• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Adhesive are based on (a) unmodified low molecular epoxy resins with >=2 epoxy gps/mol and (b) N,N'-dibenzylethylenediamine (I) opt. together with (c) 0.5-49 mol.% (on total amine) of further amine polyaddition components with 2 amine H atoms/mol (II) or 0.5-30 mol.% (on total amine) amine polyaddition components with >=3 reactive amine H atoms/mol (III). The adhesives have alow initial viscosity and increased pot life, but the cure time at room temp. or elevated temps. is not increased. No reactive diluents or plasticisers are required, so that the physiological properties of the compsn. are improved considerably wrt prior art compsns. The prods. are clear, colourless fog-free materials with excellent optical properties, useful for bonding high quality optical components e.g. in the prodn. of compound optics and for mounting optical gear in frames, etc.
    公开号:SU918297A1
    申请号:SU787770364
    申请日:1978-11-22
    公开日:1982-04-07
    发明作者:Ханс-Хейнрих Хернхольд；Диетер Клемм；Лудвиг Хаазе；Клаус Беллштадт；Клаус ШУБЕРТ；Ханс-Юрген Фламмерсхейм；Ролф Мэртин；Вернер Кюнцел；Кристоф ЛУДВИГ
    申请人:Феб Карл-Цейсс-Йена (Инопредприятие)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING OPTICAL ADHESIVE SUBSTANCES
    ON THE BASIS OF UNMODIFIED LOW-MOLECULAR
    . I
    The invention relates to the preparation of optical epoxy based adhesives, in which the bonding process is based on a transition into a solid by means of step polymerization reactions 1 at room temperature, the effect on which, if necessary, is also possible through controlled use of elevated temperatures.
    Adhesives serve to glue finished machined complex optical parts together into optical systems with high accuracy requirements, with the ratio of thicknesses in the middle and the diameters of individual optical components being up to 1:15, and the form factors to values V 0 ,four.
    In addition, optical adhesives are also used for temporarily bonding optical blanks and semi-finished products to each other and on the support so that they can be processed by epoxy resins.
    vat with high accuracy and performance individually or in large quantities, at the same time - when; giving shape.
    Since optical adhesives themselves should be considered as optical media, it is attached great importance to ensuring optical purity, no staining and as little as possible own color or significant colorlessness for maximum spectral permeability. Parameters such as the refractive index, V value, dispersion and possibly low double
    ts refraction at the voltage should be provided according to the requirements of the optical components to be glued. In the process of gluing or during stabilization
    20 and the hardening of the adhesive compound should not result in discoloration, opacities, partial crystallization, blistering, delamination, etc., which result in deterioration of the optical properties. In close connection with this are some properties related to the technology of using j which, unlike a set of limestone adhesives, for technical-mechanical purposes are more important for optical adhesives or even required. Thus, viscosity as a function of time and viscosity, as well as temperature, in the interests of a technologically long combination, are of the greatest importance. time of use and optimally short duration of time to achieve adhesive action or stabilize bonding for optimum technological applicability, to provide certain reproducibility in narrow tolerances of thicknesses, layers of adhesives and to carry out, if necessary, the necessary adjustments and alignments before hardening . In close connection with this, a possible small reduction in the amount of bonding and hardening of bonding leads to the elimination of stresses that lead to the deformation of optical surfaces, to the formation of cracks under stress in the layer of adhesive and, thus, to the skipping of functional Optical Parameters In the interest of realizing high optical parameters and reducing process costs, low gluing temperatures, which differ as little as possible from room temperature, are of greater importance when used. tours. Technically and economically very important is the ability to segregate adhesive joints after appropriate periods, without high technological costs and without damaging the optical parts, in order to correlate the adhesive bonding or to submit parts for further processing. Good adhesion of the adhesive layer to the i surfaces of various optical media combined with appropriate function, temperature and climatic stability and resistance to water and organic solvents are important for those skoy application. On the other hand
    in the case of separation of adhesive joints it is technologically and economically advantageous to completely release and
    amino resins with resins, it is also known to use polyamides as hardeners that clean the surfaces of optical components from adhesive residues by certain selected organic solvents, for example acetone, low molecular weight alcohols, halogen-substituted hydrocarbons.  Of particular importance are the physiological effects of compounds used as optical adhesives or as their components.  After the first known technical solutions for gluing optical parts into optical sieves, themes or for strengthening optical blanks based on a forming treatment consisted in applying molten / adhesive substances based on natural and artificial resins (economic patent jr 44 815 ; patent. Til) 46 319) and polymerization adhesives based on methacrylic acid esters (host patent.  DD 44676), the combination of epoxy resins and amino-hardeners as glue substances of stepwise polymerization or precondensation provide the best prerequisites for optimal fulfillment of requirements for technical use and optics in general.   It is known to use aliphatic polyamines, which at least contain two nitrogen-bonded hydrogen atoms and the smallest carbocyclic residue bonded to nitrogen as a hardener in epoxy resin and amine systems, to increase the time of use compared to unsubstituted aliphatic polyamines and reduce their tendency to turbidity caused by the influence of moisture (DE-PS / 01. 9461).  A significant disadvantage is that these positive effects can be realized only with a high content of organic solvents, as is the case in lacquer systems, which, however, are harmful in optical adhesives.  To increase the time of use (viability), respectively, of a relatively slow increase in initial viscosity, as a function of time during curing, epoxide contains, along with secondary, primary amino groups (DE-PS 1038278).  The same purpose is served by the use of cyanagasylation products of aliphatic polyamines as hardeners for epoxy resins (DE-PS 1034856; DE-OS 2 164 099).  .  However, the increased viability, or delayed gelation, is also associated with an increased cure time and: 1and the need for curing at elevated temperatures.  N-hydroxyalkylalkylamine polyamines are also used as curing agents for epoxy resins (DE-PS 102200 The related advantages of the improved physiological, unquestionable properties of these curing agents and the possibility of curing at low temperatures are due to the lack of very fast curing and short time of use.    To improve the viscosity-time ratio in terms of increasing the use time while simultaneously combining epoxy resin and hardening with a low initial viscosity, it is possible to use combinations of polyamines having at least three amine hydrogen atoms with aliphatic 1 cloaliphatically substituted two-secondary amines, the secondary nitrogen atoms of which linked by a poly methylene chain consisting of at most 4 carbon atoms (DE-AS 1 770 539).  In addition, for curing epoxy compounds, N-substituted diamino compounds are used, due to the presence of primary and secondary amino groups in the order of 3 hydro gen atoms for curing (DE-OS 2 043 141); All known systems of epoxy resins and amino hardeners, with the improvement of certain technological and mechanical properties (increase in time of use, increase in impact strength, flexural strength, tensile strength, heat resistance, water resistance, resistance to chemicals) harden to insoluble, non-melting, mesh products.  Significant properties of epoxy resin adhesives that are advantageous for technical and mechanical purposes.  76 do not stand in direct connection with the additionally required and previously described parameters or combinations of these special for optical adhesives.  For the realization of these optical properties used in engineering, which are important especially for systems made of epoxy resin and amine, combinations of aliphatic or cyclo-aliphatically substituted di- and polyamines c have been proposed simultaneously and to the optimum extent. low molecular weight aromatic epoxy base resins, which, as compared with conventional technical and mechanical adhesives with a very high content of monofunctional reactive diluents and emollients, are modified.  Although these optical adhesives are easier to meet most of the requirements for them, the time of use (viability) is still too small for part of the process requirements, stabilization and hardening of the adhesive bond lasts too long and the high content of reactive diluents adversely affect the physiological, properties, which causes an increase in cost of labor protection measures.  In addition, the gluing of very thin optical elements with strongly curved surfaces, and very different thickness dimensions based on a still too large volume reduction, especially after exceeding the gelation point, did not meet the very high optical requirements.  An optical adhesive based on little- or unmodified low-molecular, aromatic epoxy basic resins and 4-: or vi, N-substituted aliphatic diamines with a relatively long aliphatic chain between amine functions is known (Organic Patent No. 122,258).  Although this already meets high optical requirements and at the same time provides improved properties used in engineering, these adhesive formulations without the content of reactive diluents do not always show the optimal combination of parameters.  Thus, for example, the initial viscosity is too high and the viscosity increase is too high during the on-line fabrication of optical systems.  In this connection, it is impossible to ensure uniform thickness of the layers of adhesive in the appropriate necessary tolerances for a relatively short time: use.  The addition of reactive diluents and emollients used to reduce these deficiencies leads only to partial success. In many cases, moreover, these are physiologically active compounds.  With the technologically necessary separation of the gluing, the layer of adhesive is not completely separated by organic solvents for this purpose from optical components and surfaces.  For the thermal separation of adhesive layers, relatively high temperatures are required, which are harmful to very complex optical components.  Finally, diamines used as components of step polymerization are relatively difficult to access.  The purpose of the invention is to obtain adhesives, improve viscosity and time of the initial mixture of adhesives in the sense of being further slowed down. viscosity during use increased vitality, and the time for stabilizing and hardening the adhesive compound at room temperature does not lengthen according to the technological requirements, and the technologically required time for the gluing of glued parts even decreases.  At the same time, the solubility properties and the thermal properties of the adhesive layers should be improved so that optical adhesives can be equally used as an optical medium, for gluing very complex optical components to optical systems, and for temporarily strengthening optical blanks and semi-finished products. frameworks for further processing to shape.  In addition, physiological properties should be improved so as to reduce the technological costs of labor and health protection.  The object of the invention is to eliminate the causes of technological and physiological deficiency without the known additives of conventional, physiologically active, reactive diluents, such as monofunctional glycides or epoxy base resins and, moreover, preserve and improve the benefits. optical properties and properties used in engineering.  Particular attention should be paid to the amine components in epoxy resin adhesives, since most of the amines still used are physiologically active, as they cause allergies and skin inflammation.  Physiologically undoubtedly, N, W -dibenzylethylenediamine, as well as acting as a component of step polymerization, despite the relatively short length of the aliphatic carbon chain between the amine functions, simultaneously acts as a reactive diluent and internal softener and, moreover, causes a decrease in the initial viscosity and slowing viscosity increase as a function of time.  According to the proposed method, N, N -dibenzylethylenediamine is used as step polymerization components for epoxy resins.  If necessary, other amine components of the step polymerization can also be mixed in to improve the technologically important parameters of the initial mixtures of the adhesive substance, with a quantity of hydrogen-hydrogen atoms per molecule in an amount of 0.5 to 49 mol. % or with two or three ‑ reactive amine-hydrogen functions per molecule from 0.5 to 30 mol% relative to the total amount of amine.  For such additives, stepwise polymerization components with 2 Nn functions per molecule are particularly suitable, for example, N, N-dimethyl-3-aminomethylG, 5.5-trimethylcyclohexylamine and K, W dimethyl2, 2.4 f2, 4.4). - trimethylhexameylenediamine-1, 6.  .  Similarly, as additional amna components with three or more Nn functions per molecule, for example, 4-cyclohexyl-2) 2,4 (2,4,4) trimethylhexamethylenediamine-1, 6; - benzylethylenediamine; g 1-cyclohexylpropylene diamine-1, 3; 3-aminomethyl-3,5,5-trimethylcyclohexylamine and 2,2,4 (2,4,4) -trimethylhexamethylenediamine-1, 6. .   .  The invention is illustrated in the drawing. The abscissa is marked reaction time in minutes; on the left ordinate, dynamic viscosity in spouses (cp); on the right ordinate, dynamic viscosity -ij in similar units of the SI system (it), in both cases on a logarithmic scale.  Here, 1, 2, 3 and 5 have the following meanings: Curve 1: viscosity dependence — time of the optical adhesive of Example 1 when using N, Nj -dibenzylethylenediamine as a component of the step polymerization; Curve 2: viscosity dependence, - the time of the optical adhesive of the substance of example 2 when applying a mixture of N, H -dibenzylethylenediamine and N-benzyl-stylenediamine as components of stepwise polymerization; Curve 3: Viscosity dependence of the optical adhesive for comparison, respectively, with the economic patent GDR 122 258 Example 1 when using N, N-dimethyl-3 aminomethyl-3, 5, 5-trimethylcyclohexylamine as a stent poly component.  customization. .  Important properties of the properties of the exemplary embodiments of the shadow invented are summarized in a table.   I.   Example 1  To 6.1604 g of 2,2-bis- (4 -hydroxyphenyl) propane-digly cipher (zpoxide equivalent of 192.8 measured in W. TC. Ross J. Chem Soc.  (London), 1950, 2257) an equivalent amount of 3, N, N -dibenzylethylenediamine is added.  Within 10 minutes, the composition of the adhesive substance is well mixed and then ready for gluing optical parts at room temperature with each other or for temporarily fixing the optical blanks on the frames for further processing to give shape.  Example 2  To 3.084 of g 2,2-, -bis-C4-hydroxyphenyl) -prog 1 -an diglyce in ether (epoxy equivalent 192.8 by Rose) was added 1,2017 g {5 mmol) of N, N-dibenzylethylenediamine and 0.3004 g (2 mmol) M-benzylstilenamine.  For 10 minutes, the initial mixture of adhesive is mixed well and then it is ready for gluing, as in Example 1.  Example 3  To 8.0892 g of 2,2-bis- (4 -hydroxyfesh-propane-diglycid ether (epoxy equivalent 192.8 by Rose) were added 2.64436 g II mmol of N, N-dibenzylethylenediamine and 1.9834 g (U mmol ) M, N-dimethyl-3-aminrmethyl-3, 5,5-trimethylcyclohex silamine.  For 10. The initial mixture of adhesive material is well mixed and ready for bonding, as in Example 1.  Example 4  The initial mixture of adhesive material produced according to Example 1 serves to glue optical components into optical structural groups.  After gluing during stabilization and strengthening of the adhesive, for example, the following temperature program is maintained: a period of 2 days at room temperature; I day at +4 (fC; 1 day at 1 day at 3 days at and 4 days at.  The optical structural groups of the units glued in this way and cooled in the usual way, ensure their functional parameters, such as the absence of optical and mechanical stresses, temperature and climate resistance, stable alignment, do not require more than the usual technologically determined storage time.  The table contains some important parameters of the initial mixtures of adhesive used in the technique, which were obtained in Examples 1 to 3.  For comparison, under Example 5, the values of the optical adhesive substance obtained are similar to those obtained according to the economic patent GDR 122 258 of Example 1, when using H, s-dimethyl-3-amynomethyl-3, 5,5-trimethyl cycpohexylamine (N, N-dimethyl - IPD | and, similar to the present invention I9, without the addition of a reactive diluent (phenyl glycide ether), (cf.  economic patent 122,258, tab.  1 page 3).  The viscosity measurements were carried out with a RV RV-test instrument with a cone-stretch device, with ij means dynamic viscosity at 25 ° C after 10 min of mixing.  The determination of the separation temperature takes place on glued lenses with a diameter of 30 mm and a median thickness of 2 mm.  As the viability, a time is given before the start of drawing the thread of the adhesive agent.  The drawing demonstrates the viscosity characteristic — the time of the initial mixtures of the adhesive substance obtained according to the invention, for comparison at curve 5, the same example is used as in the table.  .   In the examples given, the explanations are applied in the technique, improved relative to the urban techniques of the properties of optical optical materials obtained by the proposed method.   Especially, a significantly low viscosity of +1 h should be distinguished, which, in combination with the simultaneously slowed down increase in KocTii depending on time, presents excellent technological possibilities of use, especially in optical flow manufacturing.  (Wed. attached table and graphic representation of viscosity-temperature dependence). -Top  the most secured. reproducible within narrow tolerances of the mass of the adhesive layer for a long time of use.  .  These advantages are achieved without the addition of reactive diluents which are partially physiologically ak-tivny.  In this connection, another technological advantage has been noted of lowering the separation temperature for thermal stratification of the kepean compound in the case of proofreading or for technological reasons, which so far has been realized only with the help of the addition of reactive diluents.  At. This should be taken into account when, in addition to the application of the amine components of the step polymerization with more than two 712 N-H functions, the above mentioned quantity limits are complied with, -. .  would preserve the described advantages of the invention, especially the thermal partitionability and solubility in organic solvents.  Interferometric research methods did not detect deformations adversely affecting the image quality on an optically active surface, which would appear in a fluidized bed in the case of mechanical stress conditions (flat optical parts with a diameter of 30 mm and a thickness of 2 mm according to the invention).  Manufactured optical adhesives are also free from double refractions when pressed.  The load on the glued optical parts is at a temperature and does not cause a decrease in these favorable properties, which is detectable at room temperature.  In addition, along with thermal separability, glue compounds also dissolve in selected organic solvents, such as acetone, alcohols, halogenated hydrocarbons, and their mixtures, even after 30 days of curing, without using elevated temperatures completely and without remaining adhesive residues.  Used according to the invention as a component of stepwise polymerization of N, n -dibenzylethylenediamine is in another connection as an additive to drugs.  Due to the obtained physiological impeccability of this component and its use without the addition of partially physiologically active, resistant diluents, the physiological properties of optical glue have been significantly improved.  The technical availability of M, -dibenzylethylenediamine is also important.  The use of an optical adhesive is feasible at room temperature.  Technologically necessary time for coiling can be reduced without harm by using appropriate. temperature program.
    权利要求:
    Claims (1)
    [1]
    The formula of the invention nents stepwise polymerization with
    A method of producing optical adhesives based on non-modification of two amine-hydrogen atoms per 20 one molecule in an amount of from 0.5 to 49 b / ol.% Or with three or more low molecular weight epoxy resins containing at least two epoxy groups per molecule, characterized in which, as components of stepwise polymerization. for epoxies, m, s'-dibenzylethylenediamine is used, and if necessary, other amine components are reactive amine-hydrogen functions per molecule from 0.5 to 30 mol% in ete all amounts of amine 'recognized tatam invention according to the results of examination by the Office on the invention of the German Democratic Republic.
    t 0 * 60 (
    700
    类似技术:
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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