DD295645A5 - Process for producing surface-sealed thin-film coating - Google Patents

Abstract

The photochemical polymerization of bisacrylamides of the structure leads to network polymers, which are sealed after a subsequent thermal addition polymerization with 3 to 6 * of a di- or polyfunctional amine based on the bisacrylamide on the surface. The inventive method allows the production of photochemically hair-hardenable adhesives, composites, films, coatings u. a. m. Structure {bisacrylamides; amines; photochemical polymerization; thermal polymerization; sealed Duennfilmbeschichtungen; adhesives; films; coatings; Protection of microelectronic devices; optoelectronic devices}

Description

Field of application of the invention

The invention relates to a process for producing surface-sealed thin-film coatings which are useful as adhesives, films or coatings, for the protection of microelectronic, optoelectronic, thermoelectric components and the like. are suitable.

Characteristic of the known technical solutions

The radical (photochemical) bulk polymerization of methacrylates and acrylates is known to result in polymer layers which are still tacky due to the influence of oxygen on the surface. This problem can be addressed in various ways. Thus, photochemical polymerization is initiated by carbonyl / amine systems to circumvent this problem (RS Davison, JW Good, Eur. Polym. J. 18 [1982, 1597] or suitable dye initiators are used to convert triplet to singlet oxygen (Decker, Decker, Makromol Chem. 180 [1979] 2027). Furthermore, surfactant initiators have been used, thiol additives have been used (CR Morgan, AD Ketley, J. Radiat, Curing 7 [1980] 10) or the photochemical thiol-ene addition has been used (CR Morgan, F.A. Magnotta, AD Ketley, J. Polym., Sci., Polym. Chem. Ed. 15 (1977) 627). Some reduction in surface tack is also achieved by filler additions.

With relatively thin coatings, however, most of these methods fail and a more or less pronounced surface tack is always observed.

The photochemical polymerization of acrylamides (see G.Smets Bull. Soc. Chim. Beiges 71 [1962] 857, G. Oster, J. Amer. Chem. Soc. 7911957] 595), and their thermal polymerization with amines in solution has been known for years (Ferruti et al., Chim. Ind. 49 (1967) 271).

Object of the invention

The object of the invention is the production of surface-sealed thin film coatings for the protection of microelectronic, optoelectronic, thermoelectric components by photochemical polymerization of acrylate monomers.

Explanation of the essence of the invention

The object of the invention is to develop surface-sealed thin-film coatings with good mechanical and thermal properties by an easy-to-implement method.

Surprisingly, it has been found that bisacrylamides of the following structural formula

011 ,, - GH-GHH ¹ -Ii-C-CiI = CU., Il II

ο o

wherein R is a monofunctional substituted or unsubstituted aliphatic araliphatic or cycloaliphatic radical and CH ₃ , C ₂ H ₅ , C ₆ H ₆ CH ₂ , C ₈ Hn and R 'represents a bifunctional aliphatic, araliphatic or cycloaliphatic radical and CH ₂ CH ₂ , CH ₂ CH ₂ OCH ₂ CH ₂ OCh ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ OCh ₂ CH ₂ CH ₂ CH ₂ , CH ₂ -CeH ₄ -CH ₂ JC ₆ H ₁₀ -CH ₂ -C ₆ H ,,, is capable of being polymerized into surface-sealed thin film coatings by a two-step process when first polymerized photochemically by UV irradiation within 30 to 300 seconds in the presence of photoinitiators such as benzil dimethyl ketal-benzoin methyl ether.-acylphosphine oxide, followed by thermal post cure of 3 to 6Ma .-% of a di- or polyfunctional amine at 60 to 13O ⁰ C in 10 to 500 minutes, which was mixed before the photochemical polymerization bisacrylamide. Suitable amines have been found to be benzylamine, N, N'-dibenzylethylenediamine, N, N'-dibenzyl-3,6-dioxa-octanediamine-1,8, N, N'-dibenzyl-O-oxanonanediamine IA N, N'- Dime'ihylethylenediamine and dipropylenetriamine.

An addition of 2Ma .-% amine to the bisacrylamide caused even after thermal aftertreatment no complete tack-free surface. For thermal post-curing, at least 3% by weight of an amine is necessary to remove the stickiness of the surface. A higher proportion than 6% by mass has adverse effects on the adhesion of the material to the substrate surface (metal, glass or ceramic surface), the mechanical properties and for water absorption and thermal behavior (see Table 1).

Table 1

Influence of the Amine Amount Used for Post Cure on the Properties of the Network Polymer

Amount of amine Surface of the polymer Adhesion to the substrate

in% by weight

The process according to the invention can also be carried out in the presence of a catalyst or accelerator. Further, the photochemical and subsequent thermal polymerization in the presence of fillers can be used to make composite materials.

The use of the bisacrylamides according to the invention differs advantageously from the bis-GMA (bismethacrylate of bisphenol A diglycidyl ethane bismethylacrylate) which is frequently used today, which has good mechanical and thermal properties in thicker volume layers, but sticks to the surface in thin film coatings like other methacrylates.

embodiments

example 1

N, N'-bisacryloyl-N, N'-dibenzyl-ethylenediamine: to 9,59g (0.106 mol) of freshly distilled acryloyl chloride in 37,5ml of dry toluene, which was cooled to -5 ⁰ C, 12,74g (0.053 mol ) Ν, Ν'-dibenzyl-ethylenediamine and 15 ml of triethylamine in 150 ml of a toluene / chloroform solution (17: 3) added dropwise with stirring so that the temperature does not exceed ^{0 0} C. The mixture was then stirred at ⁰ ° C. for a further 2 hours, the solution was filtered and the amine hydrochloride was separated off. After distilling off the solvent remained a solid residue which was recrystallized from 100 ml of hexane. Yield: 6.8 g (36.8% of theory), F _p = 76 ° CM _n (VPO) = 350 g / mol C ₂₂ H ₂₄ N ₂ O ₂ 348.5 Calc .: C 75.83 H 6 , 94 N 8.04 Found: C 76.00 H 7.26 N 8.05

2.00 g of N.N'-bisacryloyl-N.N'-dibenzylethylenediamine, 20 mg of benzoin methyl ether and 100 mg of Ν, Ν'-dibenzylethylenediamine are homogeneously mixed with gilindem heating, applied to the substrate to be coated and left for 120 seconds by UV irradiation. Irradiation with a high pressure mercury lamp HBO 200 crosslinked. The sticky polymer on the surface is then thermally treated at 100 ^° C. for 60 minutes. The result is a polymer that adheres well to glass, metal and ceramic surfaces and is surface-sealed.

Example 2

N.N'-Bisacryloyl-N, N'-dibenzyl-O-oxanonanediamine-i: To 17.02 g (0.050 mol) of N, N'-dibenzyl-5-oxanonanediamine-1.9 in 50 mL of methylene chloride was added under ice-cooling and Slowly, a solution of 9.502 g (0.105 mol) of acryloyl chloride and 4.2 g (0.105 mol) of sodium hydroxide in water was added dropwise. The mixture was then stirred for one hour at room temperature, the

sticky Well dry (sealed) Well dry (sealed) Well dry (sealed) Well dry (sealed) Well dry bad

separated organic phase after addition of 100 ml of water and the aqueous phase extracted with methylene chloride. The combined organic phases were dried over MgSO ₄ . After distilling off the solvent, a yellowish oily liquid remained

Yield: 15.3 g (68.3% of theory) M _n (VPO) = 450 g / mol C ₂₈ CH ₃₈ N ₂ O ₃ 448.6 Ben: C 74.91 H 8 * 09 N 6.24 Gef C 74.50 H 8.10 N 6.24

2.00 g of N, N'-bisacryloyl-N, N'-dibenzyl-O-oxanonanediamine, 20 mg of acylphosphine oxide and 120 mg of benzylamine are mixed together with 2.00 g of a filler (Quarzgutmehl MS 20, Berliner Kieselgutwerk) and mixed for 90 seconds with a HBO 200 irradiated. The thermal post-cure at 9O ⁰ C within 80 minutes yielded a surface-sealed composite.

Claims (3)

A process for the preparation of surface-sealed thin-film coatings, characterized in that bisacrylamides of the following structural formula Ii U
• ^Ci V = GH-CJ-Ii-U '-M- (J- (JW = UH., wherein R is a monofunctional substituted or unsubstituted aliphatic, araliphatic or cycloaliphatic radical and CH ₃ , C ₂ H ₆ , C ₆ H ₅ CH ₂ , C ₆ H ₁₁ and R 'is a bifunctional aliphatic, araliphatic or cycloaliphatic radical and CH ₂ CH ₂ , CH ₂ CH ₂ OCH ₂ CH ₂ OcH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ OcH ₂ CH ₂ CH ₂ CH ₂ , CH ₂ -C ₆ H ₁ J-CH ₂ , C ₆ H ₁ O- CH ₂ -CgHiO-JSt are polymerized to surface-sealed thin-film coatings by a two-step process when first polymerized photochemically by UV irradiation within 30 to 300 seconds in the presence of photoinitiators such as benzil dimethyl ketal, benzoin methyl ether, acyl phosphine oxide, and then 3 to 6 mA thermal post cure .-% of a di- or polyfunctional amine at 60 to 13O ⁰ C in 10 to 500 minutes, which was added to the bisacrylamide before the photochemical polymerization. 2. The method according to claim 1, characterized in that as amines for post-curing benzylamine, N, N'-dibenzylethylenediamin.NiN'-dibenzyl-S.Ö-dioxaoctandiamin-lje, N, N'-dibenzyl-5-oxanonandiamin-1, 9, N, N'-dimethylethylenediamine or dipropylenetriamine. 3. The method according to claim 1 and 2, characterized in that the polymerization is carried out in the presence of fillers.