JP2006045440A - Molding resin composition and its molded article of aromatic heat-resistant polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding modified resin composition giving detachability, mold releasability, and mold stain resistance to the surface of a molded article of a heat-resistant aromatic polymer such as PI, PBI and the like excellent in heat-resistance and to provide the surface-modified molded article of the composition by various molding methods. <P>SOLUTION: The molding resin composition of a heat-resistant aromatic based polymer modifying the surface of a molded article comprises an unmodified resin composition which is a heated mixture of an aromatic PI based or aromatic PBI based heat-resistant prepolymer of 100 pts.wt. and the primary reaction modifying agent of 1-15 pts.wt. giving a dicarboxylic anhydride group to the nitrogen heterocyclic section with the aromatic ring of a repetition structural unit of the prepolymer; and an esterification modifier prepared by reacting the esterification hydroxy group of 10-200 pts. expressed by stoichiometry percentage in a fluorine alcohol of 10<SP>2</SP>-10<SP>5</SP>molecular weight and/or a silicone with the carboxylic acid of 100 pts. expressed in stoichiometry percentage concerning the esterification reaction of all carboxylic acids contained in the unmodified resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to surface modification of an aromatic heat-resistant polymer molded body, and more specifically, an aromatic having an N heterocyclic ring with an aromatic ring as a repeating unit structure such as polyimide and polyzenzoimidazole having excellent heat resistance. As a surface modification of a heat-resistant polymer molded body, a molding resin composition imparting a polymer property such as releasability, mold releasability or mold contamination resistance, and aroma by various molding methods using the resin composition The present invention relates to a group-based heat-resistant polymer molding.

Among commercially available plastics, polyimide (PI) and polybenzimidazole (PBI), which are representative aromatic heat-resistant polymers, have excellent heat resistance, and have little change in properties with respect to temperature. It is a plastic with excellent impact and slidability, excellent dimensional stability, electrical insulation and wear resistance. Taking advantage of these features and characteristics, the electrical and electronic fields such as insulation, sealing materials, and printed circuit boards, aerospace jet engine parts, automotive engine parts, gear boxes, electrical system members, etc. It is used as a mechanical member for gears, bearings, and sliding members that require heat resistance and wear resistance. In recent years, attention has been paid to alignment film materials for liquid crystals, and polyimide alignment films with improved transparency have been developed.

The feature of the molecular skeleton of this heat-resistant polymer is that the main chain skeleton composed of the backbone skeleton of the aromatic ring chain and the trunk skeleton of the N heterocyclic ring that shares the aromatic ring is a heat-resistant polymer having a repeating unit structure. Aromatic polymer. A polymer having a structural component of a heterocyclic skeleton containing a nitrogen atom in this main chain bond species, and a polymer having a remarkably high heat resistance as compared with other resins. That is, PI having an imide bond in the connecting main chain is one of the plastics having the highest heat resistance among aromatic heat-resistant polymers. In addition, the thermoplastic PI system modified and modified in various ways includes condensation type semi-aromatic or wholly aromatic polyether imides. In addition, the thermosetting PI has heat resistance characteristics of an addition reaction type of 300 ° C. and a condensation reaction type of 250 to 360 ° C., for example, expressed by a deflection temperature under load, and has long-term heat resistance. As in the case of a wholly aromatic PI at 250 to 260 ° C. and an addition reaction system PI at 200 ° C., excellent heat resistance characteristics of various aspects are exhibited in the heat resistance characteristics.

In addition, such PI has the highest heat-resistant use temperature of 250 ° C. along with polyether ethyl ketone (PEEK), which is also an aromatic thermoplastic polymer, even at the continuous use limit temperature as heat-resistant characteristics. In addition, the polyimide (PI) which is an amorphous polymer includes a condensation type semi-aromatic type or fully aromatic type thermoplastic polyimide (PI), such as polyether sulfone (PES), polyethylene naphthalate ( PEN), reinforced polyphenylene sulfide (PPS), reinforced liquid crystal polymer (LCP: thermotropic liquid crystal polymer that melts and exhibits crystallinity, and light tropic liquid crystal polymer that exhibits crystallinity in solution), etc. Because it has characteristics, mechanical properties, and electrical properties, it is known as super engineering plastic. A sexual aromatic polymer.

  However, since PI has a high melting point, it is also a fact that it is a polymer having a high processing temperature and low molding processability. Polyamideimide (PAI) has an amide bond introduced into a polyimide main chain, and an amide group and an imide group are alternately copolymerized to link a polymer structure of repeating units with an amide bond (CONH). It is a heat resistant polymer with a wide use temperature of ˜ + 260 ° C. That is, it is a PI-based resin in which any of injection molding, extrusion molding, and compression molding can be performed by modifying the polymer characteristics as a thermal characteristic at the sacrifice of the heat resistance of PI and improving the moldability. Polyetherimide (PEI; amorphous polymer), which is a PI resin, is an amorphous thermoplastic resin that combines an imide bond and an ether bond, and similarly heat-resistant PI resin that enables injection molding. Thus, it is a PI-based heat-resistant polymer excellent in workability obtained by bonding an ether bond chain that exhibits good processability to an imide bond chain that exhibits excellent heat resistance and strength.

Thus, various proposals have been made for improving or modifying various properties of such aromatic heat-resistant polymers. For example, in [Patent Document 1], an unsaturated carboxylic acid having 3 to 10 carbon atoms with respect to 100 parts by weight of the polyimide resin (A) and a backbone polymer resin of an ethylene / α-olefin random copolymer, 0.1 to 0.1 of a liquid acid-modified ethylene / α-olefin random copolymer (B) obtained by graft polymerization of at least one carboxylic acid monomer selected from an acid anhydride and an ester and / or an ethylenically unsaturated monomer having a hydroxyl group For example, a polyimide-based molding resin composition comprising 15 parts by weight and (A) and (B) obtained by kneading the liquid resin (B) while the polyimide resin (A) is melted has been proposed. . Excellent slidability, wear resistance and molding processability. Additive kneading liquid resin (B) as a molding resin composition for applications such as gears, rotating shafts, bearings, etc. is converted into polyimide resin (A) under kneading. Described as a polyimide-based resin composition that exhibits high affinity for, and imparts excellent mold releasability and mold stain resistance to molded articles such as extrusion, injection molding, and compression molding Has been. In order to impart such processability as surface modification, in this [Patent Document 1], in particular, a graft monomer related to a graft-polymerized liquid acid-modified ethylene / α-olefin random copolymer (B). As C1-10 unsaturated carboxylic acid and its anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5 , 6-Dicarboxylic acid, (meth) acrylic acid ester, and (meth) acrylic acid ester having a hydroxyl group in the ester portion include unsaturated alcohols.

[Patent Document 2] proposes, for example, a polyimide tubular molded body used as an intermediate transfer belt of an electrophotographic image apparatus such as a facsimile, a laser beam printer, and a copying machine. A polyimide tubular molded body having a thickness of 60 to 100 μm and having a flex resistance of 5000 times or more containing carbon black, titanium oxide, and boron nitride from the viewpoint of having high thermal conductivity and exhibiting a mold release effect on a polyimide resin. Are listed. In particular, the polyimide resin constituting the molded body contains a predetermined amount of residues derived from pyromellitic dianhydride and a predetermined amount of diamine residues derived from 4,4′-diaminodiphenyl ether. is there.

[Patent Document 3] is similarly dissolved in a polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide, or the like for intermediate transfer or fixing of an electrophotographic image apparatus such as a facsimile, a laser beam printer, and a copying machine. Polyamic acid is endless with a polyimide belt thickness of 30 to 200 μm obtained by imidizing a tubular coating film in the presence of a tertiary amine compound in a cylindrical mold, resin, glass, ceramic or other mold In order to control the resistance value and thermal conductivity of the polyimide resin layer described in the belt, heat conduction of inorganic conductive powder such as carbon black with good dispersibility in polyamic acid solution, boron nitride, alumina, etc. Powder is added.

In [Patent Document 4], for example, an intermediate transfer belt or a fixing belt of an electrophotographic image apparatus such as a printer or a copying machine, which is made of a polyimide resin containing a semiconductive filler and a needle-like filler related to surface smoothness. The final molded temperature after application to a cylindrical mold is 350 to 450 ° C., particularly when heated and fired from non-thermoplastic polyamic acid, and in the case of thermoplastic polyimide, Processing is performed in a temperature range of −10 to −20 ° C. with respect to the glass transition temperature. When this molded body is used as a member of an electrophotographic image apparatus, toner releasability (or toner contamination resistance) and It is described that a fluororesin such as PTFE or PFA whose conductivity is controlled from transferability or the like is applied to the outermost layer and a film is bonded. In particular, from the viewpoint of satisfying the development of thermoplasticity, heat resistance and low water absorption, among others, a tetracarboxylic dianhydride monomer having a structure represented by the following chemical formula (3) is preferable, and this is used as a raw material. Thus, it is described that a polyimide resin having a linear expansion coefficient of 15 ppm or less and a water absorption of 1.5% or less and having little dimensional change by heating or moisture absorption can be obtained.

ここで、式（４）中、ｍ＝１〜３、ｎ＝１〜１２の整数、Ａは４価の有機酸を示す。
すなわち、ジアミントテトラカルボン酸二無水物の縮合反応で得られるポリイミドの前駆体であるポリイアミック酸を基板に塗布後、１８０〜２２０℃で加熱処理脱水閉環反応させて得られるポリイミド系密着被膜である。 [Patent Document 5] proposes a polyimide having a perfluoroalkyl group as a side chain group in a repeating structural unit represented by the following general formula (3) that is particularly excellent in adhesion to an underlying ground such as a glass plate. .

Here, in formula (4), m = 1 to 3, n = 1 to 12 and A represents a tetravalent organic acid.
That is, it is a polyimide-based adhesive coating obtained by applying polyamic acid, which is a polyimide precursor obtained by the condensation reaction of diaminetotetracarboxylic dianhydride, to a substrate, followed by heat treatment dehydration ring-closing reaction at 180 to 220 ° C. .

In [Patent Document 6], a coating obtained by applying a solution containing a polymer represented by the following general formula (5), which is a precursor of polybenzimidazole, to a substrate is usually heated and condensed at 300 to 400 ° C. A cured coating film that has been cyclized and adhered to a polybenzimidazole substrate represented by the following general formula (6) is described.

In [Patent Document 7], the average particle diameter of a thermoplastic wholly aromatic polyimide having a repeating structural unit represented by the following general formula (7) having particularly excellent heat resistance, mechanical properties and sliding properties is 500 μm. A bearing member made of a porous polyimide molded body obtained by fusing particles in a pressure heating mold at 250 to 350 ° C. is described.

JP-A-11-71439 JP 2004-075753 JP 2002-296919 A JP 2003-306553 A JP-A-9-87388 JP 2003-105259 A JP 2000-110838 A

Under such circumstances, polyimide (PI), polybenzimidazole (PBI), etc. are all excellent in heat resistance, mechanical properties, dimensional stability, specific resistance, dielectric constant, and dielectric loss tangent. Aromatic heat-resistant polymer that exhibits excellent electrical insulation properties in the past, including insulation, sealing materials, printed circuit boards, polyimide alignment film materials for liquid crystals, adhesives around semiconductors, protective films, etc. It is widely used in various applications such as electrical and electronic fields, aerospace, various mechanical members requiring heat resistance, belt base materials, and heat-resistant / insulating coating members such as electric wires. The molecular skeleton is characterized by the “anterior leaf trunk linking chain” of an N heterocyclic chain sharing an aromatic ring (hereinafter referred to as “N heterocyclic ring with an aromatic ring” in the present invention), A polymer chain formed by chain bonding as a linking chain with a “back leaf trunk skeleton linking chain” such as a cyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group to which the aromatic group is linked. Is forming.

Among the heat-resistant polymers which are so-called repeating unit structures of heat-resistant aromatic polymers (hereinafter, simply referred to as unit structures in the present invention), the polymer has the highest heat-resistant use temperature and is a polymer having a remarkably high melting point. In addition, since it is a heat-resistant polymer with little change in characteristics with respect to temperature and excellent in wear resistance, impact resistance, slidability, dimensional stability, and electrical insulation, these heat-resistant characteristics are not impaired. Moreover, in order not to impair various resistances such as electrical insulation, chemical resistance, solvent resistance, and various resistances, and to enable extrusion molding, compression molding, melt casting molding, injection molding or casting molding, etc. Various proposals for chemically modifying the molecular structure of the repeating unit structure have been made. However, various proposed modified resins do not sufficiently exhibit the desired polymer characteristics such as peelability, mold releasability, and mold contamination resistance that enable these molding methods.

As described in [Patent Document 2] and [Patent Document 3], when forming a polyimide molded body, the precursor polyamic acid solution is not melted and kneaded without modifying the PI resin or before imidization. Proposals have been made to add a well-dispersible carbon black, titanium oxide powder, boron nitride or the like to exert a releasing effect. Further, as proposed in [Patent Document 4], a specific tetracarboxylic dianhydride monomer having a structure represented by the following formula (3) is used, particularly with a thermoplastic resin, without impairing the heat-resistant polymer. Polyimide resins that are obtained and exhibit dimensional stability as polymer properties during molding are described. In order to make this polyimide resin a so-called thermoplastic resin, the “rear leaf trunk linking chain” represented by a benzene ring (R) is structurally modified in a linear direction of — ((COO—R—COO) — It is a polyimide resin in which “N heterocyclic ring with aromatic ring” which is “anterior leaf trunk skeleton linking chain” is a linking chain.

However, as is clear from [Patent Document 5], the “back lobe trunk backbone linking chain” is a chemically modified polyimide-based aromatic heat-resistant polymer, which represents the unit structure represented by the following general formula ( 4) As is clear from the polyimide resin in which a perfluoroalkyl group of -COO (CH2) m (CF2) nH is added and modified as a side chain group to the benzene monocyclic chain of the "back lobe trunk skeleton connecting chain". In particular, it is described as a polyimide resin that exhibits excellent adhesion to a glass substrate. Therefore, a polyimide resin obtained by side chain addition modification at the “back lobe trunk backbone linking chain” site tends to exhibit adhesion as a polymer property. With such a modified polyimide resin, molding such as mold releasability is likely to occur. It is difficult to express sex.

Therefore, as apparent from [Patent Document 7], as a thermoplastic wholly aromatic polyimide having a unit structure represented by the following general formula (7) having particularly excellent heat resistance, mechanical properties and sliding properties, Taking advantage of the fusibility as a polymer property, the particles having an average particle diameter of 500 μm are fused and molded in a pressure heating mold at 250 to 350 ° C., and such resin particles are fused and formed in three dimensions. By using a polyimide resin with a porous structure, it is possible to use a polyimide resin that exhibits fusing properties as a polymer property, and to create a porous structure with a fusing property, thereby reducing the fusion surface during molding. Thus, as a molded body serving as a bearing member, mold molding can be performed. Further, the polyimide resin thus proposed is modified as a wholly aromatic ether linking chain in which the “back leaf trunk linking chain” represented by the benzene ring (R) is — (R—O—R) —, and The “anterior leaf trunk skeleton linking chain” represented by “N heterocyclic ring with aromatic ring (R ′)” is also modified as a unit structure of an ether linking chain of — (R′—O—R ′) — It is.

From the above, for the purpose of modifying the polymer properties of aromatic heat-resistant polymers such as PI or PBI to express molding processability, various proposed modified aromatic heat-resistant polymers and polymer properties expressed First, the so-called “rear leaf trunk linking chain” is structurally modified as an aromatic ring linking chain via a benzene aromatic ring or various single bond groups in the direction of the linking chain, and modified into a thermoplastic resin as a polymer resin. Thus, while taking advantage of the thermoplasticity and its fusing property, a specific filler is added to impart releasability. Secondly, in order to modify the thermoplastic resin without particularly impairing the heat resistant polymer, the “rear leaf trunk skeleton linking chain” is structurally modified to be specified in the linear direction, and “anterior leaf trunk skeleton linking chain is formed at both ends. "N-heterocyclic chain with an aromatic ring" that is a linking chain is a countermeasure for exhibiting moldability as a polymer characteristic during molding. Thirdly, there are many conventionally proposed countermeasures for denaturation, in which the “back lobe trunk skeleton linkage chain” is also chemically modified, but the “back lobe trunk skeleton linkage chain” The polymer properties that are added and modified as a side chain group at the site and tend to impart adhesiveness as described above, and in the polymer resin that exhibits such adhesiveness, the above-mentioned conventional polymer resins Even if various molding methods are employed, molding tends to be extremely difficult.

In addition, the conventionally proposed modification coping method searches for a previously modified tetracarboxylic dianhydride component and diamine component when synthesizing the desired modified PI and modified PBI with both starting materials used, Moreover, it is intended to achieve the modification and the desired polymer characteristics such as peelability, mold releasability, and mold contamination resistance by combining these, and at least effective and efficient. It can be said that this is not an appropriate modification and modification method.

That is, in the conventional modification countermeasures, the range in which PI or PBI can be modified is basically limited, and the main modification is already achieved by selecting a combination of an amine component and an acid anhydride component prior to synthesis. Therefore, the actual situation is that the modification that exhibits excellent moldability as a polymer characteristic that is sufficiently satisfied has not yet been made.

Therefore, the object of the present invention is to have such excellent heat resistance characteristics, various characteristics exhibited in relation to the heat resistance, and polymer characteristics of various resistances without impairing polyimide (PI) or polybenzimidazole (PBI). ) And other aromatic heat-resistant polymers, such as conventional starting materials such as tetracarboxylic dianhydride component and diamine component are modified in advance without PI, PBI and other precursors directly. Alternatively, PBI or the like is chemically post-reacted as an object to be modified to obtain a modified PI and a modified PBI resin, and a reactive modification that exhibits molding processability that is a modification desired by the present invention as a polymer characteristic. It is providing the resin composition for shaping | molding containing an agent.

Another object of the present invention is to use a molding resin composition that imparts peelability, mold releasability, and mold contamination resistance as polymer characteristics of an aromatic heat-resistant polymer molded article. It is an object to provide various aromatic heat-resistant polymer molded articles formed by molding, compression molding, melt casting or injection molding.

Accordingly, the present inventors have intensively studied to solve the above-mentioned problems, and for the commercially available thermoplastic PI that is the base polymer before modification, the “anterior ring backbone linking chain” “N with an aromatic ring” is used. Paying attention to the `` heterocyclic chain '' site, castability obtained by adding maleic anhydride and perfluorooctylalkyl alcohol, a fluoroalcohol that seems to react with this acid, under heat melting and kneading sufficiently After the heated resin material was allowed to flow down onto a stainless steel plate, an aluminum ceramic plate, and glass kept at 130 ° C. and allowed to cool slowly, it was found that this flow-down deposit was easily peeled off. The invention has been completed.

According to the present invention, the repeating unit structure is chemically modified by an after-reaction reaction with an aromatic heat-resistant polymer having a nitrogen heterocycle chain with an aromatic ring as a main chain, and an unmodified prepolymer molding before modification Molding characterized by containing an unmodified aromatic heat-resistant polymer and a reactive modifier for imparting polymer properties such as excellent releasability, mold releasability and mold contamination resistance to the body A resin composition is provided.

化学式（１ａ）において、Ｒは２価の有機基であり、ｎは１以上の整数である。

化学式（１ｂ）において、ｎは１以上の整数である。

化学式（２）において、ｎは１以上の整数である。 That is, the “first molding resin composition” (D-1) provided by the present invention is an unmodified prepolymer (A-1) of an aromatic imide-based or aromatic benzimidazole-based aromatic heat-resistant polymer. ) The nitrogenous heterocyclic chain with an aromatic ring of the prepolymer (A-1) component represented by the following general formula (1a), (1b) or the following general formula (2) is a reactive modifier contained in the component: A first reactive modifying (B-1) agent that chemically acts on a site to give a dicarboxylic anhydride group,

In the chemical formula (1a), R is a divalent organic group, and n is an integer of 1 or more.

In the chemical formula (1b), n is an integer of 1 or more.

In the chemical formula (2), n is an integer of 1 or more.

Unmodified by mixing 100 parts by weight of the prepolymer (A-1) component with 1 to 15 parts by weight of the primary reactive modifying (B-1) agent under melting or semi-melting conditions. It is the 1st characteristic to contain as a resin composition (C-1).
Moreover, with respect to 100 parts of carboxylic acid content represented by the stoichiometric percentage concerning the esterification reaction of all the carboxylic acids contained in this unmodified resin composition (C-1), it is further molecular weight 10 < ² > -10 < ⁵ >. In the range of 10 to 200 parts as the esterification group represented by the stoichiometric percentage related to the esterification modification contained in the fluorinated alcohol and / or silicone in the range of the first reactive modification (B -1) The second feature is that it contains an esterification modifier that reacts with a site modified with the agent.
Further, the “second molding resin composition” (D-1) provided by the present invention includes 100 parts by weight of the first molding resin composition (D-1) described above, and (D-1 ) 10 to 100 parts by weight of a compound having a polymerizable double bond and polymerization reactivity in the unmodified resin composition (C-1) contained therein, and a thermal radical generator (or thermal polymerization initiator) It is a resin composition for shaping | molding characterized by containing 0.1-20 weight part.

Furthermore, according to the present invention, by using the first or second molding resin composition (D-1) described above, extrusion molding, compression molding, melt casting molding or injection molding is performed, and the polymer characteristics are excellent. The present invention provides an aromatic heat-resistant polymer molded product that exhibits excellent releasability, mold releasability or mold contamination resistance.
Further, according to the present invention, the first or second molding resin composition (D-1) described above is added to 100 parts by weight of a prepolymer before modification of an aromatic imide-based or aromatic benzimidazole-based heat-resistant aromatic polymer. ) Using a “third resin composition for molding” (D-1), which is a mixed resin composition (E-1) obtained by mixing 50 to 150 parts by weight of Disclosed is an aromatic heat-resistant polymer molded article which is molded or injection-molded and exhibits peelability, mold releasability or mold contamination resistance as polymer characteristics.

Moreover, according to this invention, 10 to 200 weight of the fluorine-type alcohol and / or silicone which are in the range of molecular weight 10 < ² > -10 < ⁵ > to 100 weight part of the above-mentioned unmodified resin composition (C-1) component. And 100 to 100 parts by weight of a compound that is polymerizable and reactive with the polymerizable double bond in the unmodified resin composition (C-1) component are mixed at a temperature between room temperature and room temperature. Using the “fourth molding resin composition” (D-1), which is a mixed resin composition (E-2), extrusion molding, compression molding, cast molding, or injection molding, and release properties as polymer properties An aromatic heat-resistant polymer molded product characterized by exhibiting mold releasability or mold contamination resistance is provided.

Furthermore, according to the present invention, polybenzimidazole and / or polyimide or polyimide precursor polyamic acid is added to 100 parts by weight of the mixed resin composition (E-2) described above, and further at a temperature from room temperature to room temperature. Extrusion molding, compression molding, cast molding using “fifth molding resin composition” (D-1) which is a mixed resin composition (E-3) obtained by mixing 50 to 150 parts by weight of Alternatively, the present invention provides an aromatic heat-resistant polymer molded article which is injection-molded and exhibits releasability, mold releasability or mold contamination resistance as polymer characteristics.

Release property, mold releasability or mold contamination resistance as a polymer property modification expressed in an aromatic heat-resistant polymer molded article obtained by using the molding resin composition according to the present invention (note that the present invention (This mold contamination resistance includes, for example, an evaluation value called contamination resistance, which is referred to as toner resistance in a thermal transfer roll member used in an electrophotographic image forming apparatus or the like.) Is composed of a repeating unit structure of these polymer resins proposed by the present invention with respect to an aromatic heat-resistant polymer molded body such as polyimide (PI) or polybenzimidazole (PBI) as the main component resin. The prepolymer before modification is obtained by chemically modifying the structure of the “nitrogen heterocyclic chain with aromatic ring”, which is a “chain backbone linking chain”, by a follow-up reaction with the modifying agent composition of the present invention. For example, injection molding, extrusion molding, compression molding or melt cast molding, which are conventionally known molding methods, can be performed with resin, and is effectively expressed on the surface of the molded body at the time of molding. It can be said that this is a further polymer property.

In addition, as already explained, in the modified products listed in [Patent Document 5], [Patent Document 6] and [Patent Document 7] as the second (2) modification treatment method proposed conventionally, The denaturation site is a polymer characteristic that is expressed by chemical modification of the “back lobe trunk skeleton linkage chain” and addition modification as a side chain group at the “back lobe trunk skeleton linkage chain” site, It is an aromatic heat-resistant polymer resin that imparts adhesion. On the other hand, in the modified formulation according to the present invention, the "anterior leaf trunk skeleton linking chain" site with respect to this "posterior leaf trunk skeleton linking chain" site, as in the conventional method modified formulation shown in the above [Patent Document], In the resin composition for molding modified according to the present invention, the polymer property imparted to the molded body as its effect improves the adhesion as well as the desired side chain group is modified by addition. Further, the releasability, mold releasability or mold contamination resistance that enables molding methods such as injection molding, extrusion molding, compression molding or melt casting is further improved as a polymer property. Thus, it can be provided as a remarkably different modification treatment method, and this greatly expands the treatment region of “desired modification modification” with respect to “denaturation”.

Hereinafter, the best embodiment of the molding resin composition containing a reactive modifier for imparting molding processability as a polymer characteristic to the PI, PBI heat-resistant aromatic polymer resin molding according to the present invention will be further described. To do.

As already described above, as a further polymer characteristic of the PI and PBI aromatic heat-resistant polymer moldings according to the present invention, molding that improves the properties such as releasability, mold releasability or mold contamination resistance. In the resin composition for a resin, the repeating unit structure of this polymer resin is represented by a “nitrogen heterocyclic chain with an aromatic ring” as a linking structure of “anterior leaf trunk skeleton linkage chain” and “back lobe trunk skeleton linkage chain”. A reactive denaturing agent is included in a certain “frontal stem backbone linking chain” site, which undergoes a post-reaction to chemically modify the structure, thereby modifying and expressing desired polymer properties in the molded article. It is.

Therefore, the “first molding resin composition” (D-1) provided by the present invention as described above has an unmodified PI or PBI prepolymer (A-1) component, an aromatic imide type or an aromatic type. It is a benzimidazole-based aromatic heat-resistant polymer. In this molding resin composition, “nitrogen heterocyclic chain with aromatic ring” of the unmodified prepolymer (A-1) component represented by the following general formula (1a), (1b) or the following general formula (2) A primary reactive denaturing (B-1) agent that chemically acts to give a dicarboxylic anhydride group is contained in a certain “anterior lobe trunk skeleton chain” site.

That is, the “first molding resin composition” (D-1) according to the present invention has this primary reactivity with respect to 100 parts by weight of the unmodified PI or PBI prepolymer (A-1) component. From the viewpoint that the modification (B-1) agent is 1 to 15 parts by weight, and further, the modification that makes the desired polymer releasability sufficiently exhibited without damaging the polymer properties of the base polymer is preferable. The unmodified resin composition (C-1) obtained by mixing 5 to 12 parts by weight under melting or semi-melting can be contained. In the present invention, the total carboxylic acid contained in the unmodified resin composition (C-1) is chemically stabilized with respect to the carboxylic acid group that has undergone addition reaction as the “modified bond”. From the viewpoint, an esterification modifier that undergoes an esterification reaction can be preferably contained. As the esterification modifier, an esterification group component represented by a stoichiometric percentage related to esterification modification contained in a fluorine-based alcohol and / or silicone having a molecular weight of 102 to 105 is preferably stoichiometric. Modification in which the polymer release property intended by the present invention is sufficiently exerted in the range of 10 to 200 parts with respect to 100 parts of the carboxylic acid content expressed in terms of the target percentage, and without impairing the polymer properties of the base polymer. From the viewpoint of forming the resin composition, it is preferably a molding resin composition contained as an esterification modifier to be reacted in the range of 15 to 150 parts.

When the molding resin composition according to the present invention is molded as described above, the modified polymer resin desired by the present invention is obtained in a follow-up reaction when it is treated at a temperature of 100 to 150 ° C. Therefore, as already described above in connection with (n) shown in the above general formula (1a), (1b) or (2), in the present invention, the “anterior stem trunk skeleton linkage of PI and PBI resin before modification” For each "modified bond" of the primary reactive modifier chemically bonded to the "chain" site, the "anterior stem backbone linking chain" in the repeating unit structure of these polymer resins The number (n) of “N heterocyclic rings with aromatic rings”. In the present invention, n is preferably in the integer range of 5 to 30. If n is less than or equal to the lower limit, the modification density is too high, which is undesirable from the tendency to impair the polymer properties of the base polymer. If n exceeds the upper limit, the releasability of the polymer, which is the purpose of modification, may be reduced. It cannot be expressed sufficiently, which is not preferable.

<Unmodified PI or PBI prepolymer (A-1) component>
Therefore, as already described above, the unmodified PI and unmodified PBI aromatic heat-resistant polymer resin (or unmodified prepolymer) used in the present invention is defined as a “frontal stem backbone linking chain” in the present invention. If the “nitrogen heterocyclic chain with aromatic ring” portion is a PI and PBI aromatic heat-resistant polymer resin that is not chemically modified at all, it is suitably used as a prepolymer resin before modification. Therefore, as an unmodified aromatic heat-resistant polymer resin suitably and suitably used in the present invention, for example, a thermoplastic polyimide resin having a unit structure represented by the following general formula (8) described in JP-A-7-145321 is used. Can be mentioned.

As a raw material of the above chemical formula (8), butanetetracarboxylic dianhydride, cyclopentanebutanetetracarboxylic dianhydride, pyromellitic anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4.5.8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2- (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether Anhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1, 1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexachloropropane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 ′-(p-phenylenedioxy) diphthalic acid dianhydride Thing, 4,4'- m-phenylenedioxy) diphthalic dianhydride, 4,4'-diphenyl sulfide dioxybis (4-phthalic acid) dianhydride, 4,4'-diphenylsulfone dioxybis (4-phthalic acid) dianhydride , Methylenebis- (4-phenyleneoxy-4-phthalic acid) dianhydride, ethylidenebis-4-phenyleneoxy-4-phthalic acid) dianhydride, isopropylidenebis- (4-phenyleneoxy-4-phthalic acid) ) Dianhydride, hexafluoroisopropylidenebis- (4-phenyleneoxy-4-phthalic acid) dianhydride, and the like. On the other hand, examples of the aromatic diamine include bis [4- (3-aminophenoxy). Phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ketone 4,4′-bis (3-aminophenoxy) phenyl] biphenyl, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenylmethane, 1,1-di (p -Aminophenyl) ethane, 2,2-di (p-aminophenyl) -1,1,1,3,3,3-hexafluoropropane and the like, and these aromatic tetracarboxylic dianhydrides and these Each of the above aromatic diamines alone or in combination of two or more thereof is used as an unmodified aromatic heat-resistant polymer in the present invention. It can be suitably suitably used as.

Moreover, the thermoplastic polyimide resin which has a unit structure shown to following General formula (9) described in Unexamined-Japanese-Patent No. 10-298441 is mentioned. In the formula (9), R1 to R4 are alkyl groups having 1 to 5 carbon atoms, X is a hydrocarbon group having 1 to 10 carbon atoms, Y is a monocyclic aromatic group or a condensed polycyclic aromatic group. To express.

In addition, although the structural formula as its detailed unit structure is unknown, a thermoplastic polyimide resin synthesized from the following tetracarboxylic dianhydride component and diamine component is used as an unmodified aromatic heat-resistant polymer. It is done. Examples of the tetracarboxylic dianhydride component include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5 dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, dicyclo [2,2,2] -oct-7-ene-2,3,5,5 , 6-tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4 4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′- Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, Bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 1,3,3a, 4,5,9b-hexahydro- 2,5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5 9b-Hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5 9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, etc. For example, p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3 , 3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-diaminobenzanilide, 3,5-diamino-3′-trifluoro Oromethylbenzanilide, 3,5-diamino-4′-trifluoromethylbenzanilide, 3,4′-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino- 5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4 -(4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4 Aminophenoxy) benzene, 4,4-bis (4-aminophenoxy) -biphenyl, 1,3′-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′ -(P-phenyleneisopropylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane 4,4′-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 1,1-metaxylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine , Octamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4- Aminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylene diamine, hexahydro-4,7-methanoin danylene dimethyl methylene diamine, etc., each of these tetracarboxylic dianhydrides and these diamines alone, or A thermoplastic polyimide resin obtained by a commonly known method using two or more kinds can be suitably used as an unmodified aromatic heat-resistant polymer in the present invention.

Moreover, although the structural formula as the detailed unit structure is unknown, a non-thermoplastic polyimide resin is also suitably used as an unmodified aromatic heat-resistant polymer in the present invention. As the non-thermoplastic polyimide resin, a composition synthesized from a specific diamine and a specific tetracarboxylic dianhydride is used. As the specific diamine, o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminophenyl ether, 3,4-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, and the like. On the other hand, as a specific tetracarboxylic dianhydride, Acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, and the like. Non-thermoplastic polyimides that are appropriately synthesized using at least one kind can be used. Further, as commercially available non-thermoplastic polyimide resins, for example, Upilex S, Upilex SGA, Upilex SN, manufactured by Ube Industries, Ltd., Kapton H, Kapton V, Kapton EN, Kanetake manufactured by Toray DuPont Co., Ltd. Chemical A Co., Ltd. Apical AH, Apical NPI, Apical HP, etc. are mentioned.

<Primary reactive modifying agent (B-1) for imparting a carboxylic anhydride group>
Therefore, in the present invention, as the carboxylic acid anhydride which is the primary reactive modifying (B-1) agent, for example, as a compound having one acid anhydride group in the molecule, for example, acrylic acid, Methacrylic acid, tetrahydrophthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-Na sulfoisophthalic acid Unsaturated carboxylic acid anhydrides such as, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid; Derivatives include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, hexahydrohydrofuran Le acid, methylcyclohexyl anhydride, methylcyclohexyl tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid anhydride.

<Esterification modifier: fluorinated alcohol>
In the present invention, an esterification modifier (or an esterification modifier (or a first reactive modification agent (B-1)) contained in the unmodified resin composition is esterified with respect to the total carboxylic acid content (or The fluorinated alcohol component as the secondary reactive modifier) is preferably a fluorinated alcohol having a molecular weight in the range of 10 ² to 10 ⁵ , which is 100 parts of carboxylic acid expressed in stoichiometric percentage. On the other hand, it can be made to react suitably suitably in the range of 10-100 parts as a hydroxyl content represented by the stoichiometric percentage concerning esterification reaction. When the alcohol component of the esterification modifier deviates from the above blending ratio, the polymer releasability expressed as the object of the present invention is preferably in the range of 20 to 80 parts by weight from the viewpoint of thermally stabilizing even under heating. And can be used more suitably. Therefore, as specific examples of the fluorinated alcohol as the esterification modifier, for example: 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 6 -(Perfluoroethyl) hexanol, 2-perfluorobutylethanol, 3-perfluorobutyl-2-propen-1-ol, 6- (perfluorobutyl) hexanol, 2- (perfluorohexyl) ethanol, 3- ( Perfluorohexyl) propanol, 6- (perfluorooctyl) hexanol, 6- (perfluoro-1-methylethyl) hexanol, 2- (perfluoro-3-methylbutyl) ethanol, 1H, 1H, 5H-octafluoropentanol 2,2-bis (trifluoromethyl) propano A monool compound such as 3- (2-perfluorohexyl) ethoxy-1,2-dihydroxypropane, 3- (2-perfluoro-n-octyl) ethoxy-1,2-dihydroxypropane, 3- ( 1H, 1H-pentatecafro-1-octyl) oxy-1,2-dihydroxypropane, 3- (1H, 1H-perfluoro-1-lauryl) oxy-1,2-dihydroxypropane, 3- (2,2,2 -Trifluoroethyl) oxy-1,2-dihydroxypropane, 3- (hexafluoropropyl) oxy-1,2-dihydroxypropane, 3- (2-perfluoro-n-butyl) ethoxy-1,2-dihydroxypropane , 3- (4,4,4-trifluoro-3,3, -dimethoxybutyl) oxy-1,2-dihydroxypropane 3- (n-perfluoro-n-octyl) methyloxy-1,2-dihydroxypropane, 3- (perfluoro-n-octyl) -1,2-dihydroxypropane, 3- (perfluoro-n-butyl) -1,2-dihydroxypropane, 3- (perfluoro-n-hexyl) -1,2-dihydroxypropane, 1,4-bis (1,2-dihydroxypropyl) -perfluoro-n-ptane, 2,2 3,3,4,4,5,5-octafluoro-1,6-hexanediol, 3,3,4,4,5,5,6,6-octafluorooctane-1,8-diol, 2,3,3-tetrafluoro-1,4-butanediol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4 , 5,5-octafluoro -1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7-1,8-octanediol and the like.

<Esterification modifier; content of esterification group contained in silicone>
In the present invention, as a specific example of the silicone-based esterification modifier, as a reactive organic radical introduced from a silane compound containing a hydroxyl group, for example, a vinyl group, an epoxy group, a (meth) acryl group, an amino group, etc. Can be mentioned. That is, examples of the silicone compound (or silane compound) include silane compounds such as alkoxysilane, acyloxysilane, and silane coupling agents. For example, as alkoxysilane, Si (OMe) 4, MeSi (OMe) 3, Me2Si (OMe) 2, Me3Si (OMe), C2H5Si (OMe) 3, n-C3H7Si (OMe) 3, n-C6H13Si (OMe) 3, n-C10H21Si (OMe) 3, CH2 = CHSi (OMe) 3, C6H5Si (OMe) 3, (C6H5) 2Si (OMe) 2; in particular, NH2CH2CH2NHCH2CH2CH2MeSi (OMe) ) 3, NH2CH2CH2NHCH2CH2CH2SiMe (OMe) 2, HSCH2CH2CH2Si (OMe) 3, C6H5NHCH2CH2CH2Si (OMe) 3, CH2 = (Me) CCOOCH2CH2CH2Si (OMe) 3; 2, Me3SiOEt, etc. Examples of the acyloxysilane include MeSi (OCOMe) 3, C2H5Si (OMe) 3, CH2 = CHSi (OCOMe) 3, and silicon-containing vinyl such as vinyltrimethoxysilane and vinyltriethoxysilane. System monomers can also be used as appropriate. Here, Me is a methyl group and Et is an ethyl group.

Then, the following 2nd-5th molding resin composition can be provided in this invention by making use of the characteristics of the 1st molding resin composition by this invention mentioned above.

<Second molding resin composition>
The “second molding resin composition” provided by the present invention comprises 100 parts by weight of the first molding resin composition (D-1) described above, and the unmodified content contained in the (D-1). Contains 10 to 100 parts by weight of a compound having a polymerizable double bond and polymerization reactivity in the resin composition (C-1), and 0.1 to 20 parts by weight of a thermal radical generator (or thermal polymerization initiator). It is the resin composition for shaping | molding characterized by doing.

Examples of the compound having a polymerizable double bond and polymerization reactivity in (C-1) include, for example, 2-chloroacetic acid, 3-chloropropionic acid, 3-chloro-2-hydroxypropyl methacrylate, β-methacryloylloy. Ruoxyethyl hydrogen phthalate; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl laurate, vinyl stearate, vinyl benzoate, pt-butylbenzoic acid Vinyl esters such as vinyl and vinyl salicylate; vinyl halide compounds such as vinylidene chloride, vinyl chlorohexanecarboxylate, 2-chloroethyl (meth) acrylate and 2-chloroethyl methacrylate; aminoethyl (meth) acrylate, (Meth) propylaminoethyl acrylate, (meth) a Alkyl ester derivatives of (meth) acrylic acid such as dimethylaminoethyl silylate, aminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate; N-vinyldiethylamine, Vinylamine derivatives such as N-acetylvinylamine; allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine; N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, acrylamide, N-methylacrylamide Acrylamide derivatives such as: aminostyrenes such as p-aminostyrene; monomers having an ethylenically unsaturated bond such as 6-aminohexyl succinimide and 2-aminoethyl succinimide; Lenglycol di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1 , 1,1-trishydroxymethylethanediacrylate, 1,1,1-trishydroxymethylpropanetriacrylate and other compounds having two or more (meth) acryloyl groups in the molecule; methyl (meth) acrylate, (meta ) Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) Ak (Meth) acrylic acid alkyl esters such as 2-ethylhexyl formate, octyl (meth) acrylate, lauryl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate; (Meth) acrylic acid phenyl; (meth) acrylic acid methoxyethyl, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid butoxyethyl, (meth) acrylic acid ethoxypropyl, etc. (meth) acrylic acid alkoxyalkyl ester; glycidyl Epoxy group-containing (meth) acrylates such as (meth) acrylates; acrylates of alicyclic alcohols such as cyclohexyl (meth) acrylate; di (meth) acrylates of ethylene glycol, di (meth) of diethyl glycol ) Acrylic acid ester, poly Di (meth) acrylic acid esters of (poly) alkylene glycols such as di (meth) acrylic acid esters of ethylene glycol, di (meth) acrylic acid esters of dipropylene glycol, and di (meth) acrylic acid esters of tripropylene glycol Etc. Examples of amide group-containing vinyl monomers include: methacrylamide, N-methylol methacrylamide, N-methoxyethyl methacrylamide and the like, acrylamide derivatives such as acrylamide and N-methylacrylamide, p-amino Examples include aminostyrenes such as styrene, (meth) acrylamides such as N-methylol (meth) acrylamide and diacetone acrylamide, 6-aminohexyl succinimide, and 2-aminoethyl succinimide. Further, for example, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinyl Vinylamine derivatives such as amines, allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, and acrylamides such as acrylamide and N-methylacrylamide Derivatives, aminostyrenes such as N-aminostyrene, monomers having an ethylenically unsaturated bond such as 6-aminohexyl succinimide, 2-aminoethyl succinimide; styrene, Alkyl styrenes such as styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, chloromethyl Examples thereof include halogenated styrene such as styrene; nitrostyrene, acetyl styrene, methoxy styrene, α-methyl styrene, vinyl toluene, and the like. The amount of these compounds is more preferably 20 to 60 parts by weight from the viewpoint of not preventing the reaction of the carboxylic acid group as the modified bond contained in (D-1).

<Third molding resin composition>
Further, according to the present invention, the first or second molding resin composition (D-1) described above is added to 100 parts by weight of a prepolymer before modification of an aromatic imide-based or aromatic benzimidazole-based heat-resistant aromatic polymer. It is possible to provide a “third molding resin composition (D-1)”, which is a mixed resin composition (E-1) obtained by mixing 50 to 150 parts by weight of .

<Fourth resin composition for molding>
Moreover, according to this invention, 10 to 200 weight of the fluorine-type alcohol and / or silicone which are in the range of molecular weight 10 < ² > -10 < ⁵ > to 100 weight part of the above-mentioned unmodified resin composition (C-1) component. And 100 to 100 parts by weight of a compound that is polymerizable and reactive with the polymerizable double bond in the unmodified resin composition (C-1) component are mixed at a temperature between room temperature and room temperature. It is possible to provide a “fourth molding resin composition (D-1)” which is a mixed resin composition (E-2).

<Fifth molding resin composition>
Furthermore, according to the present invention, polybenzimidazole and / or polyimide or polyimide precursor polyamic acid is added to 100 parts by weight of the mixed resin composition (E-2) described above, and further at a temperature from room temperature to room temperature. It is possible to provide a “fifth molding resin composition (D-1)”, which is a mixed resin composition (E-3) obtained by mixing 50 to 150 parts by weight. Therefore, in this fifth molding resin composition, the unmodified PI, unmodified PBI and unmodified aromatic imide polymer precursor polyamic acid (hereinafter abbreviated as PIPA) PIPA prepolymer species, Although there are some differences, from the viewpoint of improving the polymer characteristics more preferably and effectively, a more preferable resin composition for molding can be suitably used in the range of 60 to 120 parts by weight.

<Aromatic heat-resistant polymer moldings by various molding methods>
From the above, when the first to fifth molding resin compositions according to the present invention described above are used, these molding resin compositions are usually hot melted or semi-melted at 250 to 350 ° C. during molding. By subjecting to a preheating treatment, extrusion molding, injection molding, blow molding or stretch molding can be appropriately performed as a desired modified resin as long as thermoplasticity is not impaired by modification according to the present invention. In addition, cast molding, injection molding, or compression molding can be appropriately performed as long as the thermosetting property is not impaired by the modification according to the present invention. Under this preheating treatment, the reactive modifier composition according to the present invention chemically reacts with the “N-heterocyclic chain with an aromatic ring” site, which is the “frontal stem backbone linking chain” of the prepolymer. Chemical structural modification is performed without impairing this “N heterocyclic ring with aromatic ring”. By this modification, the above-described extrusion molding is imparted to the molded product of the unmodified PI, unmodified PBI, and unmodified PIPA prepolymer resin by providing polymer characteristics such as releasability, mold releasability or mold stain resistance. , Compression molding, melt casting, injection molding, blow molding or stretch molding. This modification makes use of the polymer characteristics at the time of molding, and can be used for various applications in various shapes that can be exhibited without damaging the heat resistance, electrical insulation, chemical resistance, dimensional stability, etc. of this polymer resin. A heat-resistant molded article can be provided.

In the present invention, various conventionally known additives can be added in advance to the molding resin composition according to the present invention as long as the desired polymer properties are not impaired by modification before molding. . For example, curing accelerators, low shrinkage agents, thickeners, internal mold release agents, dispersants, plasticizers, lubricants, film forming aids, release agents, antifoaming agents, flameproofing agents, flame retardants, electrification Add inhibitors, conductivity enhancers, ultraviolet absorbers, ultraviolet sensitizers, fluorescent brighteners, antibacterial / antifungal agents, fibrous organic and inorganic fillers, dyes, pigments, etc. as necessary. Can do. Further, in the present invention, these additives may be blended individually, or may be suitably blended in combination of two or more, and the addition amount depends on the additive species, but usually, 0.01-100 parts by weight, preferably 50 parts by weight or less, more preferably 20 parts by weight or less, can be suitably added per 100 parts by weight of the prepolymer resin before modification.

Among the above-mentioned additives, for example, various fine powders and scales related to improvement / reinforcement of the tensile strength of the sheet material, prevention of bending, improvement of characteristics such as AB (anti-blocking) property of the sheet surface, etc. A fibrous (or whisker-like) inorganic / organic filler can be added as appropriate. Examples of such fillers include calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, magnesium hydroxide, alumina powder, bengara, silica, synthetic smectite, synthetic zeolite, magnesium titanate, and synthetic basic lithium carbonate / aluminum salt. Synthetic basic lithium carbonate / magnesium salt, synthetic calcium silicate, synthetic magnesium silicate, synthetic mica, orastite, nepheline site, talc, diatomaceous earth, miker, kaolin, glass powder, various organic polymer fine particles, etc. . These may be used alone or in combination of two or more. Examples of the fiber reinforcing material include glass fiber, carbon fiber, organic fiber, potash titanate fiber, and the like. These fibers have a length of 0.1 to 20 mm, preferably 1 to 10 mm. . In addition, these fine powders and fibrous fillers may be surface-treated with, for example, a silane-based or titanate-based coupling agent in advance from the viewpoint of compatibility with the resin of the present invention and dispersibility. A suitable dispersing agent can be used in combination as appropriate. In particular, as the colorant, bengara, black ferrite, titanium oxide, and the like, which are inorganic oxide pigments, are mentioned because they are heat resistant.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

To the unmodified prepolymers of PI (polyimide) and PBI (polybenzimidazole), which are aromatic heat-resistant polymers, to the “N-heterocyclic chain with aromatic ring” site, which is the “anterior leaf trunk linking chain”, By using a heat-resistant resin composition for molding which forms a molded article having excellent releasability, which is an object of the present invention, containing a modifying agent that chemically modifies these unmodified prepolymers by a follow-up reaction. The formation of a heat-resistant polymer molded article having excellent mold release properties will be described.

(Example 1) and (Comparative Example 1)
A 10% dimethylacetamide solution of PBI [Clariant Japan Co., Ltd., PBIMRSolution], which is a prepolymer (A-1) component, is added to a 1-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube. Next, maleic anhydride, which is the first reactive modifying (B-1) agent, is added in a variable amount within a range of 1 to 10 parts by weight per 100 parts by weight of PBI resin solid content, and 90 ° C. The mixture was mixed under semi-melting for 3 hours to prepare a primary modified resin composition (C-1) solution of unmodified PBI. Subsequently, in each of these primary modified resin compositions (C-1), polydimethylsilyl group-containing alcohols as esterification modifiers (or secondary reactive modifiers) in the blending amounts shown in Table 1 are used. FM-0421 (manufactured by Chisso Co., Ltd.) and / or CHENINOX-FA (manufactured by Nippon Mectron Co., Ltd.) of a fluorinated alkyl group-containing alcohol is added in a predetermined amount to form a heat-resistant resin composition for molding according to the present invention in the form of a solution. A product was prepared.
Next, a stainless steel cylindrical mold having a radius of 50 mm, a plate width of 50 mm and a wall thickness of 1 mm is dipped into the resin solution, and the resin solution is applied to the outside and inside of the cylindrical tube, After rotating at a high speed in the axial direction of 1000 rpm to form a centrifugal coating film, the surface state (surface smoothness) immediately after film formation was evaluated by maintaining it in a rotating state at 120 ° C. for 1 hour and drying and solidifying it. Next, this mold was subsequently subjected to a curing treatment (baking and compacting) at 350 ° C. for 3 hours to form an endless PBI polymer sheet molded body having a sheet thickness of about 10 μm on the outside and inside of the cylindrical tubular mold. . Subsequently, in order to evaluate the surface smoothness and peelability of the endless sheet molded article by the method described below and clarify the patentability of the present invention, the results including comparative examples are shown in Table 1.

<Smoothness of molded product surface>
By visual observation,
(1) ○ mark; the surface is smooth.
(2) Δ mark: Spotted pattern is seen.
(3) x mark; spotted or striped patterns with different thicknesses are seen on the surface.
In the present invention, the state (2) or (3) on the surface of the molded body is a modified body not evaluated as a modified molded body targeted by the present invention.
<Removability of molded product>
After attaching a commercially available cellophane tape to the surface of the molded body and exposing it to 23 ° C. × 65 HR% × 15 minutes and 23 ° C. × 65 HR% × 24 hours, “after 15 minutes of attachment” and “attachment 24”, respectively. After 90 hours, 90 ° peel strength (N / cm) was measured to evaluate the peelability of the molded body. In this simple peelability evaluation method, it is important that the peel strength (N / cm) is a value that does not exceed at least 2.9 (N / cm).

(Example 2) and (Comparative Example 2)
In Example 1, with the prepolymer (A-1) component as PI, a polyamic acid which is a precursor of PI [Ube Industries, U-Varnish] in a 20% N-methyl-2-pyrrolidone solution In the same manner as in Example 1, except that the prepolymer (A-1) component, the first reactive modifying (B-1) agent, and the esterification modifying agent are mixed in the form of a solution. A heat-resistant resin composition for molding according to the present invention was prepared, and a molded body was prepared in the same manner. The evaluation results including comparative examples are shown in Table 1.

(Example 3)
Experiment No. 1 of Example 1 8 and 100 parts by weight of the PBI molding resin composition according to the present invention, 5 parts by weight of polymerizable double bond-containing polydimethylsiloxane compound FM-0721 (manufactured by Chisso Corp.), A molding resin composition solution was prepared by adding 5 parts by weight of a fluorinated alkyl compound containing a heavy bond and 0.1 parts by weight of perbenzoic acid. Subsequently, the surface state (surface smoothness) of the PBI application body of the coating board which dried and solidified the PBI coating board apply | coated on the glass plate at 120 degreeC x 1 hour was evaluated. Subsequently, this coated plate was subsequently subjected to a curing treatment (baked and hardened) at 350 ° C. for 3 hours to form a PBI polymer sheet-like molded body having a film thickness of about 15 μm on the glass plate, and then the same as in Example 1. As a result of measuring 90 ° peel strength (N / cm) of “after 15 minutes of pasting” and “after 24 hours of pasting”, it was 0.9 N / cm and 1.0 N / cm, respectively. A PBI molded article excellent in peelability was obtained. Moreover, a PBI molded body having a smooth molded body surface and excellent resistance to mold contamination could be prepared.

(Comparative Example 3)
In Example 3, the experiment No. 1 in Example 1 was performed. In place of the resin composition for molding prepared in step 8 in the same manner as in Example 3, except that 100 parts by weight of PBI resin and 1 part by weight of maleic anhydride were used, polydimethyl having a polymerizable double bond was used. A siloxane compound, a fluorinated alkyl compound containing a polymerizable double bond, and perbenzoic acid were added to form a PBI polymer sheet-like molded body on a glass plate, and “after 15 minutes pasting” ”And“ After 24 hours of pasting ”, the 90 ° peel strength (N / cm) was measured and found to be 1.7 N / cm and 3.5 N / cm, respectively. No body was obtained.

“N-heterocyclic chain with an aromatic ring”, which is an “anterior stem backbone linking chain”, is a remarkably simple follow-up reaction to commercially available unmodified prepolymers such as PI, PBI and PI precursor polyamic acid. "Aromatic heat-resistant polymer molding such as PI, PBI, etc., in which a chemically acting dicarboxylic acid anhydride is mixed, and then an esterification modifier such as fluorine alcohol is added to the carboxylic acid content" A molding resin composition for modifying the polymer characteristics of a body can be provided.
Using such a molding resin composition, a heat-resistant sheet-like molded body such as PI and PBI having excellent peelability is prepared by curing on a heat-resistant substrate such as glass, ceramic, and stainless steel plate. can do.
Also, by using such a molding resin composition, it is possible to perform injection molding, extrusion molding, compression molding or melt casting molding of aromatic heat-resistant polymers such as PI and PBI, which have been difficult in the past. It is possible to provide an industrially simple polymer modification method for aromatic heat-resistant polymers such as PI and PBI.

Claims (7)

An aromatic heat-resistant polymer resin with a repeating unit structure consisting of a nitrogen heterocyclic ring with an aromatic ring as the main chain is chemically modified by a follow-up reaction to give a prepolymer molded product before modification, a mold, In a molding resin composition containing a reactive modifier that imparts polymer properties such as releasability or mold contamination resistance,
The prepolymer (A-1) component is an aromatic imide-based or aromatic benzimidazole-based aromatic heat-resistant polymer, and the reactive modifier contained in the molding resin composition is: A dicarboxylic acid anhydride group is chemically reacted with the nitrogen heterocyclic chain site with an aromatic ring of the prepolymer (A-1) component represented by the general formula (1a), (1b) or the following general formula (2). In the first reactive modifying agent (B-1) that imparts
Unmodified by mixing 100 parts by weight of the prepolymer (A-1) component with 1 to 15 parts by weight of the first reactive modifying (B-1) agent under melting or semi-melting conditions. A resin composition (C-1);
The molecular weight is in the range of 10 ² to 10 ⁵ with respect to 100 parts of carboxylic acid represented by the stoichiometric percentage related to the esterification reaction of all carboxylic acids contained in the unmodified resin composition (C-1). And an esterification modifier to be reacted in the range of 10 to 200 parts as an esterification group represented by a stoichiometric percentage related to esterification modification contained in the fluorine-based alcohol and / or silicone. A molding resin composition.

[Wherein R is a divalent organic group, and n is an integer of 1 or more. ]

[N is an integer of 1 or more. ]

[N is an integer of 1 or more. ]   N in the general formulas (1a), (1b) and (2) is an integer of 5 to 30, and is modified in the first reactive denaturing (B-1) agent which is chemically bonded. 2. The molding resin composition according to claim 1, wherein the number of N heterocyclic rings with an aromatic ring as the repeating structural unit per bond is 2.   100 parts by weight of the molding resin composition (D-1) according to claim 1 or 2, and polymerizability 2 in the unmodified resin composition (C-1) contained in the (D-1). A molding resin composition comprising 10 to 100 parts by weight of a compound having polymerization reactivity with respect to a heavy bond and 0.1 to 20 parts by weight of a thermal radical generator (or thermal polymerization initiator). .   A molded article obtained by extrusion molding, compression molding, melt casting molding or injection molding using the molding resin composition according to any one of claims 1 to 3, has excellent releasability and mold as polymer characteristics An aromatic heat-resistant polymer molded article that exhibits mold releasability or mold contamination resistance.   100 parts by weight of an aromatic imide-based or aromatic benzimidazole-based heat-resistant aromatic polymer as a prepolymer before modification, and any of the molding resin compositions (D-1) according to any one of claims 1 to 3 A molded product obtained by extrusion molding, compression molding, cast molding or injection molding using the mixed resin composition (E-1) with 50 to 150 parts by weight of the above, releasability, mold releasability or An aromatic heat-resistant polymer molded product, which is provided with a polymer property that is resistant to mold contamination.   100 parts by weight of the unmodified resin composition (C-1) component, 10 to 200 parts by weight of a fluorinated alcohol and / or silicone having a molecular weight of 102 to 105, and the unmodified resin composition ( C-1) A mixed resin composition (E-2) obtained by mixing 10 to 100 parts by weight of a polymerizable double bond and a polymerization reactive compound in a component at a temperature of room temperature to room temperature or lower. The molded product obtained by using extrusion molding, compression molding, melt casting molding or injection molding is provided with polymer characteristics such as releasability, mold releasability or mold contamination resistance. Aromatic heat-resistant polymer moldings. The mixed resin composition (E-2) according to claim 6 is further mixed with 50 to 150 parts by weight of polybenzimidazole and / or polyimide or polyimide precursor polyamic acid at a temperature from room temperature to room temperature or lower. A polymer obtained by extruding, compression molding, casting or injection molding using the mixed resin composition (E-3), and having a release property, mold releasability or mold contamination resistance An aromatic heat-resistant polymer molded article characterized by imparting characteristics.