Polyamide resin composition and moulded product

FIELD: chemistry.

SUBSTANCE: invention relates to a polyamide resin composition, intended for obtaining a moulded product. The polyamide resin composition contains: (A) a polyamide, containing a unit of dicarboxylic acid and a diamine unit, including not less than 30 wt % of an m-xylenediamine unit, (B) a compound based on an aromatic secondary amine and (C) a compound on an organosulphuric base, where the mixed amount of the compound of the organosulphuric base (C) constitutes from 0.2 to 5 wt.p. counted per 100 wt.p. of the polyamide, and the weight ratio (B)/(C) in the polyamide resin composition is in the range from 0.1 to 5.0. The composition is characterised by a coefficient of oxygen-permeability not higher than 1 cm3·mm/m2·day·atm, at 23°C and 75% relative humidity (RH). Also described is the moulded product such as a hose or a pipe.

EFFECT: improved resistance to thermal ageing with the simultaneous preservation of permeability characteristics.

21 cl, 1 tbl, 23 ex

 

Area of technology

The present invention relates to a polyamide resin composition exhibiting excellent resistance to thermal aging and gas impermeability characteristics, and to a molded product containing it.

The level of technology

Given the prevoskhodnost polyamides from the point of view of characteristics such as strength, rigidity, resistance to solvents, formability and the like, they are used as materials for injection molding, such as in the case of automotive or electrical and electronic parts and the like, or packaging materials for foods, beverages, chemicals, electronic parts and the like. First of all, high stiffness, and excellent characteristics of impermeability to various gases or chemicals, and the like demonstrate polyamides having m-xylene group in the main polymer chain, and thus, they are widely used as materials for injection molding or packaging materials.

However, given the ease of formation of methylene radical in the position of the benzyl in polyamides with m-xylene group in the main chain of the polymer, from the viewpoint of structure, they are low in heat resistance or resistance to t�micheskogo aging in comparison with polyamides, such as nylon 6 and the like. For this reason, there are use cases in which polyamides having m-xylene group, are unlikely to be used as a molding material that determines the severity of the environment or application conditions, such as high-temperature environment and the like.

In recent years in the field of automotive parts and the like, in which the required characteristics of the gas tightness and resistance to thermal aging, despite a study of the use of polyamides for the above reasons, find it difficult to use polyamides having m-xylene group in the main polymer chain.

For this reason, suggestions were made for improving the heat resistance and resistance to thermal aging polyamides. For example, in patent document 1 describes a heat-resistant polyamide formed from a polyamide having m-xylene group in the main polymer chain, copper compounds, halide, spatial hindered phenol and/or prostranstvennym method is the appropriate method for extruded fibers, but it was an unsatisfactory method for improving the resistance to thermal aging products molded or extruded products used for automotive parts and such�CSOs.

In addition, for example, in patent document 2 proposes a method in which in connection with the forming processing of the polyamide having m-xylene group in the main chain of the polymer, adding at least one representative selected from a lubricant, a stabilizer on organophosphorus-based, spatial derivative of hindered phenol and a derivative of the spatial hindered amine, in an amount in the range from 0.005 to 0.5 mass part, thereby preventing for polyamide passage of gelation. However, this method represents a method of preventing the passage of gelation during the forming processing, but it was an unsatisfactory method for improving the resistance to thermal aging after forming.

In addition, for example, in patent document 3 as a molding material for high precision components is described one example in which as heat stabilizer in the polyamide include compound on the basis of aromatic secondary amine. However, this methodology is the methodology suitable for nylon 66, but the effects in respect of polyamides having excellent skeleton of the polymer, will not be considered.

In light of the above, particularly with respect to the above polyamides, demonstrating the superior performance of gashapons�the occurrence frequencies, modern art is that still not found the technique of improving the resistance to thermal aging, while maintaining the characteristics of the gas tightness.

The prior art documents

Patent documents

Patent document 1: JP-A-10-130497

Patent document 2: JP-A-2001-164109

Patent document 3: JP-A-2006-28327

Summary of invention

The problem solved by the present invention

One objective of the present invention is to offer a polyamide resin composition having an m-xylylene group in the main polymer chain, which can solve the above problems and which is excellent from the point of view of the characteristics of the gas tightness and resistance to thermal aging, and a molded product containing it.

A means of addressing

The inventors have conducted extensive and intensive research. As a result, it was found that the above resolve the problem when using the polyamide resin composition, comprising (A) polyamide consisting of diamino link containing 30 mol%. and more m-xylylenediamine link, and link dicarboxylic acid, and (B) the connection on the basis of aromatic secondary amine, wherein the polyamide resin composition characteristics�isoamsa the oxygen permeability coefficient, not more than 1 CC·mm/m2·day·ATM at 23°C and 75% relative humidity (RH).

The effect of the invention

The polyamide resin composition of the present invention is excellent from the point of view of the characteristics of the gas tightness and resistance to thermal aging. A molded product containing it may be used for automotive parts and the like, where required characteristics of the gas tightness and resistance to thermal aging, and its industrial value is very high.

The methods of the invention

The polyamide resin composition

The polyamide resin composition of the present invention includes (A) a polyamide consisting of diamino link containing 30 mol%. and more m-xylylenediamine link, and link dicarboxylic acid, and (B) the connection on the basis of aromatic secondary amine, and its coefficient of oxygen permeability is not more than 1 CC·mm/m2·day·ATM at 23°C and 75% RH. In this regard, in the present invention diamino link" denotes constituting the polymer element derived from diamino component material a raw material for polyamide, and "link dicarboxylic acid" refers constituting the polymer element derived from dicarboxylic acid material is a raw material for polyamide. Pre�respectful is additional content in the polyamide resin composition of organic sulfur compounds on the basis of (C).

The polyamide (A) used in the present invention is a polyamide containing 30 mol%. or more, preferably 50 mol%. or more, more preferably 70 mol%. and more, still more preferably 80 mol%. and more, particularly preferably 90 mol%. and more m-xylylenediamine link. As a result of adjustable storage, the levels of m-xylylenediamine diamino link in the link equal to 30 mol%. and more, can be made suitable gas impermeability characteristics and characteristics of the gas tightness at high humidity polyamide (A). As for the polyamide (A), as examples, for example, the polyamides obtained by polycondensation diamino component formed mainly of m-xylylenediamine, and dicarboxylic acid component of any type, and the like. The polyamide may be a homopolymer or a copolymer. Consider the polyamide shows a high gas impermeability characteristics and is suitable from the viewpoint of heat resistance and processability of the molding. The polyamide (A) can be used individually or as a mixture of the plurality of resin.

In addition, as diamino link to m-xylylenediamine link can be added p-xylylenediamine link. Adding to �-xylylenediamine link p-xylylenediamine link can be improved melting point, the glass transition temperature and heat resistance of the polyamide (A). Currently when you hit the levels of p-xylylenediamine link as a result of adding arbitrary fractions in the range not exceeding 70 mol%., you controlled to withstand temperature resistance, impermeability characteristics and processability of the molding.

As for djaminovich components that differ from the m-xylylenediamine that can be used to obtain a polyamide (A), as examples can be presented aliphatic diamines, such as tetramethylaniline, pentamethylene, 2-methylpentylamine, hexamethylendiamine, heptamethylnonane, octamethylene, monomethylaniline, decamethylenediamine, documentrenderer, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and the like; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)position, bis(aminomethyl)tricyclodecane and the like; diamines containing aromatic ring, such as bis(4-aminophenoxy) ether, p-phenylenediamine, p-xylylenediamine, bis(aminomethyl)naphthalene and the like; and the like. However, it should be considered that the present�tense invention limited to this.

The polyamide (A) used in the present invention is a polyamide as a link dicarboxylic acid containing 50 mol%. or more, preferably 70 mol%. or more, more preferably 80 mol%. and more, and still more preferably 90 mol%. and more, link, α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms. As a result of the controlled solidification of content level level α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms in chain dicarboxylic acid, 50 mol%. and more, can be made suitable gas impermeability characteristics and characteristics of the gas tightness at high humidity polyamide (A).

As dicarboxylic acid component that can be used to obtain a polyamide (A), as examples can be represented by aliphatic dicarboxylic acids such as succinic acid, glutaric acid, Emelyanova acid, cork acid, azelaic acid, adipic acid, sabotinova acid, undecanoate dikelola, dodekanisa dikelola and the like; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-natalijagolosova acid and detailed; and the like. However, it should be understood that the infusion of�her invention is not limited to this.

In addition, the polyamide (A) used in the present invention, as the dicarboxylic acid component may be used a mixture of α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and isophthalic acid. When using the above-mentioned mixture of the polyamide (A) can be improved temperature resistance and processability of the molding.

Mixing ratio between the amounts of α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and isophthalic acid (molar ratio of (α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms)/(isophthalic acid)) is preferably in the range from 50/50 to 99/1, and more preferably from 70/30 to 95/5.

In addition, when used as a component of the dicarboxylic acid mixture of adipic acid and sabatinovka acids can arbitrarily control the heat resistance, gas impermeability characteristics and crystallinity. With intention to reduce the degree of crystallinity or in case of transfer systems in amorphous state mixing ratio between the amounts of adipic acid and sabatinovka acid (molar ratio (sabotinova acid)/(adipic acid)) will preferably be in the range of�from 80/20 to 30/70, and more preferably from 70/30 to 40/60. With regard to the above-mentioned ratio between the amounts of components in the mixture, in the case of imparting the importance of the characteristics of effective gas tightness of a decrease in the proportion sabatinovka acid in the mixture. Specifically, the ratio of components in the mixture is preferably not more than 50/50, more preferably not greater than 40/60, and even more preferably not greater than 30/70. With regard to the above-mentioned ratio between the amounts of components in the mixture, in the case of imparting the importance of effective thermal resistance of a decrease in the proportion sabatinovka acid in the mixture. Specifically, the ratio of components in the mixture is preferably not greater than 60/40, more preferably not greater than 40/60, and even more preferably not greater than 30/70.

In addition to the above diamino component and dicarboxylic acid component as copolymerization component can also be used lactam, such as ε-caprolactam, laurolactam and the like, or aliphatic aminocarbonyl acid, such as aminocaproic acid, aminoundecanoic acid and the like, within the range in which the effects of the present invention will not deteriorate.

As for cobordism�IDA (A), which can be used in the present invention, as examples can be represented by poly(m-xylylenediamine) (PA-MXDI), copolymers of caprolactam/m-xylylenediamine (PA-6/MXDI) and the like.

As for the polyamide (A), which preferably can be used in the present invention, as examples of the polyamide obtained by polycondensation of a diamine comprising mainly m-xylylenediamine, and adipic acid, (hereafter in this document referred to as "polyamide (a)"); a polyamide obtained by polycondensation of a diamine comprising mainly m-xylylenediamine, and sabatinovka acid (hereafter in this document referred to as "polyamide (b)"); polyamide resulting from the polycondensation of a diamine comprising mainly m-xylylenediamine, adipic acid and sabatinovka acid; and the like. In this case, under the above-mentioned term "mainly" means a content of 50 mol%. or more of the total amount of diamine.

For example, with regard to the polyamide (a), as an example, can be represented by poly(m-xylylenediamine); as for the polyamide (b), as an example, can be represented by poly(m-xylylenediamine). In addition, with regard to the polyamide (A), concurrently�e examples can be presented polyamide, the resulting polycondensation of m-xylylenediamine, p-xylylenediamine and adipic acid; and a polyamide obtained by polycondensation of m-xylylenediamine, p-xylylenediamine and sabatinovka acid.

In addition, with regard to the polyamide (A), which can be preferably used in the present invention, as an example, can be represented by a mixture of the above-mentioned polyamide (a) and polyamide (b). As a result of mixing the above-mentioned polyamide (a) and polyamide (b) it is possible to arbitrarily control the heat resistance and gas impermeability characteristics, while maintaining the degree of crystallinity. As to the ratio between the amounts of the polyamide (a) and polyamide (b) in the mixture (mass ratio ((polyamide (b))/(polyamide (a))), in the case of imparting the importance of the characteristics of effective gas tightness will decrease in the proportion of polyamide (b) in the mixture. More specifically, the ratio of components in the mixture is preferably not more than 50/50, more preferably not greater than 40/60, and even more preferably not greater than 30/70.

As for the polyamide (A), which preferably can be used in the present invention, more specifically, as examples can be presented polyamides,�scientists as a result of polycondensation of each component of the dicarboxylic acid, comprising 50 mol%. or more, preferably 70 mol%. or more, more preferably 80 mol%. and more, and still more preferably 90 mol%. or more α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, each diamino component comprising 30 mol%. or more, preferably 50 mol%. or more, more preferably 70 mol%. and more, still more preferably 80 mol%. and more, particularly preferably 90 mol%. and more, m-xylylenediamine.

With regard to the above-mentioned α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, for example, as examples can be represented by aliphatic dicarboxylic acids such as succinic acid, glutaric acid, Emelyanova acid, cork acid, azelaic acid, adipic acid, sabotinova acid, undecanoate dikelola, dodekanisa dikelola and the like. Among them, preferred are adipic acid and sabotinova acid.

As for the polyamide (A), which preferably can be used in the present invention, specifically, as examples can be presented polyamides formed from diamino management, incorporating m-xylylenediamine link and p-xylylenediamine link and link dicarboxylic acid comprising 50 mol%. � more level α,ω-linear aliphatic dicarboxylic acid, containing from 4 to 20 carbon atoms. As for the polyamide (A), more preferably in the examples presented polyamides formed from diamino link, comprising 30 mol%. and more m-xylylenediamine link and from 1 to 70 mol%. p-xylylenediamine link, and link dicarboxylic acid comprising 50 mol%. and more level α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms.

In addition, with regard to the polyamide (A), which preferably can be used in the present invention, specifically, as examples of the polyamides formed from link dicarboxylic acid comprising an element α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and link isophthalic acid and diamino link comprising 70 mol%. and more m-xylylenediamine link. More specifically, as examples are polyamides formed from link dicarboxylic acid comprising 50 mol%. and more level α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and from 1 to 50 mol%. link isophthalic acid and diamino link comprising 70 mol%. and more m-xylylenediamine link. More preferable examples can be presented polyamides formed from intermediates� dicarboxylic acid, comprising 70 mol%. and more level α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and from 1 to 30 mol%. link isophthalic acid and diamino link comprising 70 mol%. and more m-xylylenediamine link.

The polyamide (A) in connection with its acquisition of any specific restrictions are not applied, and it can be obtained by using the widely known method and conditions for polymerization. During the polycondensation to obtain a polyamide as a molecular weight modifier may be added a small amount of monoamine or monocarboxylic acid. For example, polyamide (A) is prepared according to the method in which the nylon salt, formed from m-xylylenediamine and adipic acid, is subjected to a temperature increase in the state at an elevated pressure in the presence of water and polymerized in a molten state while removing the added water and condensing water. The polyamide (A) also get in the way in which m-xylylenediamine add directly to adipic acid in a molten state, and the mixture was subjected to polycondensation at atmospheric pressure. In this case, for the purpose of maintaining the reaction system in a uniform molten state to adipic acid is continuously added m-KS�lilangeni and, meanwhile, give the opportunity to proceed the polycondensation under the simultaneous effect on the reaction system raise the temperature so that the reaction temperature was not lower than the melting temperature obtained oligoamide and polyamide.

In addition, the polyamide (A) can be obtained by carrying out solid-phase polymerization in the implementation of the heat treatment in the solid state after receipt by the method of polymerization in the melt. The polyamide (A) in connection with its acquisition of any specific restrictions are not applied, and it can be obtained by using well-known techniques and conditions for polymerization.

Having a number average molecular weight (Mn) of the polyamide (A) is preferably in the range of 18,000 to 70,000, and more preferably from 20,000 to 50,000, while its expression using the values given to the value for PMMA (polymethylmethacrylate) when using the measurement by GPC method (gel permeation chromatography). In case of contact having a number average molecular weight (Mn) of the polyamide (A) within the given range will be obtained by appropriate heat resistance and processability of the molding.

The melting point of the polyamide (A) used in the present invention preferably is in the range from 150 to 300°C. In case�AE hit the melting temperature of the polyamide (A) within the given range when mixing the polyamide (A) with (B) a connection on the basis of aromatic secondary amine will be facilitated melting resin in the extruder, and will be obtained by matching the performance and processability of the molding.

In this regard, the melting point and the glass transition temperature can be measured by the DSC method (differential scanning calorimetry). For example, the measurement can be carried out as a result of selection of about 5 mg sample and heating it from room temperature to 300°C in conditions when the rate of temperature increase of 10°C/min when using DSC-60, manufactured in the company Shimadzu Corporation. As for the gas atmosphere, it may be provided with a flow of nitrogen at 30 ml/min. with regard to the transition temperature, we used the so-called midpoint temperature (Tgm). In this regard, as is widely known, the value of Tgm is the temperature of the midpoint between the points of intersection of the tangent lines to the base lines of the glassy state and supercooled state (kauchukopodobnoe state) and a tangent line with a slope transition in the DSC curve.

The polyamide (A) in order to improve the stability during processing during molding in the melt or in order to prevent staining of polyamide (A) may be added a compound of phosphorus. As phosphorus compounds in a suitable case, use phosphorus compounds containing alkali metal or alkaline earth meta�l, and their examples include salts of phosphoric acid, salts phosphonoacetic acid and salts of phosphorous acid and an alkali metal or an alkaline earth metal such as sodium, magnesium, calcium and the like. In particular, preferably used those connections that use salt phosphonoacetic acid and alkali metal or alkaline earth metal, because they are particularly excellent in terms of the effect of preventing staining of polyamide. The concentration of phosphorus in the polyamide is preferably in the range from 1 to 1000 part per million, more preferably from 1 to 500 part per million, more preferably from 1 to 350 part per million, and especially preferably from 1 to 200 part per million, based on the number of phosphorus atoms.

The polyamide resin composition of the present invention as comprising a component composition different from that of the polyamide (A), contains (C) a derivative of an aromatic secondary amine. As a derivative of the aromatic secondary amine (V), preferred are compounds having diphenylamine skeleton, compounds having phenylnaphthylamine skeleton, and compounds having dinitramine skeleton; and more preferred are compounds having diphenylamine skeleton, and compounds having phenylnaphthylamine skeleton�. Specifically, as examples, may be represented by compounds having diphenylamine skeleton, such as n,n'-dialkyldiphenyl (the number of carbon atoms in the alkyl group: 8 to 14), acceleratory diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluensulfonyl)diphenylamine, N,N'-diphenyl-para-phenylenediamine, N-phenyl-N'-isopropyl-para-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-para-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-para-phenylenediamine and the like; compounds having phenylnaphthylamine skeleton, such as N-phenyl-1-naphthylamine, N,N'-di-2-naphthyl-para-phenylenediamine and the like; compounds having dinitramine skeleton, such as 2,2'-dinitramine, 1,2'-dinitramine, 1,1'-dinitramine and the like; and mixtures thereof. However, it should be considered that the present invention limited to this. Among them, more preferred are 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, N,N'-di-2-naphthyl-para-phenylenediamine and N,N'-diphenyl-p-phenylenediamine; and especially preferred are N,N'-di-2-naphthyl-para-phenylenediamine and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

The number of such derived aromatic secondary amine (V) in the mixture is preferably in the range from 0.01 to 5 mass parts, more preferably from 0.1 to 2.0 mass parts, and particularly preferably from 0.2 �about a 1.0 mass part, per 100 parts by weight of polyamide (A). In case of contact with a given amount in the mixture is in the range from 0.01 to 5 parts by weight will produce the effect of improving the resistance to thermal aging, and suitable for the surface of the molded product, and thus it is preferable.

Preferably, the polyamide resin composition of the present invention further contains (C) a connection on organic sulfur basis. Among the organic sulfur compounds on the basis of preferred are compounds in mercaptobenzimidazole-based, connection-based dithiocarbamates acid compounds on tiomochevinoi based and connection-based organic timeslot; and more preferred are compounds in mercaptobenzimidazole based and connection-based organic timeslot. Specifically, as examples can be presented based compounds mercaptobenzimidazole, such as 2-mercaptobenzimidazole, 2-mercaptobenzimidazole, metal salts of 2-mercaptobenzimidazole and the like; compounds based on organic timeslot, such as dilauryl-3,3'-thiodipropionate, Dimyristyl-3,3'-thiodipropionate, DISTEARYL-3,3'-thiodipropionate, pentaerithrityl(3-lawrenceofarabia) and the like; compounds on �Snov, dithiocarbamates acid, such as metallic salts diethyldithiocarbamic acid, metal salt dibutyldithiocarbamate acid and the like; compounds with thiourea, such as 1,3-bis(dimethylaminopropyl)-2-thiourea, tributylamine and the like; and mixtures thereof. However, it should be considered that the present invention limited to this. Among them, preferred are 2-mercaptobenzimidazole, 2-mercaptobenzimidazole, Dimyristyl-3,3'-thiodipropionate, DISTEARYL-3,3'-thiodipropionate and pentaerithrityl(3-lawrenceofarabia); more preferred are pentaerithrityl(3-lawrenceofarabia), Dimyristyl-3,3'-thiodipropionate and 2-mercaptobenzimidazole; and especially preferred is pentaerithrityl(3-lawrenceofarabia).

The amount of such organic sulfur compounds on the basis of (C) in the mixture is preferably in the range from 0.01 to 5 mass parts, more preferably from 0.1 to 2.0 mass parts, and particularly preferably from 0.2 to 1.0 mass parts, per 100 parts by weight of polyamide (A). In case of contact with a given amount in the mixture is in the range from 0.01 to 5 parts by weight will produce the effect of improving the resistance to thermal aging, and suitable for the surface of the molded product, and thus, it is preferred�rapidly.

With regard to the aforementioned compounds based on aromatic secondary amine (V) and organic sulfur compounds on the basis of (C), can be added one type or two or more types of compounds based on aromatic secondary amine (V), and can be added one type or two or more types of organic sulfur compounds on the basis of (C). In addition, it is preferred to use compounds based on aromatic secondary amine (V) and organic sulfur compounds on the basis of (C) in combination. In the case of compounds based on aromatic secondary amine (V) and organic sulfur compounds on the basis of (C) in a combination of the polyamide resin composition is suitable resistance to thermal aging in comparison with what occurs in the case of individual use of each of these compounds.

More specifically, with regard to suitable combinations of compounds based on aromatic secondary amine (V) and organic sulfur compounds on the basis of (C), as an example, presents a combination of at least one element selected from 4,4'-bis(α,α-dimethylbenzyl)diphenylamine and N,N'-di-2-naphthyl-p-phenylenediamine, as compounds based on aromatic secondary amine (B); and at least one element selected from Dimyristyl-,3'-thiodipropionate, 2-mercaptobenzimidazole and pentaerithrityl(3-lawrenceofarabia), as organosulfur compounds on the basis of (C). In addition, more preferred is the combination of N,N'-di-2-naphthyl-p-phenylenediamine as compounds based on aromatic secondary amine (C) and pentaerithrityl(3-lowestappropriate) as organosulfur compounds on the basis of (C).

In addition, the ratio between the levels of the aforementioned compounds based on aromatic secondary amine (V) and organic sulfur compounds on the basis of (C) (mass ratio (B)/(C)) in the polyamide resin composition is preferably in the range from 0.05 to 15, more preferably from 0.1 to 5.0, and even more preferably from 0.2 to 2.0.

As a result of harmonization of relations between levels of a compound based on the secondary amine (V) and organic sulfur compounds on the basis of (C) in the polyamide resin composition in the range from 0.05 to 15 can be effectively improved resistance to thermal aging, while maintaining the characteristics of impermeability.

To the polyamide resin composition of the present invention can be blended with one type or more types of resins such as polyamide, different from the polyamide (A), complex, polyester, polyolefin, Polyphenylene sulfide, polycarbonate and�such, within the range, which will not be worsened the achievement of the goals.

First of all, may preferably be blended with polyamide different from that of the polyamide (A). More preferably, may be blended with the aliphatic polyamide resin. It is preferred to use aliphatic polyamide resin, because it is able to improve the mechanical physical properties of a molded product. As the aliphatic polyamide resins may be used individually or in combination nylon 6, nylon 66, nylon 11, nylon 12, nylon 46, nylon 610, nylon 612, nylon 666, and the like.

The polyamide resin composition of the present invention may contain an inorganic filler. When using the inorganic filler can be improved rigidity and stability of the geometric dimensions of a molded product. The inorganic filler includes a wide range of fillers having a fibrous, powdery, granular, plate, or cloth-like meteoritnuyu form. Their examples include fiberglass, carbon fiber, graphite fiber, carbon black, calcium carbonate, talc, Catalpa, wollastonite, silica, alumina, diatomaceous earth, clay, kaolin, mica, granulated glass, flaked glass, hollow glass, gypsum, CRA�tion ferrioxide pigment, metallic fiber, titanium dioxide, whiskers of potassium titanate, whiskers of aluminum borate, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, aluminum, aluminum oxide, aluminum hydroxide, copper, stainless steel, zinc oxide whiskers of metals and the like.

To the polyamide resin composition of the present invention may be added additives such as a matting substance, a weather-resistant stabilizer, UV absorbers, nucleating agent, plasticizer, flame retardant, antistatic, remedy painting, a means of preventing gelation, colorant, releasing agent and the like, within the range that does not deteriorate the achievement effects of the present invention.

From the polyamide resin composition of the present invention requires the demonstration of the oxygen permeability coefficient not more than 1 CC·mm/m2·day·ATM at 23°C and 75% RH. In the case under consideration, the oxygen permeability coefficient not greater than 1, the most appropriate characteristics of impermeability to various gases, such as freon, carbon dioxide, hydrogen, alcohol, and the like. The coefficient of oxygen permeability is preferably not greater than 0.7 CC·mm/m2·day·ATM, and more preferred�Uo no more than 0.5 CC·mm/m2·day·ATM.

A molded product

A molded product containing the polyamide resin composition of the present invention, demonstrates how the characteristics of gas impermeability, and resistance to thermal aging and can be used for the manufacture of various automotive parts, electrical parts products and the like, and thus it is preferable. In particular, as a molded product containing a composition of a polyamide resin, preferably can be used hoses or pipes.

Examples

Later in this paper present invention is described in more detail with referring to examples and comparative examples, but is not necessary to consider what is the present invention limited to this. In this regard, in the present examples was performed various measurements as further techniques.

(1) the characteristics of the gas tightness

The coefficient of oxygen permeability (CC·mm/m2·day·ATM) of the film was measured in an atmosphere at 23°C and 75% RH in accordance with the document JIS K7126. To measure the used appliance OX-TRAN 2/21, manufactured in the company's Modern Controls Inc.. Means that the smaller will be the value, the more suitable is the characteristics of the gas tightness.

(2) Stoikos�ü to thermal aging

First of all, the film was subjected to heat treatment at 130°C for 72 hours when using a dryer heated by hot air. Then before and after the heat treatment tests were subjected to the mechanical characteristics tensile film in accordance with the document JIS K7127, thereby, determining the rupture stress (MPa). In this regard, the measurement was carried out using the apparatus of the device Strograph made in the company of Toyo Seiki Seisaku-sho, Ltd., in conditions in the form of the sample width of 10 mm, the distance between the clamps 50 mm, the stretching speed of 50 mm/min, the temperature between 23°C and humidity in the measurement of 50% RH. The ratio between the destructive voltages before and after the heat treatment was defined as the degree of preservation of the limit of the tensile strength and the degree of preservation of the limit of tensile strength (%) was calculated according to the following next expression (1). It is implied that the greater the degree of preservation of the ultimate strength in tension, the more excellent will be the resistance to thermal aging.

The degree of preservation of the limit of tensile strength (%)= [{rupture stress (MPa) of the film after the heat treatment}/{Deplete voltage�s (MPa) of the film before the heat treatment}]×100 (1)

(3) the melting point and the glass transition temperature of polyamide

The melting temperature and the glass transition temperature was determined by the method of differential scanning calorimetry (DSC) when using DSC-60, manufactured in the company Shimadzu Corporation. As for the conditions of measurement, approximately 5 mg of sample were exposed to the effect of increasing the temperature at 10°C/min, and when it reaches a temperature of 300°C the sample is abruptly cooled and again subjected raise the temperature conditions at 10°C/min.

(4) having a number Average molecular weight

Having a number average molecular weight was determined with the expression using the values given to the value for PMMA using the measurement by GPC method using instrument HLC-8320GPC made in the company Tosoh Corporation. In this regard, as the column to measure the used device TSKgel Super HM-H, solvent used hexafluoroisopropanol (HFIP) containing dissolved therein triptorelin sodium in 10 mmol/l; and temperature measurements exhibited at 40°C. in addition, a calibration curve was obtained by dissolving the PMMA in HFIP with six levels and the measurement for the solution.

Example 1

The synthesis of the polyamide (A1)

After heating and melting at 170°C in the reactor to sabatinovka acid (TA grade, manufactured in the company Ito Oil Chemicals Co., Ltd.) dropwise gradually added m-xylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Company, Inc.) at a molar ratio with sebacinales acid 1/1 while stirring the contents, and, meanwhile, the temperature was increased to 240°C. after the addition the temperature was increased to 260°C. Upon completion, the reaction contents were extracted in the form of strands and pelletized using a pelletizer. The resulting granules were loaded into a rotating drum and subjected to solid phase polymerization under reduced pressure, thereby obtaining a polyamide (A1) having a regulated molecular weight.

The polyamide (A1) had a melting point of 191°C, the glass transition temperature of 60°C and having a number average molecular weight of 30000. Its the oxygen permeability coefficient was 0.8 CC·mm/m2·day·ATM.

Example 2

The synthesis of the polyamide (A2)

After heating and dissolving in a nitrogen atmosphere in the reactor to adipic acid (produced by the company Rhodia) was gradually dropwise added a mixture of diamino p-xylylenediamine (PXDA, manufactured by Mitsubishi Gas Chemical Company, Inc.) and m-xylylenediamine at a molar ratio of (PXDA/MXDA) 3/7, getting the molar ratio between �Eminem and dicarboxylic acid 1/1, while stirring the contents, and, meanwhile, the temperature was increased. Upon completion pocataligo add stirring and the reaction was continued until the viscosity of the prescribed value. After that, the contents extracted in the form of strands and pelletized using a pelletizer, thereby obtaining a polyamide (A2). The polyamide (A2) had a melting point of 258°C, the glass transition temperature of 90°C and having a number average molecular weight of 25000. Its coefficient of oxygen permeability rate was 0.15 CC·mm/m2·day·ATM.

Example 3

Synthesis of polyamide (A3)

Polyamide (A3) was synthesized in the same manner as in example 2, except for using sabatinovka acid instead of adipic acid in example 2. Polyamide (A3) had a melting point of 215°C, the glass transition temperature of 63°C, having a number average molecular weight of 19000 and the oxygen permeability coefficient of 0.8 CC·mm/m2·day·ATM.

Example 4

Synthesis of polyamide (A4)

Polyamide (A4) was synthesized in the same manner as in example 2, except for using in example 2 diamine mixture of p-xylylenediamine and m-xylylenediamine, the molar ratio of (PXDA/MXDA) which was 6/4. Polyamide (A4) had a temperature plavini� 288°C the glass transition temperature of 95°C, having a number average molecular weight of 21000 and the oxygen permeability coefficient of 0.3 CC·mm/m2·day·ATM.

Example 5

Synthesis of polyamide (A5)

After heating and dissolving in a nitrogen atmosphere in a reactor a mixture of dicarboxylic acids from adipic acid and isophthalic acid (manufactured by A. G. International Chemical Co., Ltd.) at a molar ratio of 9/1 was gradually dropwise added m-xylylenediamine, getting the molar ratio between the diamine and dicarboxylic acid 1/1, while stirring the contents, and, meanwhile, the temperature was increased. Upon completion pocataligo add stirring and the reaction was continued until the viscosity of the prescribed value. After that, the contents extracted in the form of strands and pelletized using a pelletizer. The resulting granules were loaded into a rotating drum and subjected to solid phase polymerization under reduced pressure, thereby obtaining a polyamide (A5) having a regulated molecular weight.

Polyamide (A5) had a melting point of 226°C, the glass transition temperature of 94°C, having a number average molecular weight of 48,000, and the oxygen permeability coefficient of 0.13 CC·mm/m2·day·ATM.

Example 6

Synthesis of polyamide (A6)

Polyamide (A6)was synthesized in the same manner, as in the example of getting 3, except for using the sample receiving 3 diamine mixture of p-xylylenediamine and m-xylylenediamine, the molar ratio of (PXDA/MXDA) which was 4/6. Polyamide (A6) had a melting point of 221°C, the glass transition temperature of 64°C, having a number average molecular weight of 23,000 and the oxygen permeability coefficient of 0.9 CC·mm/m2·day·ATM.

Example 7

Synthesis of polyamide (A7)

Polyamide (A7) was synthesized in the same manner as in the example of getting 3, except for using the sample receiving 3 diamine mixture of p-xylylenediamine and m-xylylenediamine, the molar ratio of (PXDA/MXDA) which was 2/8. Polyamide (A7) had a melting point of 207°C, the glass transition temperature of 62°C, having a number average molecular weight of 28000 and the oxygen permeability coefficient of 0.8 CC·mm/m2·day·ATM.

Example 8

Synthesis of polyamide (A8)

Polyamide (A8) was synthesized in the same manner as in the example of getting 3, except for using the sample receiving 3 diamine mixture of p-xylylenediamine and m-xylylenediamine, the molar ratio of (PXDA/MXDA) which was 5/5. Polyamide (A8) had a melting point of 227°C, the glass transition temperature of 66°C, having a number average molecular weight of 18,000 and the coefficient kislorodoprovoda�bridges 1,0 CC·mm/m 2·day·ATM.

Example 1

100 parts by weight of the polyamide obtained by polycondensation of adipic acid and m-xylylenediamine, (N-MXD6, manufactured by Mitsubishi Gas Chemical Company, Inc., MX nylon, brand: S6007) and 0.2 mass parts of N,N'-di-2-naphthyl-p-phenylenediamine (Nocrac White, manufactured in the company Ouchi Shinko Chemical Industrial Co., Ltd.) was stirred in a dry condition and subjected to extrusion forming using a twin-screw extruder equipped with a screw having a diameter of 30 mm, and the T-shaped extrusion head, thereby obtaining a film thickness of 100 microns.

When using the above-mentioned films were evaluated by the above-mentioned characteristics of the gas tightness and resistance to thermal aging. The evaluation results shown in table 1.

Examples 2 to 14 and 16 to 18

Films were obtained in the same manner as in example 1 except for changing the composition of a polyamide resin in example 1 to each of those described in table 1, and then evaluated in the same manner. The evaluation results shown in table 1.

Comparative examples 1 to 6

Films were obtained in the same manner, except for the replacement of polyamide and additives(additives) loaded in a twin-screw extruder and subjected to extrusion molding in example 1 to those that �opisyvayutsya in table 1, respectively, and then evaluated in the same manner. The evaluation results shown in table 1.

Example 15

The polyamide and the additives used in example 2, and nylon 6 (made in the company Ube Industries, Ltd., brand: V) was stirred under a dry condition at a weight ratio ((polyamide and additives)/(nylon 6)) 3/7 (added amount of nylon 6 was 233,8 mass parts per 100 mass parts of a polyamide resin and molded when using a single-screw extruder equipped with a screw having a diameter of 25 mm, and the extrusion head, thereby obtaining a tubular molded product with a thickness of 200 microns. This molded product was cut out a sample for the measurement limit of the tensile strength, which was subjected to heat treatment at 130°C for 72 hours. The degree of preservation of the limit of the tensile strength of the sample after the heat treatment was 92%. In addition, the oxygen permeability coefficient was of 0.45 CC·mm/m2·day·ATM.

In this regard, each of the abbreviations described in table 1, represents the following:

- A1: polyamide (A1) obtained in example 1

- A2: polyamide (A2) obtained in example 2

- A3: polyamide (A3) obtained in the example of getting 3

- A4: polyamide (A4) obtained�th in the example of getting 4

- A5: polyamide (A5) obtained in the example of getting 5

A6: polyamide (A6) obtained in the example of getting 6

- A7: polyamide (A7) obtained in the example of getting 7

A8: polyamide (A8) obtained in example obtain 8

- N-MXD6 (S6007): polyamide obtained by polycondensation of adipic acid and m-xylylenediamine, (manufactured by Mitsubishi Gas Chemical Company, Inc., MX nylon, brand: S6007, melting point: 240°C, having a number average molecular weight: 45000)

- N-MXD6 (S6121): polyamide obtained by polycondensation of adipic acid and m-xylylenediamine, (manufactured by Mitsubishi Gas Chemical Company, Inc., MX nylon, brand: S6121, melting point: 240°C, having a number average molecular weight: 65000)

- B1: N,N'-di-2-naphthyl-p-phenylenediamine (Nocrac White, manufactured in the company Ouchi Shinko Chemical Industrial Co., Ltd.)

- B2: 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Nocrac CD manufactured in the company Ouchi Shinko Chemical Industrial Co., Ltd.)

- C1: Pentaerithrityl(3-lawrenceofarabia) (Sumilizer TP-D, manufactured in the company of Sumitomo Chemical Co., Ltd.).

- C2: 2-mercaptobenzimidazole (Sumilizer MB made in the company of Sumitomo Chemical Co., Ltd.)

- C3: Dimyristyl-3,3'-thiodipropionate (Sumilizer TPM, manufactured in the company of Sumitomo Chemical Co., Ltd.)

- D1: 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5·5]Formica Sumilizer GA-80, manufactured in the company of Sumitomo Chemical Co., Ltd.)

- D2: P�interfraternity[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010, manufactured in the company Ciba-Geigy AG)

- Nylon 6: Made in the company Ube Industries, Ltd., brand: V

As demonstrated in the above examples, the compositions of polyamide resins, comprising (A) polyamide and (B) the connection on the basis of aromatic secondary amine, as demonstrated outstanding characteristics of impermeability and resistance to thermal aging, while the compositions of polyamide resins that do not meet the specified conditions, and the like, have been unsatisfactory from the standpoint of resistance to thermal aging.

Table 1
PolyamideThe diamine (ratio is a molar ratio)Dicarboxylic acidSupplements (the number in brackets represents the added mass part)The ratio (mass ratio) (B)/(C)The coefficient of oxygen permeability (at 75% S) (CC·mm/m2·day·ATM)The degree of preservation of the limit of tensile strength (%) (at 130°C for 72 hours)
Derived aromatic secondary amine (In)The connection on organic sulfur-based (C)Another connection
Example 1N-MXD6 (S6007)MXDAAdipic acidB1 (0,2)---0,1590
Example 2N-MXD6 (S6007)MXDAAdipic acidB1 (0,02)C1 (0,2)-0,100,15110
Example 3N-MXD6 (S6121)MXDAAdipic acidB2 (0,5)C3 (0,1)-5,00,15100

Example 4 A1MXDASabotinova acidB1 (0,7)C2 (0,05)-140,895
Example 5A2PXDA/MXDA 3/7Adipic acidB1 (0,1)C3 (1,0)-0,10,1593
Example 6A3PXDA/MXDA 3/7Sabotinova acidB2 (2,0)C1 (0,3)-6,70,8105
Example 7A4PXDA/MXDA 6/4Adipic acidB2 (1,0)C1 (0,5)-2,00,3108
Example 8 A5MXDAAdipic acid/ isophthalic acid 9/1B1 (0,4)C1 (2,0)-0,200,13111
Example 9N-MXD6 (S6007)MXDAAdipic acidB1 (0,5)C1 (0,5)-1,00,15115
Example 10N-MXD6 (S6007)MXDAAdipic acidB1 (1,0)C1 (1,0)-1,00,15120

Example 11N-MXD6 (S6007)MXDAAdipic acidB1 (0,05)C1 (0,05)- 1,00,1580
Example 12N-MXD6 (S6007)MXDAAdipic acidB1 (0,15)C1 (0,15)-1,00,1589
Example 13N-MXD6 (S6007)MXDAAdipic acidB1 (0,9)C1 (0,09)-100,1590
Example 14N-MXD6 (S6007)MXDAAdipic acidB1 (1,5)C1 (0,5)-3,00,1595
Example 15N-MXD6 (S6007)MXDAAdipic acidB1 (0,02)C1 (0,2) Nylon 6 (233,8)0,100,4592
Example 16A6PXDA/MXDA 4/6Sabotinova acidB1 (0,5)C1 (0,5)-1,00,9116
Example 17A7PXDA/MXDA 2/8Sabotinova acidB1 (1,0)C1 (1,0)-1,00,8119

Example 18A8PXDA/MXDA 5/5Sabotinova acidB1 (0,2)C1 (0,2)-1,01,0100
Comparative example 1N-MXD6 (S6007)MXDA Adipic acid----0,1550
Comparative example 2N-MXD6 (S6007)MXDAAdipic acid--D1 (0,5)-0,1540
Comparative example 3N-MXD6 (S6007)MXDAAdipic acid--D2 (0,5)-0,1545
Comparative example 4N-MXD6 (S6007)MXDAAdipic acid-C1 (0,5)--0,1555
Comparative example 5 N-MXD6 (S6007)MXDAAdipic acid-C1 (0,5)D1 (0,5)-0,1560
Comparative example 6A1MXDASabotinova acid----0,850

1. The polyamide resin composition used for obtaining a molded product that includes
(A) a polyamide consisting of diamino link containing 30 mol.% or more m-xylylenediamine link, and link dicarboxylic acid,
(B) a connection on the basis of aromatic secondary amine and
(C) connection on organic sulfur-based,
where
the polyamide resin composition is characterized by a coefficient of oxygen permeability not greater than 1 cm3·mm/m2·day·ATM at 23°C and 75% RH,
mix the amount of organic sulfur compounds on the basis of (C) is from 0.2 to 5 mass parts per 100 mass parts of the polyamide (A), and
the weight ratio between the compound on �Snov, aromatic secondary amine (V) and the compound for organic sulfur-based (C), the weight ratio (B)/(C) in the polyamide resin composition is in the range from 0.1 to 5.0.

2. The polyamide resin composition according to claim 1, wherein the diamino link contains 50 mol.% and more m-xylylenediamine link.

3. The polyamide resin composition according to claim 1, wherein the diamino link contains 70 mol.% and more m-xylylenediamine link.

4. The polyamide resin composition according to claim 1, wherein the diamino link contains m-xylylenediamine link and p-xylylenediamine link.

5. The polyamide resin composition according to claim 1, wherein the diamino link contains m-xylylenediamine link and p-xylylenediamine link and share m-xylylenediamine diamino link in the link is 30 mol.% and more.

6. The polyamide resin composition according to claim 1, where the link of the dicarboxylic acid contains 50 mol.% and more level α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms.

7. The polyamide resin composition according to claim 1, where the link of the dicarboxylic acid contains an element α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and link isophthalic acid.

8. The polyamide resin composition according to claim 1, where the link of the dicarboxylic acid contains an element α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and link isophthalic acid, and share the link of α,ω-linear aliphatic d�carboxylic acids in chain dicarboxylic acid is 50 mol.% and more.

9. The polyamide resin composition according to claim 1, where the link of the dicarboxylic acid contains an element α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, and link isophthalic acid, and share the link of α,ω-linear aliphatic dicarboxylic acid in chain dicarboxylic acid is 70 mol.% and more.

10. The polyamide resin composition according to any one of claims. 6-9, where the link of the linear aliphatic dicarboxylic acid is a part of adipic acid.

11. The polyamide resin composition according to any one of claims. 6-9, where the link of the linear aliphatic dicarboxylic acid is a link sabatinovka acid.

12. The polyamide resin composition according to any one of claims. 1-9, where the connection on the basis of aromatic secondary amine (b) are one or more representatives selected from compounds having diphenylamine skeleton, compounds having phenylnaphthylamine skeleton, and compounds having dinitramine skeleton.

13. The polyamide resin composition according to any one of claims. 1-9, where the connection on the basis of aromatic secondary amine (b) are one or more representatives selected from compounds having diphenylamine skeleton, and compounds having phenylnaphthylamine skeleton.

14. The polyamide resin composition according to any one of n�. 1-9, where the connection on the basis of aromatic secondary amine (b) are one or more representatives selected from N-phenyl-1-naphthylamine, p,p'-dialkyldiphenyl in which the number of carbon atoms in the alkyl group is from 8 to 14, accelerando of diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)of diphenylamine, p-(p-toluensulfonyl)of diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine, 2,2'-dinitramine, 1,2'-dinitramine and 1,1'-dinitramine.

15. The polyamide resin composition according to any one of claims. 1-9, where the connection on the basis of aromatic secondary amine (b) are one or more representatives selected from N,N'-di-2-naphthyl-p-phenylenediamine and 4,4'-bis(α,α-dimethylbenzyl)of diphenylamine.

16. The polyamide resin composition according to any one of claims. 1-9, where the connection on organic sulfur-based (C) are one or more representatives selected from compounds based mercaptobenzimidazole, compounds based on dithiocarbamates acid, compounds based on thiourea and compounds based on organic timeslot.

17. The polyamide resin composition according to any one of claims. 1-9, where the connection �and organic sulfur-based (C) are one or more representatives, selected from compounds based mercaptobenzimidazole and compounds based on organic timeslot.

18. The polyamide resin composition according to any one of claims. 1-9, where the connection on organic sulfur-based (C) are one or more representatives selected from 2-mercaptobenzimidazole, 2-mercaptobenzimidazole, Dimyristyl-3,3'-thiodipropionate, DISTEARYL-3,3'-thiodipropionate and pentaerithrityl(3-lawrenceofarabia).

19. The polyamide resin composition according to any one of claims. 1-9, where the connection on organic sulfur-based (C) are one or more representatives selected from pentaerithrityl(3-lawrenceofarabia), Dimyristyl-3,3'-thiodipropionate and 2-mercaptobenzimidazole.

20. A molded product containing the polyamide resin composition according to any one of claims. 1-19.

21. A molded product according to claim 20, which represents a hose or pipe.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to polymer films, intended for application in field of electrical engineering, in particular, as carrier of flexible printed circuit boards. Described is subjected to biaxial stretching polymer film, obtained from polyamide composition, which contains at least 80 wt % counted per the total weight of polymer composition of semi-crystalline semi-aromatic polyamide, which has melt temperature (Tm), equal to at least 300°C. Polymer film is characterised by average coefficient of thermal expansion in plane in temperature range 20°C-Tg, measured in plane by method, corresponding to ASTM D969-08, and equal, to at least, 40 ppm/K. Semi-crystalline semi-aromatic polyamide contains repeating units, produced from dicarboxylic acid, consisting of 70-100 mol. % of terephthalic acid, diamines, and other repeating units in quantity 0-5 mol. %. Also described is method of polymer film obtaining, application of polymer film as belt carrier in production of printed circuit boards, as flexible carrier. Flexible printing board, electronic system or printed circuit board in assembly is described.

EFFECT: stability of geometric dimensions, resistance to high temperature and good dielectric properties of polymer films.

13 cl, 2 tbl, 2 ex

FIELD: process engineering.

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Transparent films // 2528728

FIELD: chemistry.

SUBSTANCE: group of inventions relates to an optically transparent polymer product, such as a film or a three-dimensional extrudate, made from a polymer composition and a method for production and use thereof. The optically transparent polymer product, such as a film or a three-dimensional extrudate, is obtained from a polymer composition containing a semi-crystalline polyamide (A) wherein the semi-crystalline polyamide (A) has a melting temperature (Tm-A) of at least 270°C and is present in an amount of at least 60 wt % if the semi-crystalline polyamide (A) consists of a semi-aromatic semi-crystalline polyamide or a mixture of a semi-aromatic semi-crystalline polyamide and an aliphatic semi-crystalline polyamide, or at least 75 wt % if the semi-crystalline polyamide (A) consists of an aliphatic semi-crystalline polyamide, where the wt % is relative to the total weight of the polymer composition. The polymer composition has a melting point (Tm-C) of at least 270°C, and the film or part of the extrudate is characterised by haze of less than 12% and light transmittance of at least 88%, measured with the method according to ASTM D1003A. The method of producing a transparent polymer film includes steps of heating and melt-extruding a polymer composition through a slit die to form an extruded polymer layer, passing the extruded polymer layer over a chilling roll having a temperature below 40°C, thereby forming a polymer film, and collecting the polymer film. According to the after-treatment method, the transparent polymer film is subjected to drawing wherein the film is stretched, and/or heat setting and/or annealing, wherein transparent polymer film, having a glass transition point (Tg) and a melting point (Tm), is heated to or kept for a certain period at a temperature between the Tg and Tm. The method of producing the extrudate includes steps of: melt-extruding a polymer composition through a die, passing the extruded polymer composition through a quenching liquid having a temperature below 40°C, thereby forming a solid product, and collecting the solid product. According to another version of the group of inventions, a steam-sterilisable medical article comprising an extrudate is disclosed. According to yet another version, the transparent polymer product is used in packaging materials or in electrical engineering or electronics.

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15 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an aramid particle containing a peroxide radical chain polymerisation initiator, wherein the particle contains 3-40 wt % of a radical chain polymerisation initiator with respect to the weight of the aramid particle. The peroxide initiator is introduced into the aramid particle by saturating the aramid particle with a solution of the peroxide initiator in an organic solvent with subsequent evaporation of the latter. The aramid particle is fibre, crushed fibre, staple fibre, fibrid, fibril, powder or granules. Also described is an elastomer composition with aramid particles, an article made from skimmed latex which contains the elastomer composition with aramid particles, an industrial rubber article and a method of curing an elastomer in the presence of an aramid particle.

EFFECT: reduced Payne effect and hysteresis of rubber or other elastomeric articles, improved adhesion properties.

12 cl, 16 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of a composition for making at least one component of a car adjusting device. The composition contains partially crystalline, partially aromatic polyamide and is modified by at least one elastomer with weight ratio from 1% to 10% of the composition. The composition is used to make an adjusting device for changing the position of the controlled car component, having at least one gear wheel of a drive mechanism, one guide element and/or one sliding element.

EFFECT: invention enables to use the composition to make at least one component of an adjusting device and an adjusting device without considerable expenses with mechanical properties sufficient for operation.

14 cl, 7 dwg, 2 tbl, 2 ex

Foam from polymers // 2461589

FIELD: chemistry.

SUBSTANCE: method involves steps of a) preparing a solution containing 1-20 wt % polymer in NMP/CaCl2 or sulphuric acid; b) adding particles to the polymer solution; c) solidifying the polymer containing particles and d) optionally washing, drying and/or heating the polymer matrix. At step b) i) the particles are inert hollow particles in which the hollow part is a vacuum or gas-filled cells; or ii) the particles are solid particles which are insoluble in the solvent; wherein at step c) the solid particles are removed from the polymer matrix by dissolving in a second solvent or iii) the particles are expanded particles which, when dissolved at step b) and/or when heated at step c), release gas bubbles which form polymer foam. The polymer is selected from aramid and a rigid rod polymer.

EFFECT: method is universal for producing foam and foam-like materials.

14 cl, 13 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to production of cross-linkable aramide copolymer compositions and articles made therefrom. The composition contains an aramide copolymer obtained from monomers containing 1,4-phenylenediamine and tetraphthaloyl dichloride, and having at least one arylene-carboxylic acid link and at least one hydroxyarylene link. Alternatively, the composition contains an aramide copolymer obtained from monomers containing 1,4-phenylenediamine and tetraphthaloyl dichloride, and having at least one arylene-carboxylic acid link or at least one hydroxyarylene link and a covalent cross-linking agent. The invention also relates to cross-linked copolymers obtained from said composition and moulded articles containing such cross-linked copolymers.

EFFECT: invention enables to obtain materials with improved operational properties.

15 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing completely para-substituted aromatic polyamide particles for use as filler, which comprises the following steps: a) adding an aramide polymer solution to a water-based coagulation liquid to obtain a hydrogen-containing moulded product and b) crushing the frozen non-dried or partially dried moulded product, having water content from 10 to 99 wt %.

EFFECT: method enables simple and efficient production of small aromatic polyamide particles which cannot be obtained through traditional grinding methods.

8 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: composition contains a mixture of polyamide, where the ratio of terminal amino groups in the terminal carboxyl groups of the polyamide polymer is less than 0.2, polyester which is capable of crystallising and an interfacial tension reducing agent.

EFFECT: composition enables to obtain dispersed particles with average size of less than 200 nm when stretched, good colour composition which will not exhibit high increase in turbidity with increase in the amount of dispersed material, or has acceptable turbidity during production, and has good colour, especially in the absence of cobalt.

7 cl, 3 tbl, 18 ex, 8 dwg

FIELD: machine building.

SUBSTANCE: procedure consists in condensing polyamide moulding blend, polyamide of which has at least 30 % of end groups in form of end amino-groups of polycarbonate with 0.005 to 10 wt % in terms of used polyamide. At stage a) there is prepared polyamide moulding blend, b) there is produced mixture of polyamide moulding blend and polycarbonate, c) if necessary, blend is stored and/or transported by point b) and d) mixture is processed by point b) into a moulded item. The item corresponds to a hollow item or hollow profile with external diametre at least 30 mm and thickness of wall at least 1 mm. Condensing occurs only at stage of processing.

EFFECT: increased stiffness of melt at simultaneous reduced pressure during processing and insignificant load on engine, simplification of moulded items production.

6 cl, 1 ex, 2 tbl

Polyamide resin // 2544013

FIELD: chemistry.

SUBSTANCE: invention relates to polyamide resin, method of its obtaining, to composition based on polyamide resin, as well as to moulded product. Polyamide resin includes units of diamine, containing 90 mol % or more paraxylenediamine and units of dicarboxylic acid, containing 90 mol % or more units of sebacic acid and/or units of azelaic acid. Polyamide resin has concentration of phosphorus atoms from 50 to 1000 ppm and YI value 10 or lower in colour difference test in accordance with JIS-K-7105. Method of obtaining polyamide resin includes stage of polycondensation in melt of diamine component, containing 90 mol % or more of paraxylenediamine and component based on dicarboxylic acid, containing 90 mol % or more sebacic acid and/or azelaic acid, in presence of compound, containing phosphorus atoms. Composition, used for obtaining moulded product, includes 100 wt. p. of said polyamide resin and from 0.01 to 2 wt. p. of nucleating agent.

EFFECT: invention makes it possible to obtain polyamide resin, possessing good heat resistance, water absorption resistance, chemical stability, high physical and mechanical properties, and at the same time forms little amount of gel, is characterised by good colour tone and mouldability.

14 cl, 6 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention relates to application of moulded component for contact with supercritical medium. Moulded component represents sleeve or tube and contains inner thermoplastic layer made of moulding mass. Moulding mass contains at least 50 wt % of components, wt. p.: a) from 0 to 99 of polyamide, obtained from combination of diamine and dicarboxylic acid, as well as ω-aminocarboxylic acid and respective lactam and b) from 1 to 100 of polyamide elastomer, selected from the group, including polyether/polyester-amide and polyetheramide, with the sum of weight parts of components a) and b) constituting 100. Moulding mass contains additional components, including minimum to 9 wt % of plasticiser.

EFFECT: absence or small content of plasticiser makes it possible to nearly completely eliminate increase of rigidity and longitudinal product shrinkage.

13 cl

FIELD: chemistry.

SUBSTANCE: invention relates to a polyamide resin composition, which has excellent properties, such as thermal stability, resistance to chemical impact, strength, wear resistance and mouldability, and therefore is widely applied for the production of moulded products as an engineering plastics. The polyamide resin composition includes: a polyamide (A), containing a unit, representing diamine and containing not less than 70 mol% of a unit, representing p-xylylenediamine, and a unit, representing dicarboxylic acid and containing not less than 70 mol% of a unit, representing a linear aliphatic dicarboxylic acid, which has from 6 to 18 carbon atoms; and a filling agent (B). The polyamide (A) includes a polyamide with the concentration of phosphorus atoms, constituting from 50 to 1000 ppm, and a value YI, which by results of differential colorimetric analysis in accordance with JIS-K-7105, does not exceed 10. The content of the filling agent (B) constitutes from 1 to 200 wt.p. counted per 100 wt.p. of the polyamide (A).

EFFECT: invention makes it possible to obtain the resin with better mouldability and the moulded products based on the said polyamide resin with better thermal stability, low water absorption, and excellent sliding properties.

20 cl, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to composition based on polyamide resin for manufacturing moulded products. Composition contains polyamide, consisting of diamine units, containing units of 1,3-bis(aminomethyl)cyclohexane and units of dicarboxylic acid, including units of adipic and/or sebacic acid, (B) compounds of aromatic secondary amine, (C) organic sulphur-based compound and (D) phenolic oxidant. Weight ratio of components (B)/(C) in said composition constitutes from 0.5 to 10 and weigh ratio (D)/(C) in composition constitutes from 0.5 to 10. Polyamide resin-based composition is characterised by the fact that it has oxygen permeability coefficient not higher than 1.5 cubic cm·mm/m2.day·atm at temperature 23°C and relative humidity 75%. Moulded product, in particular hose or pipe is also described.

EFFECT: increased resistance to thermal ageing with preservation of gas-barrier properties of polyamides and products manufactured from them.

14 cl, 1 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to fire-resistant compositions of polyamide resin. Claimed is a fire-resistant composition of the polyamide resin, including a polyamide (A), which contains a unit, representing diamine and containing not less than 70 mol% of a unit, representing p-xylylenediamine, and a unit, representing dicarboxylic acid and containing not less than 70 mol% of a unit, representing a linear aliphatic dicarboxylic acid, which has from 6 to 18 carbon atoms; an organohalogen compound (B), which serves as fire-protective means; an inorganic compound (C), which serves as auxiliary fire-protective means; and an inorganic filling agent (D), where the polyamide (A) includes a polyamide, which has the concentration of phosphorus atoms, constituting from 50 to 1000 ppm, and a value YI, which by results of differential colorimetric analysis in accordance with JIS-K-7105, does not exceed 10, and the content of the organohalogen compound (B), the content of the inorganic compound (C) and the content of the inorganic filling agent (D) constitutes from 1 to 100 wt.p. from 0.5 to 50 wt.p. and from 0 to 100 wt.p., respectively, counted per 100 wt.p. of the polyamide (A). Also claimed is the moulded product from the said composition.

EFFECT: composition has excellent mouldability, mechanical properties, heat resistance and low water absorption.

15 cl, 4 tbl, 21 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polymer films, intended for application in field of electrical engineering, in particular, as carrier of flexible printed circuit boards. Described is subjected to biaxial stretching polymer film, obtained from polyamide composition, which contains at least 80 wt % counted per the total weight of polymer composition of semi-crystalline semi-aromatic polyamide, which has melt temperature (Tm), equal to at least 300°C. Polymer film is characterised by average coefficient of thermal expansion in plane in temperature range 20°C-Tg, measured in plane by method, corresponding to ASTM D969-08, and equal, to at least, 40 ppm/K. Semi-crystalline semi-aromatic polyamide contains repeating units, produced from dicarboxylic acid, consisting of 70-100 mol. % of terephthalic acid, diamines, and other repeating units in quantity 0-5 mol. %. Also described is method of polymer film obtaining, application of polymer film as belt carrier in production of printed circuit boards, as flexible carrier. Flexible printing board, electronic system or printed circuit board in assembly is described.

EFFECT: stability of geometric dimensions, resistance to high temperature and good dielectric properties of polymer films.

13 cl, 2 tbl, 2 ex

Copolyamides // 2533377

FIELD: chemistry.

SUBSTANCE: copolyamide includes units resulting from a reaction of polycondensation of the following precursors: terephthalic acid (a), aliphatic diamine (b), including x carbon atoms, where x represents an integer number between 6 and 22, and aminocarboxylic acid and/or lactam (c). Aminocarboxylic acid and/or lactam includes a basic chain and, at least, one linear or branched alkyl branching, with the total number of carbon atoms being equal to a value between 12 and 36. The method of the copolyamide obtaining consists in the fact that polycondensation of the precursors (a), (b), (c) is carried out. The composition includes, at least, one copolyamide.

EFFECT: invention makes it possible to obtain the copolyamide with high melting temperature and good flexibility, increase the copolyamide plasticity and impact strength.

30 cl, 3 tbl

Polyamide resin // 2525311

FIELD: chemistry.

SUBSTANCE: invention relates to polyamide resin, suitable for application in production of articles of industrial and household purpose, such as automobile components, components of electrotechnical and electronic equipment, components of machines. Polyamide resin is obtained by polycondensation of diamine component and component based on dicarboxylic acid, where 70 mol.% or more of diamine component represent p-xilylene diamine of constituting units, component based on dicarboxylic acid represents aliphatic dicarboxylic acid, containing from 6 to 18 carbon atoms. Polyamide resin has number average molecular weight Mn from 10000 to 50000 and degree of dispersity, expressed as Mn/Mw= weight average molecular weight/number average molecular weight, satisfying the following formula (1): 1.5≤(Mw/Mn)≤6.0(1) where Mn and Mw are determined by gel-penetrating chromatography GPC, with polyamide resin having molar balance with excess of carboxylic acid. Also described is composition, based on polyamide resin, used for obtaining moulded articles.

EFFECT: particularly high ability of moulding and processing, high heat resistance, low water absorption, high chemical resistance and good physical-mechanical properties.

5 cl, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to copolyamide, method of its obtaining, to polyamide-containing composition, application of polyamide and hypophosphorous acid or, at least, one of its salts. Copolyamide contains, at least, two links, corresponding to the following general formula: A/10.T. A is selected from the link, obtained from amino acid, link, obtained from lactam, and link, corresponding to the formula (Ca-diamine).(bibasic Cb-cycloaliphatic acid), where a stands for the number of diamine carbon atoms and b stands for the number of carbon atoms of bibasic acid. Each of a and b is in the range from 4 to 36. 10.T stands for the link, obtained as a result of polycondensatuon of 1,10-decandiamine and terephthalic acid. Copolyamide has polydispersion coefficient, measured by the method of gel permeation chromatography, denotes as lp, lower or equal to 3.5. Method of copolyamide obtaining lies in the following: stage of polycondensation of the following comonomers of monomer, resulting in A link, 1,10-decandiamine, and terephthalic acid, and optionally monomer, resulting in Z link, is carried out. polycondensation is carried out in presence of hypophosphorous acid or, at least, one of its salts in the amount in the range from 0.05 to 3.00 wt % with respect to the total weight of monomers. Application of hypophosphorous acid makes it possible to obtain polydispersion coefficient lower or equal to 3.5. Copolyamide is applied in form of powder, granulated products, monolayer structure, or, at least, one layer of multi-layer structure as additive and/or filling agent with improved thermal resistance. Such copolyamide is used in composition, which contains, at least, one additive, selected from filling agents, glass fibre, dyes, stabilisers, in particular UV-stabilisers, plasticisers, shock resistance modifiers surface active substances, pigments, bleaches, antioxidants, natural waxes, polyolefins and their mixtures.

EFFECT: invention makes it possible to obtain copolyamide with improved mechanical properties and shock resistance.

17 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to copolyamide, method of its obtaining, copolyamide-containing composition, as well as to application of copolyamide and composition. Copolyamide contains, at least, two different links and corresponds to the following general formula: A/X.T. A is selected from the link, obtained from amino acid, link, obtained from lactam, and link, corresponding to formula (Ca-diamine).(Cb-diacid), Ca stands for the number of carbon atoms in diamine. Cb stands for the number of carbon atoms in diacid. Each of a and b is in the range from 4 to 36, preferably from 9 to 18. X.T stands for the link, obtained by polycondensation of linear aliphatic Cx-diamine and terephthalic acid. X stands for the number of carbon atoms and is in the range from 9 to 36, preferably from 10 to 18. Copolyamide has content of end amino groups larger or equal to 20 milli-equiv/g, content of acid end groups lower or equal to 100 milli-equiv/g, content of non-reactive end groups larger or equal to 20 milli-equiv/g. Method of copolyamide obtaining lies in carrying out polycondensation of the following copolymers: monomers, resulting in links A and X, terephthalic acid and, optionally, monomer, resulting in link Z, and, at least, one chain growth regulator. Composition contains, at least, one said copolyamide and, at least, one additive, selected from group, including filling agents, glass fibre, dyes, stabilisers, in particular UV-stabilisers, plasticisers, modifiers of shock viscosity, surface active substances, pigments, bleaches, antioxidants, natural waxes, polyolefins and their mixtures. Composition and copolyamide are applied in form of powder, granules, monolayer structure or, at least, one layer of multilayer structure. Composition and copolyamide are used as additive and/or filling agent in production of components or parts of electric and electronic equipment, automobile equipment, equipment for transportation and transfer of gas, oil and their compounds.

EFFECT: invention makes it possible to increase mechanical properties of copolyamides.

31 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to composition based on polyamide resin for manufacturing moulded products. Composition contains polyamide, consisting of diamine units, containing units of 1,3-bis(aminomethyl)cyclohexane and units of dicarboxylic acid, including units of adipic and/or sebacic acid, (B) compounds of aromatic secondary amine, (C) organic sulphur-based compound and (D) phenolic oxidant. Weight ratio of components (B)/(C) in said composition constitutes from 0.5 to 10 and weigh ratio (D)/(C) in composition constitutes from 0.5 to 10. Polyamide resin-based composition is characterised by the fact that it has oxygen permeability coefficient not higher than 1.5 cubic cm·mm/m2.day·atm at temperature 23°C and relative humidity 75%. Moulded product, in particular hose or pipe is also described.

EFFECT: increased resistance to thermal ageing with preservation of gas-barrier properties of polyamides and products manufactured from them.

14 cl, 1 tbl, 16 ex

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