-containing functional radicals with two or more acrylate groups and a compound containing an acid radical which is a carboxylic acid. The invention also relates to an article obtained using the following method. The base-coating method involves mixing the coating composition with said additive, depositing the mixture onto the base and adhesion of the deposited mixture. The invention relates to a coating composition which contains a resin selected from epoxy, acrylic, polyurethane or any combination thereof, a dye and said additive.

EFFECT: articles with the coating composition are characterised by prolonged use.

9 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: antistatic coating composition, containing an acrylate- and polyaniline-based resin modified with cyanate-acrylate, which is capable of chemically bonding with acrylate-based resin. The antistatic coating composition can additionally contain a plasticiser, a photosensitiser and organic solvents. The antistatic coating composition, where the cyanate-acrylate-modified polyaniline is obtained using a two-step method: 1) obtaining cyanate-acrylate through a reaction of hydroxyacrylate (formula (1)): O=C=N-R1-N=C=O, where R1 denotes alkylene or arylene containing 10 or less carbon atoms) and diisocyanate (formula (2)): where R2 denotes alkylene or arylene containing 10 or less carbon atoms) and 2) covalent bonding of cyanate-acrylate to the polyaniline backbone chain to form a polyaniline-acrylate copolymer.

EFFECT: formation of a film with excellent adhesion properties and surface tension with UV curing.

13 cl, 8 ex

FIELD: chemistry.

SUBSTANCE: electroplating composition contains cyclic guanidine and a polymer which contains a functional group. Said polymer contains a functional group which reacts with said cyclic guanidine and said functional group includes an epoxy group. In the composition, said polymer with cyclic guanidine forms a reaction product. Said cyclic guanidine is 1,5,7-triazabicyclo[4.4.0]dec-5-ene. Use of cyclic guanidine in said composition can cut and/or completely eliminate the need for metallic catalysts such as tin and/or bismuth.

EFFECT: invention enables to form a coating which endows a substrate with corrosion resistance, wear resistance, resistance to damages caused by impact, fire resistance and heat resistance, chemical resistance, resistance to UV light and structural integrity.

67 cl, 33 ex

FIELD: chemistry.

SUBSTANCE: acrylic lacquer contains an acrylic copolymer dispersion Primal AC-4800ER, a coalescent additive Nexcoat NX-795, a wax additive Aquacer 502, Orotan 681 dispersant, a polyurethane thickener Acrisol RM-2020, a neutraliser - 20% aqueous ammonia solution, an antifoaming agent Nopko NXZ, a preservative Kathon LXE and water.

EFFECT: with the given combination of components, the acrylic lacquer is characterised by good working characteristics and forms a high-lustre transparent coating on wooden articles.

2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: acrylic lacquer contains an acrylic copolymer dispersion Primal AC-4800ER, a coalescent additive Nexcoat NX-795, a wax additive Aquacer 502, Orotan 681 dispersant, a polyurethane thickener Acrisol RM-2020, a neutraliser - 20% aqueous ammonia solution, an antifoaming agent Nopko NXZ, a preservative Kathon LXE and water.

EFFECT: with the given combination of components, the acrylic lacquer is characterised by good working characteristics and forms a high-lustre transparent coating on wooden articles.

2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: acrylic lacquer contains an acrylic copolymer dispersion Primal AC-4800ER, a coalescent additive Nexcoat NX-795, a wax additive Aquacer 502, Orotan 681 dispersant, a polyurethane thickener Acrisol RM-2020, a neutraliser - 20% aqueous ammonia solution, an antifoaming agent Nopko NXZ, a preservative Kathon LXE and water.

EFFECT: with the given combination of components, the acrylic lacquer is characterised by good working characteristics and forms a high-lustre transparent coating on wooden articles.

2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: concentrated aqueous dispersion of the polymer contains: a) a polymer carrier obtained via hetero-phase radical polymerisation of at least one ethylenically unsaturated monomer selected from a group comprising C1-C18-acrylates, C1-C18-methacrylates, acrylic acid, (meth)acrylic acid, styrene, vinyl toluene, containing hydroxy groups, arcylates or (meth)acrylates, acrylates or (meth)acrylates formed from alkoxylated alcohols, and containing several functional groups of acrylates or (meth)acrylates or mixture thereof, in the presence of b) a photoinitiator selected from a group comprising alpha-hydroxyketones, bisacyl phosphine oxides or phenyl glyoxylates or mixture thereof and c) optionally nonionic, cationic or anionic surfactant. The ratio of the mass of the photoinitiator to the mass of the polymer carrier in the aqueous dispersion of the polymer is equal to or greater than 35 parts of the photoinitiator per 100 parts of the polymer carrier. The invention describes a method of producing a concentrated aqueous dispersion of the polymer and a powdered composition of the photoinitoator polymer, as well as use of the aqueous dispersion of the polymer, the powdered composition of the photoinitiator polymer, in aqueous or non-aqueous compositions, coatings, ink, adhesives or compositions of materials for electronics.

EFFECT: obtaining a stable concentrated aqueous polymer dispersion and coatings based on said dispersion with good working characteristics.

8 cl, 10 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: concentrated aqueous dispersion of the polymer contains: a) a polymer carrier obtained via hetero-phase radical polymerisation of at least one ethylenically unsaturated monomer selected from a group comprising C1-C18-acrylates, C1-C18-methacrylates, acrylic acid, (meth)acrylic acid, styrene, vinyl toluene, containing hydroxy groups, arcylates or (meth)acrylates, acrylates or (meth)acrylates formed from alkoxylated alcohols, and containing several functional groups of acrylates or (meth)acrylates or mixture thereof, in the presence of b) a photoinitiator selected from a group comprising alpha-hydroxyketones, bisacyl phosphine oxides or phenyl glyoxylates or mixture thereof and c) optionally nonionic, cationic or anionic surfactant. The ratio of the mass of the photoinitiator to the mass of the polymer carrier in the aqueous dispersion of the polymer is equal to or greater than 35 parts of the photoinitiator per 100 parts of the polymer carrier. The invention describes a method of producing a concentrated aqueous dispersion of the polymer and a powdered composition of the photoinitoator polymer, as well as use of the aqueous dispersion of the polymer, the powdered composition of the photoinitiator polymer, in aqueous or non-aqueous compositions, coatings, ink, adhesives or compositions of materials for electronics.

EFFECT: obtaining a stable concentrated aqueous polymer dispersion and coatings based on said dispersion with good working characteristics.

8 cl, 10 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for extreme media used in agriculture, cosmetology and everyday life. The compositions contain a surfactant based on an organosilicon compound of the formula: MM', where M=R1R2R3SiO1/2; M'=R4R5R6SiO1/2; where R1 is selected from a group consisting of a branched monovalent hydrocarbon radical containing 3-6 carbon atoms, and R7, where R7 has the formula: R8R9R10SiR12, R8, R9 and R10 are each independently selected from monovalent hydrocarbon radicals containing 1-6 carbon atoms and monovalent aryl or alkylaryl hydrocarbon radicals containing 6-13 carbon atoms, and R12 is a divalent hydrocarbon radical containing 1-3 carbon atoms, R2 and R3 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R1, with R4 in form of alkyl polyalkylene oxide of general formula: R13(C2H4O)a(C3H6O)b(C4H8O)cR14, where R13 is a divalent straight or branched hydrocarbon radical, having the structure: -CH2-CH(R15)(R16)dO-, where R15 is H or methyl; R16 is a divalent alkyl radical with 1-6 carbon atoms, where the subscrip d is equal to 0 or 1; R14 is selected from a group consisting of H, monovalent hydrocarbon radicals with 1-6 carbon atoms and acetyl, where subscripts a, b and c are equal to zero or positive numbers and satisfy the following relationships: 2≤a+b+c ≤20 for a≥2, and R5 and R6 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R4. The compositions have hydrolysis resistance in a wide pH range.

EFFECT: invention increases hydrolytic stability of the compositions.

65 cl, 21 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for extreme media used in agriculture, cosmetology and everyday life. The surfactant compositions for extreme media contain organically modified hydrolysis-resistant disiloxane surfactants which are based on an organosilicon compound of formula: MM', where M = R1R2R3SiO1/2; M' = R4R5R6SiO1/2; where R1 is selected from a group consisting of a branched monovalent hydrocarbon radical containing 3-6 carbon atoms, and R7, where R7 has the formula: R8R9R10SiR12, R8, R9 and R10 are each independently selected from a group of monovalent hydrocarbon radical containing 1-6 carbon atom and monovalent aryl or alkylaryl hydrocarbon radical containing 6-13 carbon atoms, and R12 is a divalent hydrocarbon radical containing 1-3 carbon atoms, R2 and R3 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R1, with R4 in form of alkylpolyalkylene oxide of general formula: R13(C2H4O)a(C3H6O)b (C4H8O)cR14, where R13 is a divalent straight or branched hydrocarbon radical, having the structure: -CH2-CH(R15)(R16)dO-, where R15 is H or methyl; R16 is a divalent alkyl radical consisting of 1-6 carbon atoms, where the subscript d can be equal to 0 or 1; R14 is selected from a group consisting of H, monovalent hydrocarbon radicals consisting of 1-6 carbon atoms and acetyl, where subscripts a, b and c are equal to zero or positive numbers and satisfy the following relationships: 2≤a+b+c≤20 for a ≥2, and R5 and R6 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R4. The compositions are resistant to hydrolysis in a wide pH range.

EFFECT: invention increases hydrolytic stability of the compositions.

65 cl, 21 tbl, 13 ex

FIELD: process engineering.

SUBSTANCE: invention relates to protection of articles from thermoplastic polymer against scratches. Proposed method comprises application of protective layer by co-extrusion, or extrusion, or multi-moulding, and, at least, one thermoplastic polymer. Said protective layer comprises acrylic polymer including the following components in wt %: 80 - 99.8% of methyl methacrylate (MMA); 0 - 20%, of, at least, one copolymer capable of radical copolymerisation with MMA, and 0.2 - 10% of toxilic anhydride, or acrylic and/or methacrylic acid and, not obligatorily, anhydride groups of the following formula: wherein R1 and R2 stand for H- or methyl radical.

EFFECT: improved impact strength.

13 cl, 1 tbl, 6 ex

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