DE19821226A1 - Resin composition useful as electrically resistive element or moisture resistant coating - Google Patents

Abstract

A resin composition (I) comprises a low molecular compound (II) and a crosslinkable polymer (III) whereby (II) contains terminal crosslinkable groups and a structure containing 2-7 benzene rings connected by means of an ether linkage, methylene oxide linkage, ketone linkage or a sulphonyl linkage. Each unit of (III) contains a multiplicity of benzene rings connected by an ether, methylene oxide, ketone or sulphonyl linkage and the polymer has terminal crosslinkable groups. (III) has a higher mol. wt. than (II). Also claimed are : (i) a hardened resin material obtained by hardening of (I) and (ii) an electrically resistive element containing hardened (I).

Description

The present invention relates to a cured resin material excellent thermal resistance, chemical resistance and excellent mechanical properties and also good ones electrical properties for use as, for example, electrical resistance elements and moisture resistant Coating materials, and a curable resin composition for this.

As a technical plastic with excellent thermal resistance, chemical resistance and excellent mechanical Properties were known polyether ether ketone.

Because the polymer is characteristically highly crystallizable, however, the polymer itself is in organic solvents essentially insoluble. For the use of the polymer at Various objects can only be extruded onto the polymer or compression molding can be used. Hence, the objects for the polymer can be used.

After various studies to modify the polymer, therefore, that it is soluble in organic solvents alkyl-substituted aromatic polyether ketone found. The alkyl-substituted aromatic polyether ketone that is used in organic Solvents can be dissolved in various ways after dissolution organic solvents are used, and therefore that is Polymer (aromatic polyether ketone) usable as lacquer or Varnish for use in a wide variety of areas.

The alkyl-substituted aromatic soluble in organic solvents However, polyether ketone disadvantageously has a poor chemical  Resistance and solvent resistance so that the polymer (the aromatic polyether ketone) cannot be used for items where those properties are required.

As a resin composition with increased chemical resistance and solvent resistance, J. de. Abajo, et al. in Polymer, Vol. 33, (15), 3286 (1992) reports the composition represented by the following chemical formula.

The manufacturing reaction is like an acylation reaction Schotten-Baumann reaction of 3- or 4-ethynylbenzoyl chloride with corresponding aromatic diol.

However, the product produced is in common organic solvents not sufficiently soluble, so that those applicable to the product Molding agents are limited.

Because of the introduction of the acetylene group by the Scots Baumann reaction, the product produced has a structure that is one Contains ester bond. Hence its hygroscopicity is so great that the product is likely to be moisture resistant is deficient. In addition, the product is in contact with steam and the like hydrolyzed. Because the product is not a polymer, can be Molecular weight cannot be adjusted, and therefore the Network density of the product should never be adjusted.  

In addition, TM Miller et al. Macromolecules, Vol. 26, 2395 (1993) describes the composition represented by the following formula.

The composition is a polymer that has been synthesized under Use of an aromatic ether monomer with acetylene end and of an aromatic ketone monomer with acetylene end by means of Tetramethylethylenediamine and a Cu catalyst.

Unfortunately, the polymer with higher Molecular weight poorly dissolved in organic solvents, and its molecular weight is released with great difficulty set.

Then a soluble polyether ketone with acetylene end, which in the Is able to overcome the disadvantages in Japanese Patent Application No. Hei 8-73548. The soluble Polyether ketone with acetylene end in itself is in organic Solvents highly soluble, but through a cross-linking reaction the crosslinking groups in the polymer (the soluble Polyether ketone with acetylene end) to form a hardened Crosslinked resin material, so that the resulting product in organic solvents is insoluble with the resulting Improvement in solvent resistance, chemical Resistance and thermal resistance. In such a state that the resulting product is soluble in organic solvents is, therefore, the product can be applied as different  Matrix resins for shaping many shaped objects using different Shaping devices; the product has a high usability, and by crosslinking and then curing after molding the resulting product has a very high solvent resistance, show chemical resistance and mechanical strength. thats why the product can be used as an excellent resin material and particularly preferred as an electrical resistance element.

Electrical resistance elements, for example carbon Resistance elements such as a variable resistor made by Dissolving or mixing carbon and a binder resin (Matrix resin) in an organic solvent to remove from the mixture to make a paste, and by printing the paste on a substrate before sintering for use.

Furthermore, the sintering temperature of the electrical resistance element from the standpoint of thermal resistance of such Restricted substrate. More specifically, commonly used as a substrate for the resistance element of a variable resistor Phenolic substrate ("bake" substrate) used, but the most tolerable Temperature of the substrate is 250 ° C for about 15 minutes.

The curing temperature varies depending on the molecular weight of soluble polyether ketone with acetylene end (exothermic peak (Peak) temperature by DSC), but the temperature is im general up to around 300 ° C (see Table 1 of the publication). When the process of thermally curing the polyether ketone a temperature tolerated by the phenolic substrate the polymer (the soluble polyether ketone with acetylene End) are not sufficiently hardened. Therefore a Resistance to solvents required for hardened resin materials is necessarily required not to be created or her Hardening process takes a long time. Therefore, unfortunately, is a  such soluble acetylene-terminated polyether ketone with such high curing temperature can never be used for a phenolic substrate.

In addition, the soluble polyether ketone is for substrates with high thermal resistance applicable as a ceramic substrate, however such substrates are expensive.

If the polyether ketone for those substrates with high thermal Stability is applied, should also necessarily sufficient sintering an oven can be used, the high Can withstand temperatures, even without possible impact on the Substrates. Common furnaces for use in sintering electrical ones Resistance elements using phenolic substrates are usable for binder resins, the phenolic resin and epoxy resin and these ovens are at a temperature of about 200 used up to 250 ° C.

If these are commonly used furnaces for curing phenolic resin and epoxy resin are used for thermally curing the polyether ketone are, the heating temperature is so insufficient that the Polyether ketone cannot be cured sufficiently, which unfortunately too inadequate training of hardened resin materials as essential solvent resistance or to the Requires a long curing time.

Electrical properties for general resistance elements are inevitably required, also for electrical Resistance elements required, for example what Temperature behavior, namely no temperature dependence on Resistance value, and the moisture resistance belongs.

The present invention has been made to solve these problems executed.

It is an object of the present invention to be a curable Provide resin composition in organic solvents is soluble and easy to use; and it's a job of present invention to provide a cured resin material which was produced by curing the curable resin composition with good thermal resistance, chemical resistance and Resistance to solvents and the ability to at a relatively low Temperature to bring about a hardening reaction, and also with great electrical performance.

The curable resin composition of the present invention characteristically contains a low molecular compound having a crosslinking group attached at the end of such a structure that two to seven benzene rings have any one or more of the bonds ether bond, methylene oxide bond (typical group -OCH ₂ - ), Ketone bond (carbonyl group -CO- as a typical group) and sulfonyl bond are bonded together; and contains a crosslinking polymer having polymerized units, each of which has a structure such that a plurality of benzene rings are bonded to one another through any one or more of the ether bond, ketone bond, and sulfonyl bond, with a crosslinking group attached to it the end of a polymer is bound with a molecular weight greater than that of the low molecular weight compound.

In addition, the low molecular weight compound preferably has two benzene rings linked by an ether bond.

Otherwise, the low molecular weight compound has three to seven Benzene rings linked by ether linkage and ketone linkage are.  

Among the bonds between the benzene rings in the low molecular compound and the bond between the Benzene ring at the end and the cross-linking group are at least one or more of these bonds in the meta or ortho position.

If the number of benzene rings in the low molecular compound 5 to 7, has at least one or more of the Benzene rings prefer substituents.

The benzene rings are in the units of the crosslinking polymer preferably by means of ether bonding and ketone bonding with one another connected.

Among the bonds between the benzene rings within the units of the crosslinking polymer and the bonds between the units are at least one or more of these bonds in meta- or ortho position.

In addition, at least one of the benzene rings in the crosslinking one Polymer a substituent.

The bonded to the benzene ring in the crosslinking polymer An alkyl group is preferably a substituent.

The crosslinking group attached to the low molecular compound or the crosslinking polymer should be bound, is preferably one thermally crosslinkable crosslinking group.

In addition, the crosslinking group preferably forms one when crosslinking three-dimensional conformation.

Such a crosslinking group preferably contains an ethynyl group.  

In addition, it may be satisfactory that the three-dimensional conformation-capable networking group Crosslinking is only bound to the low molecular weight compound.

More specifically, the crosslinking group in the low molecular compound forms a three-dimensional conformation by crosslinking, and the crosslinking group in the crosslinking polymer preferably contains a vinyl group, an allyl group and at least one or more of the groups represented by the following formulas 1 to 9 are shown.

The crosslinking polymer preferably has a molecular weight Number average from 1,000 to 60,000.

The cured resin material of the present invention is made by Curing such a curable resin composition.

The electrical resistance element of the present invention includes the hardened resin material.

The curable resin composition of the present invention is one Mixture of such a special low molecular compound and a crosslinking polymer, and the composition itself is highly soluble in organic solvents, but is implemented to a hardened resin material which after the crosslinking reaction in organic solvents is insoluble.

Low molecular compound

In the low molecular compound according to the present Invention is a cross-linking group at the end of a structure bound, in which two to seven benzene rings are bound together by any or more of the ether linkages, Methylene oxide bond, ketone bond and sulfonyl bond.

Such low molecular weight compounds include, for example, those represented by the following chemical formulas.

in which R ₁ and R _{2 are} crosslinking groups.

In particular, those included are shown below.

Low molecular weight compounds which contain at least one methylene oxide bond are, for example, the compounds shown below.

Low molecular weight compounds that have at least one sulfonyl bond are included, for example, those by chemical formula 7 compounds shown and those shown below Links.

By the presence of such a low molecular weight compound the curing temperature can be reduced. The low Molecular weight lowers the curing temperature and increases it also the solubility in organic solvents. Furthermore the higher solubility brings synergistically the effect of a higher Transferability of the networking group and the effect of a strong Lowering the hardening temperature with itself.  

By inserting a substituent into the benzene ring like this The solubility can be further described below be increased, but the introduction of the substituent affects the Resistance to solvents after curing is relatively disadvantageous. Therefore the solubility can be improved by further reducing the Molecular weight without the introduction of any substituent what the Solvent resistance of the resulting cured resin material increases.

The connection with two benzene rings, for example through the Chemical formula (1) shown compound can be an extreme have a low curing temperature and a good one Gain solvent resistance after connecting to a hardened material has been implemented. In addition, the Compound can be easily synthesized. Furthermore, the Synthesis promoted more easily due to the lack of necessity any substituent.

Individual benzene rings in such a low molecular weight compound can be linked satisfactorily through any or more of the bonds ether bond, methylene oxide bond, Ketone bond and sulfonyl bond. By linking through a such binding can be from the low molecular weight compound derived hardened materials have great thermal resistance and chemical resistance and good mechanical properties and received the like. Among them are those with an ether Binding or ketone binding preferred. In addition, the connection can be easily synthesized with ether linkage.

A compound having three or more benzene rings may preferably have one have such a structure that the compound is both an ether bond contains a ketone bond as well, as it does in chemical formulas (2-i) and (2-ii) is shown. Because of the presence of the ketone bond the packing ability of the molecular chain is improved, and thereby  their crystallinity is improved, which reduces the Hygroscopicity causes. Because of the presence of the ether bond the synthesis is also easily promoted or promoted.

The low molecular compound of the present invention a networking group tied to its end.

Crosslinking groups include those that are thermally crosslinkable are, those who can be networked by light, those who are through ultraviolet radiation are cross-linkable, and those through Electron radiation - can be cross-linked, including for example Ethynyl groups, allyl groups, epoxy groups, vinyl groups, Styryl groups (chemical formulas 1-3), methylene styryl groups (4-6), Phenylenallyl groups (7-9) and propenyl groups.

Among them, those that are thermally crosslinkable are preferred because they are sufficiently networked with good manageability and manageability can be. Those who can be networked by light, or those that can be cross-linked by electron radiation can Unfortunately, they can hardly be networked evenly when using inorganic fillers are mixed.

In addition, those who are networking are three-dimensional Build conformation in terms of thermal resistance and mechanical strength and the like. Preferred. As such, ethynyl Groups, biphenyl groups, benzoylcyclobutene and the like shown.

If a crosslinking group in the crosslinking reaction is a Incoming condensation, volatile components such as water formed so that the resulting connection has a higher Can have hygroscopicity. However, there is no such problem when the crosslinking group is an ethynyl group, so that the  resulting hardened material is high density and higher Possesses strength.

In addition, at least one or more of the bonds are between the benzene rings or between the benzene ring at the end and one crosslinking group preferably in the meta or ortho position, like it in the chemical formulas (b) - (g), (2-i), (3-i), (4), (5), (6) and (9) is shown.

By means of the presence of the benzene ring linked in meta- or ortho position (namely any position other than para) can Connection assume a curved conformation with the consequence lower crystallinity resulting in the improvement of the Solubility in solvents and reducing the Curing temperature for crosslinking and curing the connection, and hardened materials from the bond can be increased Have solvent resistance. The effect is particularly effective at a larger number of benzene rings.

In addition, 5 to 7 benzene rings are preferred with linked to a substituent as it is by chemical formulas (4 '), (4' ') and (6) is shown.

Examples of substituents are alkyl groups such as the methyl group, ethyl group, propyl group, isopropyl group (-CH (CH ₃ ) ₂ ), butyl group and t-butyl group; the phenyl group; Sulfone group; Alkyl ether groups such as the methoxy group and ethoxy group; and alkoxyl group. Among them, the t-butyl group (-CH (CH ₃ ) ₂ ) and the amyl group (-C ₅ H ₁₁ ) are preferred. Several types of these substituents can be used for a low molecular compound.

A compound with a larger number of benzene rings has one less solubility, but the binding of such substituents to the  Benzene rings can change the solubility of the compounds in different ways improve organic solvents. Among them can be hydrophobic Substituents solubility in hydrophobic organic solvents improve. From this point of view, the alkyl Group preferred.

Crystallinity is reduced by any association with Substituents, which is disadvantageous in terms of moisture resistance. If the substituents are hygroscopic, like the sulfone group and the Hydroxyl group, the moisture resistance is deteriorated. If they are substituents on hydrophobic alkyl groups, the However, deterioration in moisture resistance is suppressed will.

Such a low molecular weight compound can be produced by reacting an aromatic ether ketone which is on End linked with halogenated products (fluoride, or bromide Chloride), with benzene diol (dihydroxybenzene) and ethynylphenol.

In the present example, a curing composition that is linked to an ethynyl group as a crosslinking group, using ethynylphenol as a reactive substance made, but if an allyl group as a crosslinking group bound may be satisfactory instead of ethynylphenol Allylphenol or allyl alcohol can be used when an epoxy Group is bound, glycidol can be used if one Vinyl group is bound, 4-vinylbenzyl alcohol be used satisfactorily.

Crosslinking polymer

Along with the low molecular weight compound requires the curable Resin composition of the present invention is a special one crosslinking polymer as an essential component thereof.  

The repeating units in such a polymer can be, for example, those represented by the following chemical formulas.

In these polymers the units have like that Repeating units a plurality of benzene rings of such Structure that the benzene rings have at least one or more of the Bonds ether bond, ketone bond and sulfonyl bond are linked together.

Among them are the benzene rings, which are bound by ether or ketone Are linked together, preferred.  

In addition, benzene rings are three or more in number contain both an ether bond and a ketone bond prefers. Because of the presence of the ketone bond, the Packing ability of the molecular chain increases, and its crystallinity is also increased, which improves hygroscopicity. Because of the In the presence of the ether bond, the synthesis is also simple.

As exemplified in the following formula, the crosslinking groups R ₁ and R ₂ are attached to the ends of the polymer of the present invention.

Such crosslinking polymers are, for example, those illustrated below.

It is necessary that the molecular weight of the crosslinking Polymer is greater than the molecular weight of the low molecular weight Connection, and the resulting connection can be improved get electrical properties when connecting contains such high molecular weight crosslinking polymer. An easy Lowering the curing temperature to some extent can can be achieved by reducing the molecular weight of the curable Resin composition, but such a curable Resin composition may have deteriorated electrical Properties, especially poor temperature behavior. The curable resin composition of the present invention can Lowering the curing temperature without worsening the electrical properties because the composition of the low molecular compound and a crosslinking polymer with one  higher molecular weight than that of the low molecular weight compound contains.

As for the molecular weight of the crosslinking polymer, it has Polymer prefers a number average molecular weight of 1,000 to 60,000. Within the area has the resulting one Composition especially good solubility in organic Solvents and has a suitable viscosity, so that an ink the composition can have great thixotropic properties, with the resulting good image precision during printing and with excellent properties of the ink (printability).

In addition, it is particularly preferred that the molecular weight Number average is 3,000 to 15,000. If the molecular weight- Number average 3,000 or above, the resulting can be Composition as a good electrical resistance element Acquire temperature behavior; if the molecular weight is 15,000 or below that, the solubility is increased, which for Resistance elements meet the required solubility requirements can.

Accordingly, by adjusting the molecular weight Solubility can be adjusted depending on the purpose. For example, for a polymer for use as a simple paint the molecular weight can be set satisfactorily in such a way that solids in it in chloroform at ambient temperature in a Final concentration of 10 wt .-% or more can be solved.

A lower degree of polymerization causes a relative increase in Number of crosslinking groups bound at the end, so that various properties such as thermal resistance and mechanical strength can be improved if the polymer is crosslinked and converted into a hardened resin material.  

In addition, the polymer can have a smaller degree of polymerization be more easily dissolved in solvents.

At least one or more of the bonds between the benzene rings within the units or the bonds between the units are preferably in the meta or ortho position. Like the compound shown by the chemical formula below, which has a bond in the meta or ortho position (namely any position other than para), the crosslinking polymer forms a curved conformation, with the resultant reduced crystallinity and improved solubility in solvents, so that the curing temperature during crosslinking and curing can be reduced and the resulting cured material can have increased solvent resistance. In the case of the crosslinking polymer which is easily soluble in solvents, the binding in the meta or ortho position is particularly effective.

As with the low molecular compound described above includes the crosslinking group attached to the end of the polymer should be thermally cross-linkable groups, groups that can be cross-linked to light, groups crosslinkable by ultraviolet radiation and by means of Electron beam crosslinkable groups, including for example Ethynyl group, allyl group, epoxy group, vinyl group, styryt  Group (1-3), methylenstyryl group (4-6), phenylenallyl group (7-9) and propenyl group.

Among them, the thermally crosslinkable ones are preferred because they are with good manageability can be networked sufficiently. The networking Group in the low molecular compound and the crosslinking Groups in the crosslinking polymer are both preferably thermal networkable.

Also, those who are networking are three-dimensional Build conformation in terms of thermal resistance and mechanical strength and the like are preferred. As such the ethynyl group, biphenyl group, benzoylcyclobutene and the like illustrated.

A crosslinking group that in a crosslinking reaction Condensation may occur due to the presence volatile components increase hygroscopicity. Such a thing However, the problem does not occur if the networking group has a Is ethynyl group, so the resulting hardened material is a has higher density and higher strength.

It is preferred that the cross-linking group be a three-dimensional one Conformation or structure, both to the low molecular weight Compound as well as bound to the crosslinking polymer because then the crosslink density can be increased, resulting in the Improvement in thermal resistance leads. However, if the networking group should only be bound to one of them, can bind to the low molecular weight compound preferably lower the curing temperature more than that Binding to the cross-linking polymer. Therefore, from the point of view improvement of mechanical properties and thermal Resistance and lowering the curing temperature Preferred compound, which is composed of the  low molecular weight compound to which a crosslinking group bound to build a three-dimensional conformation in capable, and from the crosslinking polymer to which one crosslinking group is bound by the stronger influence of Cross-linking reaction on the part of the low-molecular compound easily is crosslinkable, including vinyl group, allyl group or any other or more of these groups by the chemical formulas 1 to 9 are shown.

In addition, the substituents in the crosslinking polymer can preferably be bound to the benzene rings, as is shown, for example, by the chemical formulas (a) to (e), (g) and (h). The substituent includes, for example, alkyl groups such as methyl group, ethyl group and isopropyl group (-CH (CH ₃ ) ₂ ); the phenyl group; the sulfone group; the alkyl ether group such as the methoxy group and ethoxy group; and the alkoxyl group. Among them, the t-butyl group (-CH (CH ₃ ) ₂ ) and the amyl group (-C _r H ₁₁ ) are preferred. Several types of these substituents can be used for a low molecular compound.

A compound with a higher molecular weight has one less solubility, but the binding of such substituents to the Benzene rings can increase the solubility of the compound in different ways improve organic solvents. Hence solubility be increased more effectively if substituents instead of the low molecular weight connection to the crosslinking polymer with more Benzene rings are bound.

Among them, the solubility can be increased while the Reduction in moisture resistance can be suppressed when the substituents are highly hydrophobic alkyl groups.

The curable resin composition of the present invention contains both the low molecular weight compound and the crosslinking one  Polymer, but if the crosslinking group of low molecular weight Compound and the crosslinking group of the crosslinking polymer Both are vinyl groups, the composition can hardly be one three-dimensional structure when the composition of the Crosslinking and curing reaction is subjected. Therefore they are mechanical properties including deformation under heat of the resulting product not so good, but the curing temperature can be reduced very well. More specifically, if one low molecular compound with a low curing temperature is mixed with a crosslinking polymer with a high Curing temperature, the curing temperature is not easy in Depending on their mixing ratio, but the Temperature is lowered synergistically because of the highly reactive crosslinking group of the low molecular weight compound Crosslinking reaction of the crosslinking group of the crosslinking group Polymers influenced. For example, because the reactivity of the vinyl Group is higher than the reactivity of the ethynyl group that Crosslinking reaction therefore at a lower temperature than that Temperature for crosslinking the ethyl groups.

If the crosslinking group of the low molecular weight compound is one Is vinyl group and the crosslinking group of the crosslinking Polymers is an ethynyl group, affects the active species of the Vinyl group of the lower molecular compound with a lower one Curing temperature less the reactivity of the ethynyl group of the crosslinking polymer. Therefore, the curing temperature depends on the curable resin composition significantly from the curing temperature of the crosslinking polymer. To reduce the It is therefore the curing temperature of the curable resin composition effective to increase the curing temperature of the crosslinking polymer lower, for example by reducing the molecular weight of the crosslinking polymer.  

If the crosslinking group of the low molecular weight compound is one Is ethynyl group and the crosslinking group of the crosslinking Polymers is a vinyl group (e.g., the one below described Examples 1 to 4), generates the crosslinking reaction of Ethinyl group vinyl radicals as a reaction intermediate. Because the radical is the crosslinking reaction of the vinyl group of the crosslinking Polymer induced or triggered, the setting of the Mixing ratio of low molecular compound and crosslinking polymer the curing temperature of the curable Significantly lower resin composition.

When the crosslinking group of the low molecular compound and the crosslinking group of the crosslinking polymer both ethynyl Are groups (e.g. Examples 5 described below to 10) is the curing temperature of the curable resin composition a temperature that results from the curing temperature the low molecular weight compound and the curing temperature of the crosslinking polymer. Accordingly, their mixing ratio be set to the curing temperature of the curable Lower resin composition.

The curable resin composition of the present invention contains at least the low molecular weight compound and the crosslinking one Polymer in blend, and in the process of making the There is no particular restriction on composition. For example the composition is made by kneading the low molecular compound and the crosslinking polymer known methods. A single-screw extruder can be used for kneading Twin screw extruder, a Brabender, a Banbury mixer, a Kneading mixers and the like can be used.

The individual given amounts of powder of low molecular weight Compound and the powder of the crosslinking polymer mixed together, followed by the addition of a solvent  the resulting mixture and subsequent kneading. Furthermore the individual powder can satisfactorily in a solvent be introduced, followed by mixing the powders together. The the latter method is favorable because of the easy transferability into it next procedure.

The mixing ratio of the low molecular weight compound and the crosslinking polymer is preferably 3: 7 to 7: 3 im Weight ratio. Within this range, that Mixing ratio can be set appropriately to properties create that are satisfactory for the purpose.

Within the range, the curable resin composition of the present invention without deteriorating the subject of The present invention can be mixed with various common ones Additives such as antioxidants, heat stabilizers, Light stabilizers, weather stabilizers, antistatic agents, anti-fogging agents, flame retardants, whiteners, Release agents, foaming agents, lubricants, non-stick agents, dyes, Pigments, colorants, flavors, ultraviolet radiation absorbents, processing aids and anti-shock Auxiliaries, with inorganic fillers such as calcium carbonate, Talc, fiberglass, mica and calcium silicate, with organic Fillers, with thermoplastic resins and with various other resins and the like.

Because the curable resin composition of the present invention has an excellent solubility in common solvents the composition using various shaping techniques different shaped objects can be shaped.

Solvents include, for example, chloroform, tetrahydrofuran (THF), N, N'-dimethyl sulfoxide (DMF), N-methyl-2-pyrrolidone, Triglyme and the like.  

The shaping techniques include, for example, hollow forms, Injection molding, extrusion and compression molding.

The cured resin material of the present invention is made by the crosslinking group in the curable resin composition is subjected to a crosslinking reaction. By such a thing Crosslinking and hardening will result in organic material Solvent insoluble to provide excellent thermal Resistance, chemical resistance and mechanical resistance, purchase along with excellent electrical properties. Therefore, the product is particularly useful as an electrical resistance element prefers.

To produce an electrical resistance element, a Resistance material like carbon black or graphite to the one in one Solvent-added curable resin composition added up to a final resistance value, and the resulting mixture is then printed on a substrate, followed by curing under Heat.

Synthesis example of the low molecular compound (1)

4-Bromophenyl ether (6.56 g; 0.02 mol) was dissolved in triethylamine (50 ml), followed by addition of 2-methyl-3-butyn-2-ol (3.55 g; 0.05 mol) ) in a stream of nitrogen. Thereafter, triphenylphosphine (0.12 g), copper iodide (0.03 g) and palladium catalyst (0.03 g) were added to the resulting mixture to react in a nitrogen flow at 80 ° C for 20 hours. The reaction solution was then filtered to recover the filtrate, which was then washed in triethylamine. Using an evaporator, the solvent was removed from the filtrate, followed by addition of chloroform and washing in 5% aqueous H ₂ SO ₄ solution and then in water. The chloroform was then removed to obtain a butyne adduct as a yellow powder after vacuum drying.

6.9 g (0.02 mol) of the butyne adduct obtained were dissolved in toluene (40 ml) dissolved, followed by addition of methanol (20 ml) to complete Resolution. The resulting mixture was added in a stream of nitrogen NaOH (2.4 g; 0.06 mol) added and at 30 ° C for 30 minutes Kept reflux. Then the temperature became gradual Evaporation of the methanol increased to 120 ° C, and then the Sufficient reaction with movement for 2 to 3 hours continued. After the reaction, chloroform became the Added reaction mixture, which was then washed in water, and the chloroform layer was extracted and over sodium sulfate dried, then it was filtered and the solvent with a Evaporator evaporates to obtain a black liquid. By vacuum drying at ambient temperature, the Liquid gradually solidified to brown di (4-ethynylphenyl) ether, represented by the chemical formula (1).

The product was identified by nuclear magnetic resonance in duterium Chloroform identified (NMR; Bruker AM-250).

¹ H NMR (CDCl ₃ ): (3.1 ppm, ethyl group) (7.5 ppm, 7.4 ppm, 7.0 ppm, 6.9 ppm, aromatic ring).

Synthesis example of the low molecular compound (2-i)

2.49 g (0.01 mol) of 4-bromodiphenyl ether and 2 g (0.01 mol) Weighed 3-bromobenzoic acid and then in PPMA (40 ml) (Methanesulfonic acid: phosphorus pentoxide = 9: 1) dissolved for a 5- hourly reaction at 80 ° C. The reaction solution was in water given, followed by neutralization with sodium hydrogen carbonate and Filtration, and the fraction obtained was placed in water several times  washed. Then the fraction was filtered and dried to make a to win pale brown powder.

Using the resulting compound (1) with bromide on End instead of the butyne adduct for the synthesis of low molecular weight Compound (1), the same process steps were carried out to which are obtained through the chemical formula (2-i).

Synthesis example of the low molecular compound (2-ii)

Using 4-bromobenzoic acid instead of 3- Bromobenzoic acid in the synthesis example of low molecular weight Compound (2-i), the same operations were carried out to the to obtain compound represented by the chemical formula (2-ii).

Synthesis example of the low molecular compound (3-i) Synthesis example 1 of the precursor

First, 4,4'-bis (3-bromophenoxy) benzophenone was used as a precursor synthesized.

3-Bromophenol (3.8 g; 22 mmol), methanol (20 ml) and benzene (20 ml) were mixed together, and to the resulting reaction system was added IN KOH (20 ml) in the gas stream of N ₂ gas while Methanol and water were removed at a temperature of 100 ° C or less. Thereafter, benzene (20 ml) was added to the resulting product before a method of distilling off the benzene at a temperature of 100 ° C or less, and 4,4'-difluorobenzophenone (2.18 g; 10 mmol) and dimethyl sulfoxide (DMSO; 30 ml) added for 4 hours of reaction at 140 ° C to obtain 4,4'-bis (3-bromophenoxy) benzophenone (3.8 g; yield about 72%).

Synthesis example 2 of the precursor

In the following procedure, 4,4'-bis (3-bromophenoxy) benzophenone be synthesized.

3-bromophenol (3 ', 8 g; 22 mmol), 4,4'-difluorobenzophenone (2.18 g; 10 mmol), dimethylacetamide (DMAC; 10 ml), toluene (15 ml) and K ₂ CO ₃ (4th , 55 g) were mixed together for one hour reaction in N ₂ gas flow at 130 ° C. The temperature was then raised to 160 ° C to remove the toluene and water in the reactor in an azeotropic mixture. Then the reaction was continued for 2 hours to recover 4,4'-bis (3-bromophenoxy) benzophenone (5.25 g; yield about 100%).

A very high yield can be achieved in the process.

The synthesized 4,4'-bis (3-bromophenoxy) benzophenone (1.4 g; 2.7 mmol) and 2-methyl-3-butyn-2-ol (0.67 g; 8 mmol) were dissolved in triethylamine ( 20 ml) and N ₂ gas was poured into the resulting reaction system for 20 minutes. Then triphenylphosphine (0.02 g), palladium catalyst ((Ph ₃ P) PdCl ₂ ) (0.005 g) and copper iodide (0.005 g) were added to the reaction system for 20 hours of reaction at 80 ° C. Thereafter, the resulting product was washed in water, followed by extraction of the reaction product with methylene chloride, and then the reaction intermediate was recovered after removing the methylene chloride. Toluene (20 ml), methanol (10 ml) and NaOH (0.8 g) were also added to the reaction intermediate, before evaporation and removal of methanol and part of the toluene at a temperature of 100 ° C. The reaction solution was then washed in water, before extraction with methylene chloride and subsequent removal of the extraction solvent by 4,4'-bis (3-ethynylphenoxy) benzophenone (1.3 g; yield 94%), which was determined by the chemical formula ( 3-i) is presented to win.

In the synthesis example herein, a tertiary alcohol having an acetylene group was used as a substituent, namely 2-methyl-3-butyn-2-ol; but instead of the alcohol, a silylacetylene such as trimethylsilylacetylene can be used satisfactorily.

(CH ₃ ) ₃ SiC∼CH).

In addition, the precursor can be synthesized using 3-ethynylphenol.

In the process using 3-ethynylphenol, the Reaction can nevertheless be carried out at about 170 ° C, and 3- Unfortunately, ethynylphenol itself is expensive.

In the process using the 2-methyl-3-butyn-2-ol can however, the reaction can be carried out at about 80 ° C, the Is easily produced at low cost (about 0.1% of the precursor Cost in the case of 3-ethynylphenol).

In the process using 3-ethynylphenol, the Addition of the ethynyl group also inevitably the Addition of the benzene ring with it, so that the process for Synthesis of a product with fewer benzene rings is not suitable; at the method using 2-methyl-3-butyn-2-ol however, only the ethynyl group can be added without propagation Benzene rings, so that the process of making a connection with less benzene rings is excellent.

Synthesis example of the low molecular compound (3-ii)

Using 4-bromophenol instead of 3-bromophenol the same steps were carried out as in the Synthesis example of the low-molecular compound (3-i) to the by to obtain the chemical formula (3-ii) represented compound.

Synthesis example of the low molecular compound (4)

4,4'-difluorobenzophenone (2.18 g) and 4-fluorophenol (1.12 g) were in Dimethylacetamide (DMAC; 20 ml) and toluene (40 ml) dissolved, followed by adding potassium carbonate (2.76 g), and for one hour Maintained 130 ° C at reflux. By subsequently increasing the Temperature to 170 ° C, toluene was distilled off and removed while the reaction was continued for 2 hours. Then that became Reaction product precipitated in water (reprecipitated), filtered and  dried to obtain a white powder. The powder was in Chloroform dissolved to separate using silica gel in bis (4-fluorophenoxy) benzophenone and aryl ether ketone with one fluorinated end (three benzene rings).

For the synthesis of an aryl ether ketone (five benzene rings) with an acetylene end on the way via an aryl ether ketone (five benzene rings) with bromide The end and the aducts were the same steps as in the Synthesis example of the low molecular compound (3-i) carried out with Except for the use of the aryl ether ketone thus obtained fluorinated end instead of 4,4'-bis (3- bromphenoxy) benzophenone.

Synthesis example of the low molecular compound (5)

The compound represented by chemical formula (5) was described in the same way as in the synthesis example of the low molecular weight Compound (4) obtained, with the exception of using bis (4-fluorophenoxy) benzophenone (four benzene rings) instead of the one in it used 4,4'-difluorobenzophenone.

Synthesis example of the low molecular compound (6)

(p-phenylenedioxy) bis (2-methyl-4 - (- fluorobenzoyl) benzene) (21.4 g) and 3-bromophenol (15.4 g) along with potassium carbonate (8.5 g) weighed, and to the resulting mixture Dimethylacetamide (DMAC; 70 ml) and toluene (70 ml) were added and refluxed for one hour at 130 ° C in a stream of nitrogen. By subsequently increasing the temperature to 175 ° C, toluene distilled off for the subsequent 2-3 hour reaction.

After the reaction, the reaction solution was poured into a large amount of water, followed by addition of NaOH to a final concentration of about 3 to 5% by weight of an aqueous NaOH solution, and followed by agitation overnight. Thereafter, after subsequent filtering and washing in water and vacuum drying at 50 ° C., a compound with a bromide end was obtained as a white powder (yield of about 100%).
¹³ C NMR: 160.35, 159.37, 156.62, 152.24 ppm.
Elemental analysis: 18.75 (calculated 19.0).

The bromine-terminated compound thus obtained was dissolved in pyridine (100 ml) and triethylamine (100 ml), followed by addition of 2- Methyl-3-butyn-2-ol (10.72 g), triphenylphosphine (0.35 g), palladium Catalyst (0.089 g) and copper iodide (0.089 g), and for 20 hours Allow to react at 85 ° C. After the reaction, the Reaction solution was filtered, and the resulting filtrate was the solvents (pyridine and triethylamine) with an evaporator removed, followed by addition of chloroform to the resulting To manufacture product in the form of a solution. The solution was in Washed about 10% sulfuric acid solution and water, followed from drying over sodium sulfate to remove the solvents and subsequent vacuum drying at 40 ° C to connect with Win the adduct end as a yellow powder (yield 100%).

The resulting adduct (34.1 g; 40.3 mmol) was dissolved in 150 ml toluene (pre-dried over potassium calcium), followed by the addition of sodium hydroxide (4.03 g; 2.5 times the molar amount / monomer) in several servings at 80 ° C. In other words, added NaOH produced gas so that further portions of NaOH were gradually added to the solution after the gas evolution had calmed down. After the addition of NaOH, the reaction was continued at 100 ° C for 1 hour. After the reaction, the solution was washed in 5% NaHCO ₃ to collect the toluene layer. In addition, the aqueous layer was extracted twice with chloroform, and the layers extracted with chloroform were combined with the toluene layer, and from the resulting mixture, the solvents were distilled off by an evaporator to obtain a black viscous product. Acetone was added to the product, and the resulting product was reprecipitated in a large amount of petroleum ether. 20-30 times the volume of the acetone solution was used from the petroleum ether. The petroleum ether was then decanted to recover the remaining viscous product, which was then dissolved in a small amount of acetone and then reprecipitated in a large amount of water. A small amount of sodium chloride was added to the water for better separation of the precipitated product. After filtering and drying, a low molecular compound having an acetylene end as represented by the chemical formula (6) was obtained as a pale yellow solid.

Synthesis example of the low molecular compound (8)

1,3-Di (4-hydroxbenzoyl) benzene (5.57g) was dissolved in tetrahydrofuran (THF) (30 ml) dissolved, for which an aqueous 33% NaOH solution (30 g) was added, followed by motion. Then was Tetrabutylammonium hydrogen sulfate (TBAH; 11.9 g) to which itself resulting mixture added, followed by agitation, and while to chloromethylstyrene (5.4 g) was added dropwise to the mixture, the mixture was kept at ambient temperature for several hours Subject to reaction. Then the reaction solution was used twice Extracted ether, and by subsequently removing the ether from the A white solid was obtained from the reaction mixture. More again Purification in hot hexane produced one through the chemical formula (8) low molecular compound shown.

Synthesis example of the low molecular compound (9)

4,4'-difluorodiphenyl sulfone (6.35 g), 3-bromophenol (9.08 g) and Potassium bicarbonate (6.9 g) was weighed and added to resulting mixture was DMAC (50 ml) and toluene (80 ml)  added and refluxed at 130 ° C for 1 hour. While the temperature was raised to 160 ° C, toluene To distill off, the reaction was continued for 2 hours. After the reaction was the reaction product in 1.5 liters of water again precipitated, followed by filtration and drying to connect with Bromide end to be obtained as a white powder.

To obtain those represented by the chemical formula (9) Compound became the same procedure as in the synthesis example of the low molecular compound (3-i), with the exception using the bromide terminated compound.

Synthesis example of the crosslinking polymer (a ¹ )

4,4-difluorobenzophenone (5.4553 g) and 2-methylresorcinol (3.4324 g) were placed in a reactor and then in N, N'- Dimethylacetamide (40 ml) and toluene (40 ml) dissolved. To yourself resulting solution was added potassium carbonate (11.5 g), followed of agitation in a stream of nitrogen at 130 ° C for one hour for boiling at reflux. By subsequently increasing the temperature to 170 ° C to remove toluene and water, the reaction was carried out on this Temperature continued for 2 hours.

A suitable amount was added to the resulting polymer solution DMAC was added and the mixture was then poured into 2 liters of aqueous Methanol solution (water: methanol = 1: 1) added to one to produce pale brown precipitation. This was filtered and vacuum dried to a hydroxy terminated polymer polymerize (7.4 g).

2.15 g of the resulting polymer was dissolved in chlorobenzene (35 ml) dissolved, for which purpose an aqueous 20% NaOH solution (2.4 g) was added, followed by addition of TBAH (0.11 g) under Move. The resulting mixture was then added dropwise  Chlorobenzene (5 ml) in which 0.05 g of chloromethylstyrene was dissolved, admitted. After that the reaction was at ambient temperature continued for several hours, followed by the addition of water and extraction in chloroform. The extract solution was concentrated and precipitated again in 1 liter of methanol. Under suction filtered off and dried in vacuo to give a crosslinking polymer, as represented by chemical formula (a), as white Winning powder. The resulting crosslinking polymer had one Number average molecular weight (Mn) of 21,000.

The molecular weight of the crosslinking polymer can be adjusted are dependent on the ratio of the monomers used. The Relationship between the conditions used and the experimental values of the molecular weights of the crosslinking Polymers is shown in Table 1. The molecular weight was determined using Gel permeation chromatography ("RI-8020" manufactured by TOSHO Corp.) on a nominal column of 500,000 (manufactured by Hitachi Chemical Co., Ltd.) and a nominal column of 60,000 (manufactured by TOSHO Corporation) using a polystyrene standard measured by chloroform as the solvent. Of the Molecular weight value is expressed as the molecular weight Number average (Mn).

Table 1

Synthesis example of the crosslinking polymer (b)

The 4,500 molecular weight crosslinking polymer as represented by the chemical formula (b) was obtained in the same manner as in the synthesis example of the crosslinking polymer (a ¹ ) except that 4,4'-difluorobenzophenone (2.182g) and t-butylhydroquinone (2.0362 g) were used.

Synthesis example of the crosslinking polymer (c ¹ )

The crosslinking polymer having a molecular weight of 4,000 as represented by the chemical formula (c) was obtained in the same manner as in the synthesis example of the crosslinking polymer (a ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) (2.0121 g) and resorcinol (0.4425 g) were used.

Synthesis example of the crosslinking polymer (c ² )

The crosslinking polymer having a molecular weight of 2,500 was obtained in the same manner as in the synthesis example of the crosslinking polymer (c ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) (1.6788 g) and resorcinol (0.4404 g) were used.

Synthesis example of the crosslinking polymer (c ³ )

The crosslinking polymer having a molecular weight of 8,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (a ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) (2.0127 g) and resorcinol (0.4404 g) were used.

Synthesis example of the crosslinking polymer (d)

4,4'-fluorobenzophenone (1.379 g) and t-butylhydroquinone (0.8543 g) were dissolved in DMAC (15 ml) and toluene (20 ml), followed by Add potassium carbonate (1.74 g) and 1 hour in a stream of nitrogen held at reflux for long at 130 ° C. By increasing subsequently the temperature to 170 ° C., toluene was distilled off and removed for another 2 hour response. After the reaction that was Reaction product precipitated again in water, filtered and dried, to obtain a fluoride terminated polymer as a pale pink powder.

The resulting fluoride terminated polymer (1.7 g), 3-ethynylphenol (0.2 g) and potassium carbonate (0.25 g) were placed in a flask introduced, DMAC (15 ml) and toluene (20 ml) added, and at Maintained at reflux at 120 ° C for 1 hour in a stream of nitrogen. Means Raise the temperature to 165 ° C to distill off toluene the reaction continued for 2 hours. After the reaction was over the resulting product reprecipitated in water, followed by Filtration and drying to form a crosslinking polymer Molecular weight of 3,000 as determined by chemical formula (d) is presented to win.

Synthesis example of the crosslinking polymer (e)

4,4'-fluorobenzophenone (1.379 g) and 2-methylresorcinol (0.6394 g) were dissolved in DMAC (15 ml) and toluene (20 ml), followed by Add potassium carbonate (1.74 g), and 1 hour at 130 ° C in Nitrogen stream kept at reflux. By subsequent increase the temperature to 170 ° C., toluene was distilled off and removed to react for another 2 hours. After the reaction that was Reaction product precipitated again in water, filtered and dried, to obtain a fluoride terminated polymer as a pale pink powder.

The resulting fluoride terminated polymer (1.6 g), 3-ethynylphenol (0.2 g) and potassium carbonate (0.26 g) were placed in a flask  introduced, DMAC (15 ml) and toluene (20 ml) added, and at Maintained at reflux at 120 ° C for 1 hour in a stream of nitrogen. Means Raise the temperature to 165 ° C to distill off toluene the reaction continued for 2 hours. After the reaction was over the resulting product reprecipitated in water, followed by Filtration and drying to form a crosslinking polymer Molecular weight of 3,000 as determined by chemical formula (s) is presented to win.

Synthesis example of the crosslinking polymer (f)

A fluoride terminated polymer was prepared in the same manner as that Synthesis example of the crosslinking polymer (d) obtained with the Exception that 4,4'-difluorobenzophenone (1.7456 g), resorcinol (0.8302 g) and potassium carbonate (1.1 g) were used.

A crosslinking polymer with a molecular weight of 4,500, such as it is represented by the chemical formula (f) was in the obtained in the same way as in the synthesis example of the crosslinking Polymers (d), except that the resulting polymer has Fluoride end (2 g), 3-bromophenol (0.1 g) and potassium carbonate (0.13 g) were used.

Synthesis example of the crosslinking polymer (g ¹ )

(p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) (1.0694 g), Hydroquinone (0.2197 g) and 3-ethynylphenol (0.032 g) were added to DMAC (5.3 g) and toluene (20 ml) dissolved, followed by addition of Potassium carbonate (0.45 g), and 1 hour at 130 ° C in a nitrogen stream Kept reflux. By subsequently increasing the temperature Toluene was distilled off at 170 ° C. in order to react for a further 2 Hours. After the reaction, the product was again in water precipitated, filtered and dried to contain a crosslinking polymer  a molecular weight of 9,000 as determined by the chemical formula (g) is shown to be obtained as a pale pink powder.

Synthesis example of the crosslinking polymer (g ² )

The crosslinking polymer having a molecular weight of 13,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (g ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene ) (1.0797 g), hydroquinone (0.2204 g) and 3-ethynylphenol (0.019 g) were used.

Synthesis example of the crosslinking polymer (g ³ )

The crosslinking polymer having a molecular weight of 16,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (g ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene ) (1.0697 g), hydroquinone (0.2204 g) and 3-ethynylphenol (0.01 g) were used.

Synthesis example of the crosslinking polymer (h ¹ )

(p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) (2.1383 g), Resorcinol (0.4316 g) and potassium carbonate (1.1 g) were weighed out, then dissolved in DMAC (10 ml) and toluene (20 ml) and at 1 hour 130 ° C in a nitrogen stream at reflux. By following Increasing the temperature to 170 ° C, toluene was distilled off for 2- hour later reaction. After the reaction, the product reprecipitated in water, filtered and dried to contain a polymer to gain a fluoride end.  

The resulting polymer (2.1 g) and 3-ethynylphenol (0.05 g) were dissolved in DMAC (10 ml) and toluene (20 ml), followed by Add potassium carbonate (0.37 g) and at 130 ° C for 1 hour Nitrogen stream kept at reflux. By subsequently increasing the Temperature to 165 ° C, toluene was distilled off for the following 2 hour response. After the reaction was over, it became Reaction product precipitated in water, followed by filtration and Dry to a crosslinking polymer with a molecular weight of 34,000 as represented by chemical formula (h) win.

Synthesis example of the crosslinking polymer (h ² )

A fluoride terminated polymer was synthesized in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) ( 5.0397 g), resorcinol (0.8479 g), DMAC (20 ml), toluene (40 ml) and potassium carbonate (2.6 g) were used.

The crosslinking polymer having a molecular weight of 3,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that the resulting fluoride-terminated polymer (5.02 g), 3-ethynylphenol ( 0.73 g), DMAC (20 ml), toluene (40 ml) and potassium carbonate (1.7 g) were used.

Synthesis example of the crosslinking polymer (h ³ )

A fluoride terminated polymer was synthesized in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) ( 2.1383 g), resorcinol (0.4041 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (1.1 g) were used.

In addition, the crosslinking polymer having a molecular weight of 10,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that the resulting fluoride-terminated polymer (2 g), 3-ethynylphenol (0 , 1 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (0.37 g) were used.

Synthesis example of the crosslinking polymer (h ⁴ )

A fluoride terminated polymer was synthesized in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) ( 2.1382 g), resorcinol (0.4151 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (1.1 g) were used.

The crosslinking polymer having a molecular weight of 15,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that the resulting fluoride-terminated polymer (2 g), 3-ethynylphenol (0, 1 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (0.37 g) were used.

Synthesis example of the crosslinking polymer (h ⁵ )

In addition, a fluoride-terminated polymer was synthesized in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) (2.1383 g), resorcinol (0.4390 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (1.1 g).

In addition, the crosslinking polymer having a molecular weight of 20,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that the resulting fluoride-terminated polymer (2 g), 3-ethynylphenol (0 , 1 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (0.37 g) were used.

Synthesis example of the crosslinking polymer (h ⁶ )

A fluoride terminated polymer was synthesized in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) ( 5.346 g), resorcinol (1.0888 g), DMAC (20 ml), toluene (40 ml) and potassium carbonate (2.6 g) were used.

In addition, the crosslinking polymer having a molecular weight of 44,000 was obtained in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that the resulting fluoride-terminated polymer (3.7 g), 3-ethynylphenol (0.7 g), DMAC (20 ml), toluene (40 ml) and potassium carbonate (0.98 g) were used.

Synthesis example of the crosslinking polymer (h ⁷ )

A fluoride terminated polymer was synthesized in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that (p-phenylenedioxy) bis (2-methyl-4- (4-fluorobenzoyl) benzene) ( 2.1383 g), resorcinol (0.4390 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (1.1 g) were used.

In addition, the crosslinking polymer having a molecular weight of 61,500 was obtained in the same manner as in the synthesis example of the crosslinking polymer (h ¹ ), except that the resulting fluoride-terminated polymer (2 g), 3-ethynylphenol (0 , 07 g), DMAC (10 ml), toluene (20 ml) and potassium carbonate (0.37 g) were used.

Synthesis example of the crosslinking polymer (i)

4,4'-fluorodiphenyl sulfone (2.4104 g) and resorcinol (0.8489 g) were added dissolved in DMAC (15 ml) and toluene (20 ml), followed by addition of Potassium carbonate (2.61 g), and at 130 ° C for 1 hour Nitrogen stream kept at reflux. By subsequently increasing the Temperature to 170 ° C, toluene was distilled off and removed to to react for another 2 hours. After the reaction that was Reaction product precipitated in water, filtered and dried, to obtain a fluoride terminated polymer as a pale pink powder.

The resulting fluoride-terminated polymer (3 g), 3-ethynylphenol (0.47 g) and potassium carbonate (0.83 g) were placed in a flask DMAC (15 ml) and toluene (20 ml) were added, and refluxed at 120 ° C for 1 hour in a stream of nitrogen. By increasing the temperature to 165 ° C around the toluene To distill off, the reaction was continued for 2 hours. After The resulting product was reacted in water again precipitated, followed by filtration and drying to a cross-linking Polymer with a molecular weight of 1,500 as defined by the chemical formula (i) is presented to win.

The synthesized low molecular weight compounds and the Crosslinking polymers were used in combinations as shown in Table 2 are shown mixed together to form curable resin compositions which were then subjected to a thermal process, around resistance elements as hardened resin materials (Examples No. 1 to 13).

First, the low molecular weight compounds and the crosslinking polymers both as resins in powder form in given Ratios placed in a container followed by addition of Methyl benzoate as a solvent with agitation until reached the target concentrations.  

Carbon black was added to the resulting curable resin compositions added, and the resulting mixtures were mixed in one given shape and in a given final film thickness on a substrate (polyphenylene sulfide resin (PPS)), a phenolic resin Layer plate ("bake"), on a ceramic (aluminum oxide) plate printed, followed by a 15 minute thermal treatment a predetermined temperature around resistance elements with it to produce trained hardened resin materials.

As the carbon (carbon black), "Ketjen Black EC" was manufactured by Ketjen Black International Company used; in Examples 4 and 10 was the carbon black with 2.4% by volume of the coating film in dry Condition included; in all of the remaining examples was carbon with 3.6 vol .-% included.

Printability was increased during film and printing evaluated during formation on the substrates. The results are shown together in Table 2.

In addition, comparative examples are shown in Table 3, in which low molecular weight compounds or crosslinking polymers individually be used.

Tables 2 and 3 also show the resistance values for individual Samples in Table 4, after thermal treatment at the highest Curing temperature.  

Table 2

Table 3

Tables 2 and 3 show that the curable resin compositions of the present invention are well dissolved in solvents and have a suitable viscosity and good printability, while Comparative Examples 1 and 2, which consist solely of low molecular weight Compounds are composed, have a lower viscosity, which is unsuitable for printing and designing. You are the one on this side View that the reason that the printability of comparative example 3 is mediocre, may be that the low molecular weight Compound has many benzene rings, namely 7, as in the chemical formula (6) is shown, and in that the molecular weight is relatively large, namely 730.

Curing temperature test

The temperature was measured, which is sufficient for crosslinking and curing Examples Nos. 1 to 13 and Comparative Examples No. 1 up to 4 is required. The test was carried out by individual Resistance elements of a thermal treatment in individual Temperatures have been subjected to the resulting elements in one Flux detergent (S-36A, manufactured by Shimada Rika Industriy) 15 Minutes were immersed, and the change in electrical  Resistance values were measured before and after immersion. With in other words, a minor change in electrical Resistance values before and after immersion means a for Solvent resistance sufficient crosslinking and hardening what means that the thermal treatment at one for crosslinking sufficient temperature is carried out. In practice there is one Change within 10% is good. The test results are in Table 4 shown.  

Table 4

Table 4 shows that the curable resin compositions of the present invention generally in a thermal Treatment can be cross-linked and hardened up to 250 ° C, so that the resultant elements show great solvent resistance can, but Comparative Example 4, the only from the crosslinking Polymer is composed, because of insufficient hardening Show solvent resistance.

In Examples 1 to 4, in which the crosslinking group in the low molecular compound is the ethynyl group, and the cross-linking group in the cross-linking polymers the vinyl group the crosslinking and curing reaction becomes lower Temperature promoted sufficiently. In particular, in Example 1 a thermal treatment at least 190 ° C is sufficient Hardening observed. The hardening reaction becomes extreme low temperature ended. In example 2 a thermal Treatment at 200 ° C sufficient hardening observed. It is indicated that in Example 3, in which the number of benzene rings 4 is, by a benzene ring more than that in the low molecular weight Compound of Example 2 are present, a thermal treatment at least 220 ° C is required.

In Examples 5 to 10, in which both the crosslinking group in the low molecular weight compound as well as the crosslinking group in the crosslinking polymer is the ethynyl group, the Crosslinking and curing reaction at a sufficiently low Temperature, but not at a temperature as low as in Examples 1 to 4.

Even example 10, in which a part of the benzene rings in the low molecular weight compound or in the crosslinking polymer a sulfonyl group is attached to the compound or the polymer, has the same properties as the other examples.  

In addition, in Example 9, the low molecular weight compound has one higher proportion by weight of the mixture than in Example 12; and the the low molecular weight compound in Example 8 has a higher one Percentage by weight of the mixture as in example 13. It is displayed that a larger amount of low molecular compound Can lower temperature. In addition, a higher one Molecular weight have a higher such effect.

Temperature dependency test of the electrical resistance value

A temperature dependency test of the electrical resistance values of Examples 1 to 12 and Comparative Examples 1 to 4 was carried out. The test was carried out by measuring the initial resistance value (A) of a resistance element, placing the element in an oven at 85 ° C and measuring the high temperature resistance value (B) in the oven 30 minutes later, and calculating the temperature coefficient (ppm / ° C) the resistance value based on the following formula. ((BA) / A) 1 (85 - temperature for measuring the initial resistance value) × 10 ⁶ .

A temperature coefficient of the resistance value within one Range of ± 800 ppm / ° C is rated great; and a Temperature coefficient within a range of ± 500 ppm / ° C classified as good. The results are shown in Table 5.  

Table 5

The cured resin materials of the present invention have excellent temperature coefficient of resistance, with a such minor change in resistance due to the Temperature when the materials only crosslinking and curing Reaction by heating up to 250 ° C were subjected.

In contrast, Comparative Examples 1 through 3 have that alone low molecular compound are composed, larger Temperature coefficient of the resistance value, indicating that the Examples have poor electrical properties.

A higher curing temperature brings a larger negative Temperature coefficient of resistance value with it, which indicates that the thermal expansion coefficient of a resin is smaller if the hardening is carried out higher, so that the negative properties of Carbon cannot be weighed.

Moisture resistance test

The moisture resistance test was carried out on Examples 1, 5, 6, 8, 9 and 11 and Comparative Examples 2 and 3. The test was carried out by measuring the initial resistance value (A) of a resistance element at ambient temperature (20 ° C, 40-70% relative humidity (RH)), placing the element in a thermostat at constant humidity and temperature at 90 to 95 ° RH and 60 ° C, and pulling the element out of the thermostat 500 hours later, and immediately measuring the resistance value (B) and calculating the change (%) in the resistance value based on the following formula.

(B-A) / A × 100.

A change within 8% is excellent and a change within ± 5% is good.  

The results are shown in Table 6.

Table 6

The crosslinking polymer (s) is produced by binding one Methyl group as a substituent on the crosslinking polymer (f), however there will be no deterioration in the moisture resistance of the Example 5 observed in comparison with Example 11. With each of these The change is excellent within ± 5% when the examples Curing temperature is 220 ° C.

The exothermic temperature in DSC (differential scanning Calorimetry) (curing temperature) (° C) and the endothermic peak  (Peak) temperature (melting point) (° C) of the low molecular weight Compounds, the crosslinking polymers and the curable Resin compositions were measured.

The exothermic temperature and the endothermic peak temperature at DSC were at a rate of temperature increase of 10 ° C / min and within a temperature range of 30-400 ° C measured using a differential scanning calorimeter (DSC; type SSC / 5200, manufactured by Seiko Electronics, Co.). The results are shown in Table 7.  

Table 7

In Table 7, * 1 corresponds to Example 3, in which the mixing ratio is 5: 5 [(3-i): (a ³ )]; * 2 corresponds to Example 12, in which the mixing ratio is 3: 7 [(6): (h ² )].

Table 7 shows that the low molecular weight compounds in generally have a low exothermic DSC temperature, but the crosslinking polymers generally have a high exothermic DSC Have temperature. In addition, the exothermic DSC temperature by mixing a low molecular weight compound with a crosslinking polymer can be reduced.

In addition, the exothermic DSC temperature is at the low molecular weight Compound (2-i) with a crosslinking bond in the meta position Group lower than with the low molecular compound (2-ii) with a crosslinking group bound only in the para position; the exothermic DSC temperature is also lower at the low molecular weight Compound (3-i) with a cross-linking bond in the meta position Group than in the low molecular weight compound (3-ii) with only in para-linked crosslinking group.

The effect of the molecular weight of a polymeric compound on their solubility in solvents has been tested.

The test was carried out by evaluating the solubility of the crosslinking polymers (h ¹ ) to (h ⁷ ) in methyl benzoate at the respective concentrations. The results of the evaluation are shown in Table 8. In Table 8 ○ expresses good solubility with viscosity; Δ expresses excessive viscosity with solubility; X expresses an insufficient amount of solvent to dissolve all of the resin.

Table 8

Table 8 shows that a higher molecular weight is a worse one Solubility in the solvent entails.

The curable resin compositions of the present invention have good solubility in organic solvents, and therefore the compositions are applicable as different Matrix resins and as coating materials and adhesives and the like, and they are applicable to molding a large number of shaped objects using various molding agents; With in other words, the compositions can be very high Achieve flexibility. More specifically, the compositions can are used otherwise than for molding and extrusion.

By crosslinking and curing the curable resin compositions Manufactured hardened resin materials are in organic Solvents are insoluble and therefore have a large solvent Resistance, chemical resistance, thermal resistance, Storage stability and excellent mechanical properties. By  Forms of materials, followed by cross-linking and hardening, can various objects with excellent such properties getting produced.

Because the curing temperature is low, the Curing reaction even using a conventional furnace in a short time with good productivity in sufficient scope be performed. In addition, the compositions for Substrates with a not as high thermal resistance as Phenol substrates.

The compositions are also excellent in terms of electrical properties such as temperature properties and Moisture resistance, and therefore the compositions particularly preferred as electrical resistance elements, which also are applicable as electrical resistance elements in difficult or harsh environments, such as battery cases.

Claims (17)

1. A curable resin composition containing a low molecular compound and a crosslinking polymer, wherein
the low molecular compound has an end-linked crosslinking group and has a structure such that two to seven benzene rings are connected by one or more of the ether bond, methylene oxide bond, ketone bond and sulfonyl bond; and where
the crosslinking polymer has polymerized units, each unit having a structure such that a plurality of benzene rings are linked by one or more of the ether linkage, ketone linkage and sulfonyl linkage, and a crosslinking group at the end of the polymer is bound, which has a higher molecular weight than the low molecular weight compound. 2. The curable resin composition according to claim 1, wherein the low molecular weight compound two with an ether bond has connected benzene rings. 3. The curable resin composition according to claim 1 or 2, wherein the low molecular weight compound three to seven using ether Bond and ketone bond linked benzene rings having. 4. A curable resin composition according to any one of claims 1 to 3, at least one of the bonds between the benzene rings in the low molecular weight compound and / or the bond between the benzene ring at the end and the cross-linking group has meta or ortho position.   5. A curable resin composition according to any one of claims 1 to 4, where the number of benzene rings in the low molecular weight Connection is five to seven and at least one of the Benzene rings has at least one substituent. 6. The curable resin composition according to any one of claims 1 to 5, where the benzene rings are in the units of the crosslinking polymer by means of ether bonding and / or ketone bonding with one another are connected. 7. A curable resin composition according to any one of claims 1 to 6, at least one of the bonds between the benzene rings in the units of the crosslinking polymer and the bonds has meta or ortho position between the units. 8. A curable resin composition according to any one of claims 1 to 7, at least one of the benzene rings in the cross-linking Polymer has at least one substituent. The curable resin composition according to claim 8, wherein the the substituent attached to the benzene ring in the crosslinking polymer is an alkyl group. 10. A curable resin composition according to any one of claims 1 to 9, where the to the low molecular weight compound or to the crosslinking polymer bound crosslinking group a thermally networkable networking group. 11. A curable resin composition according to any one of claims 1 to 10, in which the to the low molecular weight compound or to the crosslinking polymer bound crosslinking group Networking forms a three-dimensional conformation.   12. The curable resin composition according to claim 11, wherein the cross-linking group building up three-dimensional conformation is provided with an ethynyl group. 13. The curable resin composition according to claim 11 or 12, wherein which builds up the three-dimensional conformation through networking crosslinking group only to the low molecular compound is bound. 14. The curable resin composition according to any one of claims 1 to 12, wherein the crosslinking group in the low molecular compound forms a three-dimensional conformation by crosslinking, and wherein the crosslinking group in the crosslinking polymer is provided with a vinyl group, allyl group and at least one of the groups represented by the following formulas 1 to 9:
15. A curable resin composition according to any one of claims 1 to 14, in which the crosslinking polymer has a molecular weight Has a number average of 1,000 to 60,000. 16. Hardened resin material obtainable by hardening the curable resin composition according to any one of claims 1 to 15. 17. Electrical resistance element, which is a hardened resin material according to claim 16.