Polymer composition for coating

 

(57) Abstract:

The invention relates to the field of coatings, curing under the action of radiation of low energy in the wavelength range of 400-700 nm and used in such fields as dentistry, electronics, printing. The composition comprises an oligomer - algorithmidentifier - compound of General formula (I), algorithmically linear structure (comonomer I), oligodendroglial branched structure (comonomer II) esters of benzoin - product brand Trigonal-14, dimethylaniline, dinitrosobenzene acid. Technical result: get polymer coating with a high degree of crosslinking (20-25 with exposure to radiation of low energy), high hardness, wear resistance, impact strength, elasticity. Coatings can be applied in a wide range of thickness of 100-1000 μm, depending on the scope of application of the coatings. 3 table.

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The invention relates to the field of coatings, curing under the action of one of the new and promising methods of curing - curing under the action of radiation of low energy in the wavelength range of 400-700 nm. Such coatings can be used (depending on the composition and printing industry.

Known composite materials, cured under the action of radiation of the visible range of the spectrum [application 61-120867, Japan, 59-242837, MKI 09 D 3/80, 09 D 5/00; application 62-123044, Japan, 60-261331, MKI 03 D 25/02, 09 D 3/727] with relatively high speeds. Such compositions include dipentaerythrityl monomer [application 61-120867, Japan, 59-242837, MKI 09 D 3/80, 09 D 5/00] , the acrylic monomer is a urethane-type [application 62-123044, Japan, 60-261331, MKI 03 D 25/02, 09 D 3/727] , methyl methacrylate [application 61-120867, Japan, 59-242837, MKI 09 D 3/80, 09 D 5/00; application 62-123044, Japan, 60-261331, MKI 03 D 25/02, 09 D 3/727] and initiator of polymerization campagine. As a film-forming such compositions can be used acrylourethane oligomers, having in its structure, which fragments [application 61-120867, Japan, 59-242837, MKI 09 D 3/80, 09 D 5/00 (prototype)] .

These compositions have the ability to form a high speed transparent, relatively hard surface under the action of the soft radiation in the wavelength range of 400-700 nm. However, the durability and elasticity of such coatings is not high enough. As for curing such compositions need a source of radiation of a certain narrow range of wavelengths matching m is edlagaemoe is a polymeric composition, we have chosen for the prototype [application 61-120867, Japan, 59-242837, MKI 09 D 3/80, 09 D 5/00] , including the quality of the oligomer polyurethaneisocyanurate General formula

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where R is a radical of the formula [OCH2-CH2-CH-C(O)]nOR2C(O)OC-(R1)-CH or or1OC(O)C(R2)-CH, R2- H or methyl, R1is ethylene or propylene, n= 1-6.

as co monomer methyl methacrylate and initiator of photopolymerization - Campegine, when sleduushem ratio of components, wt. %:

Polyaryletheretherketone - 30-35

The methyl methacrylate - 60-65

Campagine - 0,1-5

Such compositions form a relatively hard transparent coating under the action of radiation of low energy. However, the compositions do not provide sufficient hardness and wear resistance of the coating. In addition, the disadvantage of these compositions is not sufficiently high elasticity, impact strength and high viscosity coatings, hardened for 30 s (see table 3). There is another significant problem in obtaining coatings on the basis of such compositions. For curing such composite materials necessary source of radiation of a certain narrow range of wavelengths, which coincides with the maximum absorption fot the spine, hardness, low tack, able to cure with a very high speed under the action of radiation of low energy in the presence of a universal three-component initiator system capable of initiating a polymerization reaction upon irradiation source a wide range of radiation, 400-700 nm.

This is achieved by a composition comprising the oligomer (algorithmidentifier) General formula

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n= 1-3,

and comonomers - algorithmically General formula (I),

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n= 1-3,

and algorithmically General formula (II)

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n= 1-3,

and the initiator of photopolymerization system compounds: esters of benzoin (a mixture of isobutyl and butyl ether of benzoin in the ratio 9: 1 - product brand Trigonal-14), dimethylaniline and dinitrosobenzene acid at the following ratios, wt. %:

Algorithmidentifier (oligomer) - 55-60

Algorithmically linear structure (comonomer I) 15-35

Algorithmically branched structure (comonomer II) - 3-23,5

Ethers of benzoin (product brand Trigonal-14) - 1.5-3

Dimethylaniline - 3-5

Dinitrosobenzene acid - 1.5-3

Oligourethane the tion of 2,4-toluylene diisocyanate to the degree of conversion of isocyanate groups 50% at a temperature of ~ 655oIn the presence of catalytic systems. In the second stage to Cyclotimia add monomethacrylate ether of ethylene glycol and the catalyst is a compound of tin. The synthesis takes place within 5-6 h of the Synthesis carried out in a solution of organic solvent methylethylketone, cyclohexanone, butyl acetate, ethyl acetate. The final product is a 50% solution in these solvents.

Algorithmically linear structure (comonomer I) obtained as follows. In the first stage of the synthesis get prepolymer - product of the interaction of 2,4-toluylene diisocyanate with diola (for example, DIPROPYLENE brand Laprol 502) to the degree of conversion of isocyanate groups 50% at a temperature of ~ 605oIn the presence of a catalyst. In the second stage to prepolymer add monomethacrylate ether of ethylene glycol and the catalyst is a compound of tin. The temperature of the reaction mass in the second stage ~ 255oC. Synthesis runs for 4-5 hours a Synthesis carried out in a solution of organic solvent methylethylketone, cyclohexanone, butyl acetate, ethyl acetate. The final product is a 80% solution in these solvents.

Algorithmically branched strctly 2,4-toluylene diisocyanate with dimethacrylate ether of ethylene glycol to the degree of conversion of isocyanate groups 50% at a temperature of ~ 405oIn the presence of a catalyst. In the second stage to the adduct type polyol (for example, the product of industrial grade Laprol-503) and the catalyst is a compound of tin. The temperature of the reaction mass in the second stage ~ 255oC. Synthesis runs for 4-5 hours a Synthesis carried out in a solution of organic solvent methylethylketone, cyclohexanone, butyl acetate, ethyl acetate. The final product is a 80% solution in these solvents. Characteristics of the oligomer and comonomers I and II are presented in table 1.

As can be seen from the table, data on the molecular weight, the content of urethane and methacrylic groups, IR and UV spectroscopy confirmed the structure of the oligomers.

Components fotoinitsiatora system are introduced into the composition in different forms: benzoin ethers (product brand Trigonal-14) individual connection, dimethylaniline as an individual connection, dinitrosobenzene acid as an individual compound or as 10-50% solution in methyl ethyl ketone, cyclohexanone, butyl acetate, acetone and ethyl acetate.

The composition is prepared by mixing the components at room temperature. Oligomeric base mixed CTD is by 15-30 minutes, and then mix the components of the framework. Pre-processing time of the entire composition as a whole before you make directly in the radiation zone, is ~ 30 minutes.

Formulations of the compositions are shown in table 2.

The curing conditions: temperature - 1525oWith the radiation source low energy wavelength range of 400-700 nm, the curing time is 20-25 C, optimum coating thickness is 70-150 μm. It is possible to apply compositions in the range of thicknesses - 70-1000 μm under the same curing conditions.

Data on the physical-mechanical properties of coatings, wear resistance, stickiness is given in table 3.

Evidence suggests that, compared with the prototype increases the degree of cure of the coating for 20-25 with curing under the action of radiation content of the gel-fraction is 92-97% (compared with 88% of that of the prototype for 30 s), the hardness increases to 0.82-0.87, impact strength is 50 cgsm (prototype 40 cgsm). The wear resistance of 1.5-3 times higher than that of the prototype, the stickiness through 5 after curing is 0.55-0.57 g/cm2(the prototype of 0.90 g/cm2).

Polymer composition for coating comprising the oligomer, the comonomers and initiator of photopolymerization, the < / BR>
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n= 1-3,

as the comonomers algorithmically General formula (I)

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n= 1-3,

and algorithmically General formula (II)

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where n= l-3,

and as an initiator of photopolymerization use of compounds ethers of benzoin (product brand Trigonal-14), dimethylaniline and dinitrosobenzene acid at the following mass ratio of components, wt. %:

Algorithmidentifier (oligomer) - 55-60

Algorithmically linear structure (comonomer I) 15-35

Algorithmically branched structure (comonomer II) - 3-23,5

Ethers of benzoin (product brand Trigonal-14) is 1.5-3

Dimethylaniline - 3-5

Dinitrosobenzene acid - 1,5-3

 

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