WO2018068705A1 - Polyamide, preparation method therefor, and metal adaptor - Google Patents

Abstract

The present invention provides a chained aliphatic polyamide resin having outstanding formation machining performance, thermal performance and mechanical performance, and a preparation method therefor. Main technical characteristics are as follows: the chained aliphatic polyamide resin having polyethenoxyamine blocks, the structure of each polyethenoxyamine block is represented by formula I, a, b and c in the formula I are positive numbers that are same or different, R₁, R₂ and R₃ are alkyls that are same or different and whose quantity of hydrogen atoms or carbon atoms is greater than 1 and is less than 10; the number-average molecular weight of the polyethenoxyamine block is greater than 500 and is less than 1500, and the content of the polyethenoxyamine blocks in the chained aliphatic polyamide resin is greater than 0.5 wt% and less than 15 wt% of the total weight of the chained aliphatic polyamide resin; when the chained aliphatic polyamide resin is prepared into a chained aliphatic polyamide resin solution whose content is 0.01 g/ml by using sulfuric acid at 96 wt% as a solvent, the relative viscosity ηr measured at the 25ºC is greater than 1.1 and less than 4.0.

Description

Polyamide, preparation method thereof and metal joint Technical field

The invention belongs to the field of polymer materials, and particularly relates to a chain aliphatic polyamide resin containing a polyether diamine block and a preparation method thereof.

Background technique

Polyamide resins are widely used in various molded articles such as fibers, various containers, films, electronic components, automotive parts, and machine parts because of their excellent mechanical properties and heat resistance.

In recent years, there has been an increasing demand for miniaturization of molded articles, complicated shapes, thinner walls, and lighter weight. Therefore, research and development of materials having excellent moldability and mechanical properties have become particularly important. On the other hand, lower molding temperatures and shorter molding cycles are also conducive to energy saving. In general, as the molecular weight of the polyamide resin increases, the mechanical properties of the polyamide resin also increase. However, the increase in molecular weight also brings about negative effects such as an increase in melt viscosity and a decrease in moldability.

In order to improve the melt flowability of the polyamide resin, branching of the polyamide resin is a common method (Chinese Patent Application Nos. CN101939358A, CN101421336A, CN1108329C, CN102203187A). However, the branched structure reduces the crystallization and mechanical properties of the polyamide resin.

Japanese Patent Application Publication No. JPA1986163935 discloses a polyamide resin having improved mechanical properties and moldability, the polyamide resin having an alkyl group having 6 to 22 carbon atoms and a relative viscosity of 2.5 to 6. However, the melt viscosity of the polyamide resin obtained by this method is still high, and there is still a problem that the molding processability is insufficient for the demand for miniaturization, complication, thinning, and weight reduction of the molded article which has been increasing in recent years. On the other hand, Chinese patent application CN101426833A discloses a copolymer comprising alternating polyamide resin block PA and polyether block PE, which copolymer has improved optical and mechanical properties. Another Chinese patent application CN1872897A discloses a thermoplastic elastomer which can be obtained by reactive coupling of a polyamide prepolymer having a hydroxyl end group and an isocyanate terminated polyether prepolymer. However, the polyether amide block copolymer described in the above patent has a high melt viscosity, and the problem of insufficient moldability is still present. At the same time, there are problems such as a decrease in the melting point of the polyamide homopolymer, a lower melting crystallization temperature, a slow curing speed during injection molding, and a long molding cycle.

Chinese patent application CN105400187A discloses a thermoplastic polyamide and an amine terminated a highly flowable thermoplastic polyamide resin composition of polyether, but in the composition most of the amine-terminated polyether is present in a state in which it is not chemically bonded to the polyamide, although the amine-terminated polyether present in the above state exists The melt viscosity of the polyamide resin composition can be lowered to some extent, but the effect is not remarkable. On the other hand, the above-mentioned polyamide resin composition also has a drawback that the surface amine-terminated polyether of the molded article is easily precipitated.

The international patent application publication WO 2015/182693 discloses a low melt viscosity terminally modified polyamide resin having a specific end group structure. Although the introduction of the polyether structure to the end of the polyamide greatly reduces the melt viscosity of the polyamide resin, it takes a long time to increase the degree of polymerization due to the capping action of the monoamine-based polyether on the active end of the polyamide, resulting in production. low efficiency.

The international patent application publication WO 2012/111636 discloses a semi-aromatic polyamide elastomer containing a polyether diamine block. A semi-aromatic polyamide elastomer having good heat resistance, crystallinity, and flexibility is obtained by introducing a polyether diamine block, but a tensile modulus exists in comparison with a corresponding semi-aromatic polyamide homopolymer. The problem of a significant drop in mechanical properties.

On the other hand, with the three major problems of energy, safety and environmental protection becoming more and more prominent, automobile lightweighting has received more and more attention. Due to the much lower density than metal, the application of engineering plastics in automobiles has gradually increased, but in some structural components, the mechanical strength of engineering plastics is still difficult to meet the demand. The metal/plastic hybrid composite combines the high strength of metal with the light weight of plastic, while meeting the mechanical strength requirements and lightweight requirements of automotive structural components.

At present, the metal member and the plastic are bonded together by mechanical riveting and adhesive bonding to form a hybrid composite material. However, in these joining methods, the plastic component and the metal component need to be processed separately, and then joined by riveting, gluing or the like. Together form the finished part.

In recent years, more and more research has been conducted on a method in which a resin is directly joined to a metal by injection molding. The international patent application publication WO 2012/132639 discloses a composite of a thermoplastic resin and a metal, which contains an inorganic filler capable of increasing the crystallization temperature of the resin, but the composite obtained by the method has a bond between the resin and the metal. Sex is still insufficient.

The international patent application publication WO 2015/022955 discloses a composite of a thermoplastic resin and a metal, which may be a polyether copolymer modified polyamide elastomer or a thermoplastic resin composition composed of a water-absorbing thermoplastic resin and a metal hydroxide. Things. However, the mechanical properties of polyamide elastomers are significantly reduced compared to polyamide homopolymers. On the other hand, the polyamide elastomer has a lower glass transition temperature than the polyamide homopolymer, and the curing speed is slower at the time of injection molding, and the molding cycle is lengthened. At the same time, the polyamide elastomer has poor adhesion to metals.

Chinese Patent Application Publication No. CN105479659A discloses a composite of a plastic material and a metal material comprising a polyether block amide. Although the plastic material and the metal have excellent bonding strength and provide a certain degree of sealing property, due to the polyether block amide The content of the polyether structure is high, and the mechanical properties of the polyether block amide are degraded compared with the polyamide homopolymer, and the bonding property of the polyether block amide with the metal is insufficient.

Summary of the invention

The present invention contains a flexible polyether diamine block having a specific molecular weight in a molecular chain of a chain aliphatic polyamide to achieve the purpose of lowering the melt viscosity and improving the molding processability, and contains the same as the corresponding homopolymer. The thermal properties of the polyether diamine block chain aliphatic polyamide resin are maintained, and the deterioration of mechanical properties is also controlled to a minimum. On the other hand, the polymerization time required in the preparation method of the polyamide resin is also reduced. Further, the thermoplastic resin composition containing the polyamide resin of the present invention has also been found to have excellent metal bondability.

The invention consists of the following:

A chain aliphatic polyamide resin comprising a polyether diamine block, the polyether diamine block having a structure as shown in Formula I,

In the above formula I, a, b, and c are positive numbers, and R ₁ , R ₂ , and R ₃ are the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; The number average molecular weight of the segment is 500 or more and less than 1500 and the content of the polyether diamine block in the chain aliphatic polyamide resin is 0.5% by weight or more and 15% by weight or less based on the total weight of the chain aliphatic polyamide; When the aliphatic aliphatic polyamide resin is formulated into a chain aliphatic polyamide resin solution having a concentration of 0.01 g/ml using 96 wt% sulfuric acid as a solvent, the relative viscosity ηr measured at 25 ° C is 1.1 or more and 4.0 or less.

2. The chain aliphatic polyamide resin according to the above 1, wherein 2 ≤ a + c ≤ 10, and 1.5 ≤ b ≤ 31, and R ₁ , R ₂ and R _{3 are} simultaneously methyl groups. .

3. The chain aliphatic polyamide resin according to the above 1, wherein the chain aliphatic polyamide resin contains no block other structure than the polyether diamine block.

4. The chain aliphatic polyamide resin according to the above 1, wherein the chain aliphatic polyamide resin has a formula II of 0.005 mmol/g or more and 0.1 mmol/g or less based on the total weight of the chain aliphatic polyamide resin. End group shown

-Y-(R ₄ -O) _m -R ₅ formula II;

-Y- in the above formula II is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH (OH)-CH ₂ -, m is an integer of 2 or more and 100 or less, and R _{4 is the} same or different, and is an alkylene group having 2 or more and 10 or less carbon atoms, and R ₅ is 1 or more and 30 or less. The following alkyl groups.

5. The chain aliphatic polyamide resin according to the above 1, wherein the chain aliphatic polyamide resin has a formula III of 0.005 mmol/g or more and 0.1 mmol/g or less based on the total weight of the chain aliphatic polyamide resin. End group shown

-ZR ₆ type III;

-Z- in the above formula III is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH (OH)-CH ₂ -, R ₆ is an alkyl group having 1 or more and 30 or less carbon atoms, an alkyl group substituted with an aryl group, an aryl group or an alkyl group substituted with an alkyl group.

(6) The chain-like aliphatic polyamide resin according to any one of the above-mentioned items 1 to 5, wherein the chain-like aliphatic polyamide resin has a weight average molecular weight Mw in a range of 10,000 or more and 400,000 or less. .

The chain aliphatic polyamide resin according to any one of the above 1 to 5, wherein the chain aliphatic polyamide resin has a melting point of 215 ° C or higher.

The chain aliphatic polyamide resin according to any one of claims 1 to 5, wherein the chain aliphatic polyamide resin is an ISO19095 test strip at a tensile speed of 5 mm/ The joint strength with metal aluminum measured at min is 10 MPa or more.

9. A method for preparing a chain aliphatic polyamide resin, which comprises polymerizing one or more of an aminocarboxylic acid, a lactam or a dibasic acid/diamine as a monomer to prepare a chain aliphatic polyamide resin In the process of adding a polyether diamine as shown in formula IV,

In the above formula IV, d, e, and f are each a same or different positive number, and R ₇ , R ₈ , and R ₉ are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; The polyether diamine has a molecular weight of 500 or more and less than 1,500 and the polyether diamine is added in an amount of 0.5% by weight or more and 15% by weight or less based on the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer. .

10. The method for producing a chain aliphatic polyamide resin according to the above 9, wherein d, e, and f in the formula IV satisfy 2 ≤ d + f ≤ 10, and 1.5 ≤ e ≤ 31; R ₇ , R ₈ And R _{9 are} simultaneously methyl.

11. The method for producing a chain aliphatic polyamide resin according to the above 9, further comprising a compound represented by Formula V

U-(R ₁₀ -O) _n -R ₁₁ Formula V;

In the above formula V, n is an integer of 2 or more and 100 or less, R ₁₀ is an alkylene group having 2 or more and 10 or less carbon atoms, and R ₁₁ is an alkyl group having 1 or more and 30 or less carbon atoms, and U is NH. ₂ -, HO-, HO-C(=O)-, O=C=NR ₁₂ -NH-C(=O)-O-, O=C=NR ₁₃ -NH-C(=O)-NH- or

Here, R ₁₂ or R ₁₃ are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.

12. The method for producing a chain aliphatic polyamide resin according to the above 9, further comprising a compound represented by Formula VI

WR ₁₄ type VI;

In the above formula VI, R ₁₄ is an alkyl group or an aryl-substituted alkyl group, an aryl group or an alkyl-substituted aryl group having 1 or more and 30 or less carbon atoms, and W- is NH ₂ -, HO-, HO-C (= O)-, O=C=NR ₁₅ -NH-C(=O)-O-, O=C=NR ₁₆ -NH-C(=O)-NH- or

Here, R ₁₅ or R ₁₆ are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.

13. A bonded body of a thermoplastic resin composition and a metal, wherein the thermoplastic resin composition contains the chain aliphatic polyamide resin according to any one of the above 1 to 5.

The above summary of the invention is described in detail below:

The chain aliphatic polyamide resin of the present invention contains a polyether diamine block, and the structure of the polyether diamine block is as shown in Formula I,

In the above formula I, a, b, and c are positive numbers, and R ₁ , R ₂ , and R ₃ are the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; The number average molecular weight of the segment is 500 or more and less than 1500 and the content of the polyether diamine block in the chain aliphatic polyamide resin is 0.5% by weight or more and 15% by weight or less based on the total weight of the chain aliphatic polyamide resin; When the chain aliphatic polyamide resin is formulated into a chain aliphatic polyamide resin solution having a concentration of 0.01 g/ml using 96 wt% sulfuric acid as a solvent, the relative viscosity ηr measured at 25 ° C is 1.1 or more and 4.0 or less.

The chain aliphatic polyamide resin of the present invention has a polyether diamine block as shown in the above formula I at least in a part of the molecular chain. The chain aliphatic polyamide resin described herein is preferably a polyamide resin having an aromatic component content of 20% by weight or less, more preferably a polyamide resin having an aromatic component content of 10% by weight or less and a branched structure content of 0.04% by weight or less. .

Since the structure represented by Formula I contains an ether bond, it is highly mobile and has a strong affinity with an amide bond. By introducing the flexible polyether diamine block into the molecular chain of the chain aliphatic polyamide, the flexibility of the polyamide molecule is improved, so that the molecular mobility of the polyamide is greatly increased, thereby lowering the melt viscosity and improving the molding processability. .

In the above formula I, a, b, and c are preferably positive numbers within a range of 1 or more and 31 or less each of the same or different, and when any one of the values a, b, and c exceeds 31, the melt viscosity lowering effect is deteriorated. At the same time, the heat resistance of the polyether diamine block structure is also deteriorated; and when any of the values of a, b, and c is less than 1, the crystallinity of the polyamide resin is largely impaired. In view of the effect of reducing the melt viscosity and the crystallinity of the obtained polyamide resin, a, b, and c satisfy the following conditions: 2 ≤ a + c ≤ 10 and 1.5 ≤ b ≤ 31. Further preferably, 3 ≤ a + c ≤ 8 and 7 ≤ b ≤ 15; still more preferably 5 ≤ a + c ≤ 7 and 10 ≤ b ≤ 14. Here, since the polyether diamine block has a molecular weight distribution, a+c and b herein mean an average value.

In the above formula I, R ₁ , R ₂ and R ₃ are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms. Considering the stability of the polyether diamine block structure and the interaction between the molecular chains and the complexation between the molecular chains, it is preferred that R ₁ , R ₂ and R ₃ are alkyl groups having 1 or more and 10 or less carbon atoms. . When R ₁ , R ₂ , and R ₃ are alkyl groups, the smaller the number of carbon atoms in R ₁ , R ₂ , and R ₃ , the higher the affinity with the main structural unit of the polyamide, and the polyether 2 The amine block is less likely to form a condensed state, and it is preferable that R ₁ , R ₂ and R ₃ are an alkyl group having 1 or more and 5 or less carbon atoms, and more preferably R ₁ , R ₂ and R ₃ are 1 or more carbon atoms. Further, an alkyl group of 2 or less is most preferably a methyl group at the same time as R ₁ , R ₂ and R ₃ .

The polyether diamine block represented by the above formula I has a number average molecular weight of 500 or more and less than 1,500. When the number average molecular weight is less than 500, the crystallinity and mechanical properties of the corresponding polyamide resin are deteriorated. In view of the retention of the crystallinity and mechanical properties of the polyamide resin, it is more preferable that the number average molecular weight of the polyether diamine block is 550 or more, and it is more preferable that the number average molecular weight of the polyether diamine block is 850 or more. On the other hand, when the number average molecular weight of the polyether diamine block is 1,500 or more, the effect of lowering the melt viscosity is inferior, and the improvement in moldability is limited. Further preferably, the polyether diamine block has a number average molecular weight of 1200 Further, it is more preferable that the number average molecular weight of the polyether diamine block is 1100 or less.

The polyether diamine block represented by Formula I in the chain aliphatic polyamide resin of the present invention is contained in the chain aliphatic polyamide resin in an amount of 0.5% by weight or more and 15% by weight or less (based on the weight of the chain aliphatic polyamide resin) 100 wt%, the same below), by making the polyether diamine block of the formula I having a mass content of 0.5% by weight or more, the purpose of lowering the melt viscosity and improving the moldability can be achieved. The content of the polyether diamine block in the chain aliphatic polyamide resin is preferably 1% by weight or more, more preferably 1.5% by weight or more, still more preferably 2% by weight or more; on the other hand, by the polymerization of Formula I When the mass ratio of the ether diamine block is 15% by weight or less, the crystallinity and mechanical properties of the chain aliphatic polyamide resin can be more preferably maintained, and it is preferably 11% by weight or less, further preferably 6% by weight or less, and still more preferably 4.5 wt% or less. Here, the content (wt%) of the polyether diamine block represented by the above formula I with respect to the chain aliphatic polyamide resin was obtained by 1H-NMR (nuclear magnetic resonance) test.

When the chain aliphatic polyamide resin of the present invention is formulated into a solution having a concentration of 0.01 g/ml using 96% by weight of concentrated sulfuric acid as a solvent, the relative viscosity ηr measured at 25 ° C is preferably 1.1 or more and 4.0 or less. When ηr is less than 1.1, the mechanical properties of the composition are poor. Preferably, ηr is 1.2 or more, and further preferably 1.4 or more. On the other hand, when ηr is more than 4, the molecular weight is too high, and thus the melt viscosity is too high, and the moldability is too poor, and ηr is preferably 3 or less. When the polyamide resin composition contains a filler described later in an amount of 1% by mass or more, the filler should be removed to a state where the mass content is less than 1%, and then the viscosity is measured.

The chain aliphatic polyamide resin of the present invention may contain, in addition to the polyether diamine block, a block of another structure such as a polyolefin block, a polyester block or the like. However, in consideration of the melt viscosity lowering effect and the retention of crystallinity, it is preferred that the chain aliphatic polyamide resin does not contain a block having another structure except for the polyether diamine block. The block of the other structure referred to herein means a polymer block other than the polyether diamine block having the number of repeating units of 8 or more.

The terminal group of the chain aliphatic polyamide resin of the present invention is not particularly required, and may be a reactive terminal group such as an amino group or a carboxyl group, or may be another non-reactive terminal group. In order to further lower the melt viscosity of the chain aliphatic polyamide resin of the present invention, a terminal group represented by Formula II is preferable as a non-reactive terminal group.

-Y-(R ₄ -O) _m -R ₅ formula II;

-Y- in the above formula II is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH (OH)-CH ₂ -, m is an integer of 2 or more and 100 or less, and R _{4 is the} same or different, and is an alkylene group having 2 or more and 10 or less carbon atoms, and R ₅ is 1 or more and 30 or less. The following alkyl groups. In view of the affinity with the main structural unit of the polyamide resin, -Y- in the above formula II is preferably one of -NH-, -O-, or -C(=O)-. In order for the thermoplastic resin composition used in the present invention to have a low melt viscosity, the affinity of the polyether end to the polyamide main chain is preferably high, and -Y- is preferably -NH-.

When m in the above formula II is less than 2, the effect of lowering the melt viscosity and maintaining the crystallinity is inferior, and the moldability and crystallinity are insufficient. m is preferably 4 or more, further preferably m is 8 or more, and most preferably m is 10 or more. On the other hand, when m is more than 100, the end group structure is inferior in heat resistance. m is preferably 70 or less, more preferably m is 35 or less, and most preferably m is 25 or less.

In the above formula II, R _{4 is the} same or different and is an alkylene group having 2 or more and 10 or less carbon atoms. R ₄ may specifically be -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ - , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, and the like. In view of affinity with the main structural unit of the polyamide resin, an alkylene group having 2 or more and 6 or less carbon atoms is preferable, and an alkylene group having 2 or more and 4 or less carbon atoms is more preferable. The n R ₄ groups may be composed of different alkylene groups, most preferably -CH ₂ -CH ₂ - and -CH(CH ₃ )-CH ₂ -.

In the above formula II, R ₅ is an alkyl group having 1 or more and 30 or less carbon atoms. The smaller the number of carbon atoms in R ₅ , the higher the affinity with the main structural unit of the polyamide resin. Therefore, R ₅ is preferably an alkyl group having 1 or more and 20 or less carbon atoms, and more preferably 1 carbon atom. The alkyl group of the above 10 or less is more preferably an alkyl group having 1 or more and 5 or less carbon atoms, and most preferably a methyl group.

The chain aliphatic polyamide resin of the present invention preferably contains a terminal group represented by Formula II at least at a terminal of a part of the polyamide molecular chain, and the terminal group has a content of 0.005 mmol or more in 1 g of the chain aliphatic polyamide resin. When the content of the terminal group represented by the formula II in 1 g of the chain-like aliphatic polyamide resin is controlled to be 0.005 mmol or less, the molecular weight of the polyamide resin is increased slowly during melt retention, thereby improving melting. On the other hand, the melt viscosity of the polyamide resin can be further lowered to further improve the moldability, and is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, and still more preferably 0.03 mmol/g or more. On the other hand, by controlling the content of the terminal group represented by Formula II in 1 g of the chain aliphatic polyamide resin to 0.1 mmol or less, the molecular weight of the chain aliphatic polyamide resin can be made easier. The progress is preferably 0.08 mmol/g or less, more preferably 0.07 mmol/g or less, and most preferably 0.06 mmol/g or less. Here, the content of the terminal group represented by the above formula II with respect to the polyamide resin (mmol/g) was obtained by a 1H-NMR (nuclear magnetic resonance) test. Melt retention stability by melting the polyamide resin under a nitrogen atmosphere at a melting point of Tm + 40 ° C for 1 hour, and measuring its weight average molecular weight (Mw) by GPC, and calculating its Mw increase relative to the melt retention. Rate, expressed as a percentage. The Mw increase rate is preferably 60% or less, more preferably 40% or less, still more preferably 20% or less.

As the non-reactive terminal group of the chain aliphatic polyamide resin of the present invention, the other is preferably a terminal group as shown in Formula III

-ZR ₆ type III;

-Z- in the above formula III is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH (OH)-CH ₂ -, R ₆ is an alkyl group having 1 or more and 30 or less carbon atoms, an alkyl group substituted with an aryl group, an aryl group or an alkyl group substituted with an alkyl group. In view of the affinity with the main structural unit of the polyamide resin, -Z- in the above formula III is preferably -NH- or -C(=O)-, and R ₆ is preferably an alkane having 1 or more and 20 or less carbon atoms. Base or phenyl.

The chain aliphatic polyamide resin of the present invention preferably contains a terminal group represented by Formula III at least at a terminal of a part of the polyamide molecular chain, and the terminal group has a content of 0.005 mmol or more in 1 g of the chain aliphatic polyamide resin. When the content of the terminal group represented by Formula III in 1 g of the chain-like aliphatic polyamide resin is controlled to 0.005 mmol or less, the molecular weight of the polyamide resin is increased slowly during melt retention, thereby improving melting. The retention stability is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, still more preferably 0.03 mmol/g or more; on the other hand, the terminal group represented by Formula III is aggregated at 1 g of the chain aliphatic group. When the content of the amide resin is controlled to 0.1 mmol or less, the molecular weight of the chain aliphatic polyamide resin can be more easily carried out, and it is preferably 0.08 mmol/g or less, more preferably 0.07 mmol/g or less, and most preferably 0.06 mmol/ g below. Here, the content of the terminal group represented by the above formula III with respect to the polyamide resin (mmol/g) was obtained by 1H-NMR (nuclear magnetic resonance) test.

The weight average molecular weight (Mw) of the chain aliphatic polyamide resin of the present invention is preferably 10,000 or more. When the Mw reaches 10,000 or more, the mechanical properties can be further improved. Mw is further preferably 20,000 or more, and still more preferably 30,000 or more. Further, Mw is preferably 400,000 or less. When the Mw is 400,000 or less, the melt viscosity is low and the formability is good. Mw is more preferably 300,000 or less, still more preferably 250,000 or less. The weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC).

The present invention is intended to obtain a chain-like aliphatic polyamide resin having good heat resistance. Therefore, the melting point (Tm) of the chain aliphatic polyamide resin is preferably 215 ° C or higher, and further preferably the melting point of the chain aliphatic polyamide resin ( Tm) is above 218 °C. The invention adopts the structure and number average of the polyether diamine block The above definition of the amount and content allows the decrease in the melting point and the crystallization temperature of the chain aliphatic polyamide resin after the introduction of the polyether diamine block to the minimum. The melting point of the chain aliphatic polyamide resin containing the polyether diamine block is not more than 5 ° C, and preferably the melting point is not more than 3 ° C, as compared with the melting point of the corresponding chain aliphatic polyamide homopolymer. Meanwhile, the melting crystallization temperature of the chain aliphatic polyamide resin containing the polyether diamine block is not more than 5 ° C, preferably the melting crystallization temperature, compared with the melting crystallization temperature of the corresponding chain aliphatic polyamide homopolymer. The drop does not exceed 3 °C. The melting point and melt crystallization temperature of the polyamide resin described herein are determined by differential scanning calorimetry (DSC): the polyamide resin is accurately weighed 5 to 7 mg, and the temperature is raised at a temperature rising rate of 20 ° C/min under a nitrogen atmosphere. At 20 ° C, the temperature is raised to a temperature 30 ° C higher than the peak temperature T0 of the endothermic peak, and the temperature is kept at this temperature for 2 min, and then the temperature is lowered to 20 ° C at a temperature drop rate of 20 ° C / min, during the above-mentioned cooling process. The temperature corresponding to the peak tip of the exothermic peak appearing is defined as the melting crystallization temperature (Tc), and thereafter is again raised to a temperature 30 ° C higher than T0 at a temperature increase rate of 20 ° C/min, during the second heating process. The temperature corresponding to the peak tip of the endothermic peak appearing is defined as the melting point (Tm).

The main component of the chain aliphatic polyamide resin of the present invention may be exemplified by, but not limited to, the following examples: polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene diamine (nylon) 46), polyhexamethylene pentane diamine (nylon 56), polysebacyl diamine (nylon 410), polysebacyl pentane diamine (nylon 510), polyphthalamide (nylon 610) Polydodecyl hexamethylenediamine (nylon 612) and a copolymer of the above polymers. In order to obtain characteristics such as heat resistance, toughness, or surface properties, a blend of two or more kinds of terminal-modified polyamide resins may be selected.

Further preferred are polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene pentane diamine (nylon 56), polysebacyl diamine (nylon 410), polydidecyl pentylene Diamine (nylon 510), polydecamethylenediamine (nylon 610), or polycaprolactam/polyhexamethylene adipamide (nylon 6/66).

In the present invention, in order to obtain a chain-like aliphatic polyamide resin having the above-mentioned relative viscosity range, a method for producing a chain aliphatic polyamide resin containing a polyether diamine block described later may be exemplified by amino acid, The ratio of the lactam or the dicarboxylic acid/diamine as the monomer starting material and the polyether diamine of the formula IV to the preferred total amino group amount [NH ₂ ] and the total carboxyl group amount [COOH] described later [ The ratio of NH ₂ ]/[COOH] was carried out. When the starting material is a lactam, an amount of the amino groups [NH _2] or carboxy groups [COOH] is the amount of the amino-lactam hydrolysis [NH _2] or carboxy groups [COOH].

In the present invention, in order to obtain a chain-like aliphatic polyamide resin having the above Mw range, a method for producing a chain aliphatic polyamide resin containing a polyether diamine block described later, which is a raw material, may be mentioned. The ratio of the preferred total amino group amount [NH ₂ ] and the total carboxyl group amount [COOH] of the amino acid, lactam, dicarboxylic acid and diamine and the polyether diamine of the formula IV to the following [NH ₂ ] /[COOH] is used for the ratio. When the starting material is a lactam, an amount of the amino groups [NH _2] or carboxy groups [COOH] is the amount of the amino-lactam hydrolysis [NH _2] or carboxy groups [COOH].

The melt viscosity ratio as shown in the following formula VII is also defined in the present invention:

Melt viscosity ratio (%) = {(melt viscosity of chain aliphatic polyamide resin containing polyether diamine block) / (having the same molecular weight as chain aliphatic polyamide resin containing polyether diamine block but Melt viscosity of the chain aliphatic polyamide resin not containing the polyether diamine block)} × 100 (%) (formula VII).

The chain aliphatic polyamide resin containing a polyether diamine block refers to a polyamide resin containing a polyether diamine block of the formula I in the chain aliphatic polyamide resin of the present invention. The melt viscosity ratio as defined in the formula VII of the present invention is preferably 80% or less, more preferably 60% or less, still more preferably 50% or less. The melt viscosity ratio referred to herein is an index which achieves an effect of lowering the melt viscosity by introducing a polyether diamine block into a molecular chain of a chain aliphatic polyamide resin. When the melt viscosity ratio is within the above range, the molding processability can be improved.

In the formula VII, the chain aliphatic polyamide resin having the same molecular weight but not containing the polyether diamine block as the chain aliphatic polyamide resin containing the polyether diamine block means that the Mw contains the polyether A chain-like aliphatic polyamide resin containing no polyether diamine block in a range of 95% or more and 105% or less of the chain aliphatic polyamide resin Mw of the diamine block. In order to more accurately evaluate the visbreaking effect, the closer the Mw of the chain aliphatic polyamide resin not containing the polyether diamine block to the chain aliphatic polyamide resin Mw containing the polyether diamine block, the better. That is, the preferred range of Mw of the chain aliphatic polyamide resin not containing the polyether diamine block is 100% of the chain aliphatic polyamide resin Mw containing the polyether diamine block. Alternatively, the melt viscosity can be obtained by a rotary rheometer test.

In the present invention, for the means to obtain the melt viscosity ratio in the above range, for example, a method in which the polyether diamine represented by the above formula I is within the above preferred range can be exemplified.

The chain-like aliphatic polyamide resin of the present invention has a high metal bonding strength, and preferably has a chain-like aliphatic polyamide resin having a tensile shear strength of 10 MPa or more bonded to the metal aluminum, and more preferably has a tensile shear strength of 15 MPa or more. A chain aliphatic polyamide resin having a tensile shear strength of 20 MPa or more is most preferable. The tensile shear strength of the chain-like aliphatic polyamide resin bonded to the metal described herein was measured according to ISO 19095, and was tested at a tensile speed of 5 mm/min. Further, the above-mentioned joined body is molded at a mold temperature of 120 ° C, and the above-mentioned metal aluminum is defined as an aluminum sheet A6061 which has been subjected to an NMT surface treatment method of Dacheng Chemical or a similar surface treatment method, and the surface of the metal surface subjected to the above surface treatment is electronically scanned. Microscopic observation, there is an average pore diameter of 10 or more and 100 nm or less The tiny holes. As described above, since the chain-like aliphatic polyamide resin of the present invention has excellent adhesion to a metal, when a thermoplastic resin composition containing the chain-like aliphatic polyamide resin of the present invention is used, it is possible to obtain a metal-bonding property. Joint body.

Next, a method for producing the chain aliphatic polyamide resin of the present invention will be described in detail. The chain aliphatic polyamide resin of the present invention may, but not limited to, the following production method: a raw material as a main component of the chain aliphatic polyamide resin is in the presence of a polyether diamine as described in the following formula IV A method of copolymerization. The method of copolymerization may be exemplified by one or more of a raw material such as an aminocarboxylic acid, a lactam, or a dibasic acid/diamine as a main component of the chain aliphatic polyamide resin. In the process of bulk polymerization to prepare a chain aliphatic polyamide resin, a polyether diamine as shown in Formula IV is added,

In the above formula IV, d, e, and f are a positive number, and R ₇ , R ₈ , and R ₉ are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; and the polyether diamine The molecular weight is 500 or more and less than 1,500 and the polyether diamine is added in an amount of 0.5% by weight or more and 15% by weight or less based on the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer.

In the above formula IV, d, e, and f are positive numbers in the range of 1 or more and 31 or less, and when any of d, e, and f values exceeds 31, the effect of reducing the melt viscosity may be poor, and at the same time, the polyether 2 The amine block structure is also inferior in heat resistance; and when any of the d, e, and f values is less than 1, the crystallinity damage to the polyamide resin may be large. d, e, and f satisfy the following conditions: 2 ≤ d + f ≤ 10 and 1.5 ≤ e ≤ 31. Further preferably, 3 ≤ d + f ≤ 8 and 7 ≤ e ≤ 15, and still more preferably 5 ≤ d + f ≤ 7 and 10 ≤ e ≤ 14. Here, since the polyether diamine is an oligomer having a molecular weight distribution, d+f and e herein mean an average value.

In the above formula I, R ₇ , R ₈ and R ₉ are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; in view of the stability of the polyether diamine block structure, R ₇ and R ₈ and R ₉ are preferably an alkyl group having 1 or more and 10 or less carbon atoms. When R ₇ , R ₈ and R ₉ are alkyl groups, the smaller the number of carbon atoms in R ₇ , R ₈ and R ₉ , the higher the affinity with the main structural unit of the polyamide resin, and preferably R ₇ , R ₈ and R ₉ are an alkyl group having 1 or more and 5 or less carbon atoms, and more preferably R ₇ , R ₈ and R ₉ are an alkyl group having 1 or more and 2 or less carbon atoms, and most preferably R ₇ or R ₈ and R _{9 are} both methyl.

The number average molecular weight of the polyether diamine represented by the above formula IV is preferably 500 or more and less than 1,500, and when the number average molecular weight is less than 500, the crystallinity of the polyamide resin is greatly inhibited. Considering polyamide resin The crystallinity is preferably 550 or more, and the number average molecular weight of the polyether diamine is preferably 580 or more. On the other hand, when the number average molecular weight is 1,500 or more, the effect of lowering the melt viscosity of the product is insufficient. The number average molecular weight of the polyether diamine is preferably 1200 or less, and more preferably the number average molecular weight of the polyether diamine is 1100 or less.

The polyether diamine represented by the formula IV in the method for producing the chain aliphatic polyamide resin of the present invention is preferably added in an amount of 0.5 wt% of the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer. % or more and 15% by weight or less (100% by weight based on the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer, the same applies hereinafter). When the addition amount of the polyether diamine represented by Formula IV is 0.5% by weight or more, the melt viscosity of the obtained polyamide product is lowered, and the molding process type is improved. More preferably, it is 1 wt% or more, further preferably 1.5 wt% or more, and most preferably 2 wt% or more; on the other hand, when the polyether diamine represented by Formula IV is added in an amount of 15 wt% or less, the obtained polyamide product crystallinity Can be maintained. It is more preferably 11% by weight or less, still more preferably 6% by weight or less, and most preferably 4.5% by weight or less.

The polyether diamine represented by the above formula IV may specifically be exemplified by, but not limited to, the following polyether diamines:

RE-900,

RT-1000,

One or more of ED-900 (commercial products from Huntsman) may be selected in combination of two or more kinds of polyether diamines such as those exemplified above.

The polyether diamine represented by the above formula IV may be added simultaneously with one or more of an aminocarboxylic acid, a lactam, or a dibasic acid/diamine before the start of polymerization, or may be polymerized after the start of polymerization. Add it at any time during the process.

Preparation of chain fat by copolymerization of one or more monomeric starting materials of aminocarboxylic acid, lactam, or dibasic acid/diamine in the presence of polyether diamine of formula IV In the case of the polyamide resin, a method of melt polymerization at a temperature equal to or higher than the melting point of the chain aliphatic polyamide resin may be employed, or a method of solid phase polymerization below the melting point of the chain aliphatic polyamide resin may be employed. .

Preparation of chain fat by copolymerization of one or more monomeric starting materials of aminocarboxylic acid, lactam, or dibasic acid/diamine in the presence of polyether diamine of formula IV In the case of the polyamide resin, a polymerization accelerator may be added as necessary. The polymerization accelerator is preferably an inorganic phosphorus compound such as phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid or an alkali metal salt or an alkaline earth metal salt of the above phosphoric acid, and more preferably sodium phosphite or sodium hypophosphite. The amount of use of the polymerization accelerator is preferably 0.001 part by weight or more and 1 part by weight or less (the weight of the raw material for preparing the polyamide resin other than the polyether diamine having the structure represented by the above formula IV is 100 parts by weight). The obtained polyamide can be obtained by controlling the addition amount of the polymerization accelerator to the above range of 0.001 part by weight or more and 1 part by weight or less. The mechanical properties and molding processability of the resin are well balanced.

In the present invention, in order to bring the relative viscosity ηr or the weight average molecular weight Mw of the chain aliphatic polyamide resin to the above preferred range, it is necessary to use aminocarboxylic acid, lactam, dibasic acid and diamine as raw materials and Formula IV. The polyether diamine is preferably controlled in a range of 0.95 or more and 1.05 or less in a ratio of a preferred total amount of amino groups [NH ₂ ] and a total amount of carboxyl groups [COOH] [NH ₂ ]/[COOH] described later. A preferred range of NH ₂ ]/[COOH] is 0.98 or more and 1.02 or less, and more preferably 0.99 or more and 1.01 or less. When the starting material is a lactam, an amount of the amino groups [NH _2] or carboxy groups [COOH] is the amount of the amino-lactam hydrolysis [NH _2] or carboxy groups [COOH].

Preparation of chain fat by copolymerization of one or more monomeric starting materials of aminocarboxylic acid, lactam, or dibasic acid/diamine in the presence of polyether diamine of formula IV In the case of a polyamide resin, a compound of the formula V may also be added:

U-(R ₁₀ -O) _n -R ₁₁ Formula V;

In the above formula V, n is an integer of 2 or more and 100 or less, and R _{10 is the} same or different, and is an alkylene group having 2 or more and 10 or less carbon atoms, and R ₁₁ is an alkyl group having 1 or more and 30 or less carbon atoms. , U is NH ₂ -, HO-, HO-C(=O)-, O=C=NR ₁₂ -NH-C(=O)-O-, O=C=NR ₁₃ -NH-C(=O )-NH- or

Here, R ₁₂ or R ₁₃ are the same or different alkylene groups having 1 or more and 20 or less carbon atoms. Considering the affinity with the polyamide resin, a main constituent unit, U- above formula V is preferably NH ₂ -, HO-, or HO-C (= O) - in a medium. To the thermoplastic resin composition used in the present invention has a low melt viscosity, affinity with the polyether end of the polyamide backbone higher as well, U- preferably NH ₂ -.

When n in the above formula V is less than 2, the effect of lowering the melt viscosity and maintaining the crystallinity is inferior, and the improvement in moldability is limited. Preferably, n is 4 or more, further preferably 8 or more, and most preferably 10 or more. On the other hand, when n is more than 100, the end group structure is inferior in heat resistance. Preferably, n is 70 or less, further preferably 35 or less, and most preferably 25 or less.

In the above formula V, R _{10 is the} same or different and is an alkylene group having 2 or more and 10 or less carbon atoms, and in view of affinity with a main structural unit of the polyamide resin, a subatomic ratio of 2 or more and 6 or less is preferable. The alkyl group is more preferably an alkylene group having 2 or more and 4 or less carbon atoms. Specific examples of R ₁₀ include -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ - , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, and the like. The n R ₁₀ groups may be composed of different alkylene groups, preferably -CH ₂ -CH ₂ - and -CH(CH ₃ )-CH ₂ -.

In the above formula V, R ₁₁ is an alkyl group having 1 or more and 30 or less carbon atoms. The smaller the number of carbon atoms in R ₁₁ , the higher the affinity with the main structural unit of the polyamide resin. Therefore, R ₁₁ is preferably an alkyl group having 1 or more and 20 or less carbon atoms, and more preferably 1 carbon atom. The alkyl group of the above 10 or less is more preferably an alkyl group having 1 or more and 5 or less carbon atoms, and most preferably a methyl group.

The compound represented by the above formula V may specifically be exemplified by, but not limited to, the following examples:

M-600,

M-1000,

M-2005,

M-2070 and so on.

Preparation of chain fat by copolymerization of one or more monomeric starting materials of aminocarboxylic acid, lactam, or dibasic acid/diamine in the presence of polyether diamine of formula IV In the case of a polyamide resin, a compound of the formula VI may also be added:

WR ₁₄ type VI;

In the above formula VI, R ₁₄ is an alkyl group or an aryl-substituted alkyl group, an aryl group or an alkyl-substituted aryl group having 1 or more and 30 or less carbon atoms, and W- is NH ₂ -, HO-, HO-C (= O)-, O=C=NR ₁₅ -NH-C(=O)-O-, O=C=NR ₁₆ -NH-C(=O)-NH- or

Here, R ₁₅ or R ₁₆ are the same or different alkylene groups having 1 or more and 20 or less carbon atoms. In view of the affinity with the main structural unit of the polyamide resin, W- in the above formula VI is preferably NH ₂ -, HO-, or HO-C(=O)-, and R ₁₄ preferably has 1 or more carbon atoms. An alkyl group or a phenyl group of 20 or less.

The compound represented by the above formula VI may specifically be exemplified by, but not limited to, the following examples: methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, and the like. An aliphatic monoamine such as propylamine or dibutylamine; an alicyclic monoamine such as cyclohexylamine or dicyclohexylamine; or an aromatic monoamine such as aniline, toluidine, diphenylamine or naphthylamine. The compound represented by the above monoamine type VI may be used singly or in combination of two or more.

On the other hand, the compound represented by the above formula VI may specifically be exemplified by, but not limited to, the following examples: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, and fourteen. Aliphatic monobasic acids such as alkanoic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; alicyclic monobasic acids such as cyclohexanoic acid; benzoic acid, toluic acid, α-naphthoic acid, β-naphthoic acid An aromatic monobasic acid such as methylnaphthoic acid or phenylacetic acid. Among them, acetic acid is preferred. The compound of the above monobasic acid type VI may be used singly or in combination of two or more.

The chain aliphatic polyamide of the present invention is a chain aliphatic polyamide resin prepared by using an amino acid, a lactam, or a diacid and a diamine as a main raw material, and contains the block structure represented by the above formula I. The following examples can be exemplified as the monomer raw material constituting the main structural unit of the main chain of the chain aliphatic polyamide resin. It is not limited to the following examples: amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or 4-aminomethylbenzoic acid; lactams such as ε-caprolactam or ω-laurolactam ; ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, decanediamine, undecanediamine, dodecanediamine, ten Trialkyldiamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadedioldiamine, stearyldiamine, nonadecanediamine, eicosanediamine, 2-methyl An aliphatic diamine such as keto-1,5-pentanediamine or 2-methyl-1,8-octanediamine; oxalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, Or an aliphatic dicarboxylic acid such as dodecanedioic acid. The corresponding alkyl diester and diacid chloride of the dicarboxylic acid can also be exemplified as the monomer raw material constituting the chain aliphatic polyamide main chain structure. The chain aliphatic polyamide resin in the present invention may be a chain aliphatic polyamide homopolymer prepared from a monomer raw material such as the above, or a chain aliphatic polyamide copolymer. The chain aliphatic polyamide resin may be a polyamide resin or may be composed of two or more polyamide resins. The specific structure of the chain aliphatic polyamide resin is not particularly limited, but in view of heat resistance and crystallinity, it is preferred that 80 mol% or more of the chain aliphatic polyamide main chain repeating unit is the monomer raw material exemplified above. The composition of the structural unit is more preferably 90 mol% or more, and most preferably 100 mol%. In the chain aliphatic polyamide resin of the present invention, a filler, a polymer of another type, and various additives may be added to form a chain-like aliphatic polyamide resin composition in a range not impairing the advantageous effects of the present invention. use.

The filler may be a filler for a general resin, and the addition of the filler may further improve the strength, rigidity, heat resistance and dimensional stability of the molded article obtained from the chain aliphatic polyamide resin. The filler may be exemplified by, but not limited to, the following examples: glass fiber, carbon fiber, titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber , fibrous or inorganic fillers such as gypsum fibers or metal fibers; wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, silicate, alumina, Silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, A non-fibrous inorganic filler such as boron nitride, silicon carbide or silica; and the above filler may be added in combination of two or more kinds. The filler may be hollow, and the filler may be treated with a coupling agent such as an isocyanate compound, an organosilane compound, an organic titanate compound, an organoborane compound or an epoxy compound. The above montmorillonite may also be an organic montmorillonite obtained by cation exchange of interlamellar ions through an organic ammonium salt. The above filler is preferably a fibrous inorganic filler, and more preferably glass fiber or carbon fiber.

The content of the above filler in the chain aliphatic polyamide resin composition obtained after compounding is preferably When the amount of the filler added is 5% by weight or more, the shrinkage ratio of the resin composition is reduced, and dimensional stability is good, and when used as a metal-bonding resin composition, when the filler is added in an amount of 5 wt% or more and 80 wt% or less Since the shrinkage ratio of the resin composition is reduced, the resin composition infiltrated into the fine pores of the surface-treated metal surface is melted, and the interfacial peeling of the resin composition from the metal is suppressed, thereby bonding the resin composition and the metal. It is more preferable that the filler is added in an amount of 10% by weight or more, more preferably 20% by weight or more, and most preferably 30% by weight or more based on the total weight of the resin composition. On the other hand, when the amount of the filler added is 80% by weight or less, the melt of the resin composition has good fluidity, more preferably 60% by weight or less, still more preferably 50% by weight or less. Other types of polymers to be added may be exemplified by, but not limited to, polyolefins such as polyethylene or polypropylene; modified polyolefins such as copolymers obtained by polymerizing olefins and/or conjugated diene compounds; and polyesters; Polyamide resin other than polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, or chain aliphatic polyamide resin of the present invention . The above polymers may be added in combination of two or more kinds. The addition amount of the other kind of polymer is preferably 0% by weight or more and 80% by weight or less (100% by weight of the resin composition obtained after compounding), and by controlling the added amount to the above range, a chain aliphatic group can be obtained. The low melt viscosity properties of polyamides are better reflected. It is further preferably 60% by weight or less, and still more preferably 50% by weight or less.

In order to improve the impact resistance of the molded article obtained by the thermoplastic resin composition used in the present invention and to reduce the shrinkage ratio, the above-mentioned other kinds of polymers are preferably polymers (or copolymers) obtained by polymerizing an olefin and/or a conjugated diene compound. An impact agent such as a modified polyolefin. These polymers may be used in combination of two or more kinds.

The polymer (or copolymer) may, but not limited to, the following examples: an ethylene-based copolymer, a conjugated diene-based polymer, or a conjugated diene-aromatic ethylene copolymer.

The ethylene-based copolymer means a copolymer of ethylene and another monomer. Other monomers copolymerized with ethylene may, but not limited to, the following examples: an α-olefin having 3 or more carbon atoms, a non-conjugated diene, vinyl acetate, vinyl alcohol, an α,β-unsaturated acid or a derivative thereof. Two or more kinds of the above monomers may be copolymerized with ethylene. The α-olefin having 3 or more carbon atoms may, but not limited to, the following examples: propylene, 1-butene, 1-pentene, or 3-methyl-1-pentene, preferably propylene or 1-butene. The non-conjugated diene may be exemplified by, but not limited to, the following examples: 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5 -propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-butenyl-2-norbornene, 5-(2-methyl-2-butenyl)-2 - norbornene, 5-(2-ethyl-2-butenyl)-2-norbornene, or norbornene compound such as 5-methyl-5-vinylnorbornene; dicyclopentadiene, Methyltetrahydroanthracene, tetrahydroanthracene, 1,5-cyclooctadiene, 1,4-hexadiene, 6-Methyl-1,5-heptadiene, or 11-tridecadiene, etc., preferably 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentan Diene, or 1,4-hexadiene. The α,β-unsaturated acid may be exemplified by, but not limited to, the following examples: acrylic acid, methacrylic acid, ethacrylic acid, 2-butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, or butyl Oleic acid and the like. The derivative of the α,β-unsaturated carboxylic acid may, but not limited to, the following examples: an alkyl ester, an aryl ester, a glyceride, an acid anhydride, or an imide of the above α,β-unsaturated carboxylic acid.

The conjugated diene polymer refers to a polymer obtained by polymerizing at least one conjugated diene. The conjugated diene described herein may be exemplified by, but not limited to, the following examples: 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl Base-1,3-butadiene, or 1,3-pentadiene, and the like. The conjugated diene may be copolymerized in two or more types. Additionally, the unsaturated bonds of the polymer can be partially or completely reduced by hydrogenation.

The conjugated diene-aromatic ethylene copolymer refers to a copolymer of a conjugated diene and an aromatic ethylene, and may be a block copolymer or a random copolymer. Examples of the conjugated diene may be the same as those of the above-mentioned conjugated diene-based polymer, and 1,3-butadiene and isoprene are preferable. The aromatic vinyl may, for example, be styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, or vinylnaphthalene, etc., preferably styrene. Further, the unsaturated bond other than the double bond other than the aromatic ring of the conjugated diene-aromatic ethylene copolymer may be partially or completely reduced by hydrogenation.

Specific examples of the impact agent include an ethylene/propylene copolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/propylene/dicyclopentadiene copolymer, and an ethylene/propylene/5-Asian Base-2-norbornene copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene triblock copolymer, unhydrogenated or hydrogenated styrene/butadiene/styrene triblock a salt of a part or all of a carboxylic acid group of a copolymer, an ethylene/methacrylic acid copolymer or a copolymer with sodium, lithium, potassium, zinc or calcium, an ethylene/methyl acrylate copolymer, an ethylene/ethyl acrylate copolymer , ethylene/methyl methacrylate copolymer, ethylene/ethyl acrylate-g-maleic anhydride copolymer (here "g" means grafting, the same below), ethylene/methyl acrylate-g-maleic anhydride Copolymer, ethylene/ethyl acrylate-g-maleimide copolymer, ethylene/ethyl acrylate-gN-phenylmaleimide copolymer or partial saponification of the copolymer, ethylene/methyl Glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/methacrylic acid Ester/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, ethylene/glycidyl ether copolymer, ethylene/propylene-g-maleic anhydride Copolymer, ethylene/propylene-g-maleic anhydride copolymer, ethylene/butene-1-g-maleic anhydride copolymer, ethylene/propylene/1,4-hexadiene-g-maleic anhydride copolymerization , ethylene/propylene/dicyclopentadiene-g-maleic anhydride copolymer, ethylene/propylene/2,5-norbornadiene-g-maleic anhydride copolymer, ethylene/propylene-gN-phenyl mala Imide copolymer, ethylene/butene-1-gN-phenylmaleimide copolymer, hydrogenated (styrene/butadiene/styrene-g-maleic anhydride) copolymer, hydrogenated (styrene) /isoprene/styrene-g-maleic anhydride) copolymer, ethylene/propylene-g-glycidyl methacrylate copolymer, ethylene/butene-1-g-glycidyl methacrylate copolymer , ethylene/propylene/1,4-hexadiene-g-glycidyl methacrylate copolymer, ethylene/propylene/dicyclopentadiene-g-glycidyl methacrylate copolymer, hydrogenation (styrene/butyl Diene/styrene-g-glycidyl methacrylate copolymer, nylon 12/polytetrahydrofuran copolymer, nylon 12/polypropylene glycol copolymer, polybutylene terephthalate/polytetrahydrofuran copolymer, or poly Butylene terephthalate/polypropylene glycol copolymer, and the like. The above copolymer is preferably an ethylene/methacrylic acid copolymer and a salt of a part or all of a carboxylic acid group of the copolymer with sodium, lithium, potassium, zinc or calcium, an ethylene/propylene-g-maleic anhydride copolymer, ethylene. /butene-1-g-maleic anhydride copolymer.

Specific examples of the additives include antioxidants or heat stabilizers (hindered phenols, hydroquinones, phosphorous acid or substituted products thereof, copper halides, iodine compounds, etc.), and weathering agents (resorcinol, Salicylic acid, benzotriazole, diphenyl ketone, or hindered amines, mold release agents and lubricants (fatty alcohols, aliphatic amides, aliphatic diamides, or diureas or poly Ethylene wax, etc., pigment (calcium sulfide, phthalocyanine, or carbon black, etc.), dye (aniline black, etc.), plasticizer (n-octyl p-hydroxybenzoate, or N-butylbenzenesulfonamide), antistatic Agent (alkyl sulfate type anionic antistatic agent, 4-stage ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate or trimethylglycine) Antistatic agent), flame retardant (melamine such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, A bromine-based flame retardant such as a brominated epoxy resin or a combination of the above-mentioned bromine-based flame retardant and antimony trioxide). The above additives may be selected from two or more types.

The chain aliphatic polyamide resin of the present invention can be obtained into a desired shape by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, or film forming. The molded article obtained from the chain aliphatic polyamide resin of the present invention and the composition containing the chain aliphatic polyamide resin can be applied to the following examples: resin molded articles such as electric/electronic product parts, automobile parts, mechanical parts, and the like. /Industry and other fibers, films such as packaging/electromagnetic recording, and metal joints.

detailed description

The invention is further illustrated by the following examples, which are not intended to limit the invention.

A description of the tests involved in the examples and comparative examples is as follows:

(1) Measurement of Relative Viscosity ηr: The polyamide resin samples obtained in the respective Examples and Comparative Examples were dissolved in 96 wt% of concentrated sulfuric acid to prepare a solution having a polyamide resin concentration of 0.01 g/ml at 25 ° C. The relative viscosity was measured using an Ubbelohde viscometer.

(2) Polyether diamine block content represented by Formula I: The polyamide resin having the polyether diamine block of the above formula I obtained in each of the Examples and Comparative Examples was dissolved at a concentration of 50 mg/ml. In the deuterated concentrated sulfuric acid, a 1H-NMR nuclear magnetic test was performed using Japanese electronic JEOL ECX 400P under the condition of 256 scans. a peak corresponding to hydrogen on an ethylene group (-CH ₂ -O-) adjacent to oxygen on the polyether diamine block in the above formula I in the 1H-NMR spectrum, and a polyamide main component as a main component After the peak corresponding to hydrogen on the chain repeating unit is assigned, the content of the polyether diamine block in the polyamide resin is calculated by the peak area obtained by integrating each peak and the number of hydrogen atoms contained in each structure.

(3) End group content represented by Formula II: The polyamide resin having the terminal group represented by the above formula II obtained in each of the examples and the comparative examples was dissolved in deuterated concentrated sulfuric acid at a concentration of 50 mg/ml, and was scanned. The 1H-NMR nuclear magnetic test was carried out using Japanese electronic JEOL ECX 400P under the conditions of 256 times. By assigning a peak corresponding to hydrogen on R5 in the terminal group represented by the above formula II in the 1H-NMR spectrum and a peak corresponding to hydrogen on the repeating unit of the polyamide main chain as a main component, the peaks are integrated by The peak area obtained and the number of hydrogen atoms contained in each structure were calculated to obtain the terminal group content of the formula II in the polyamide resin.

(4) End group content represented by Formula III: The polyamide resin having the terminal group represented by Formula III obtained in each of Examples and Comparative Examples was dissolved in deuterated concentrated sulfuric acid at a concentration of 50 mg/ml in the number of scans. The 1H-NMR nuclear magnetic test was carried out under the conditions of 256 times using Japanese electronic JEOL ECX 400P. By assigning a peak corresponding to hydrogen on R6 in the terminal group represented by the above formula III in the 1H-NMR spectrum and a peak corresponding to hydrogen on the repeating unit of the polyamide main chain as a main component, the peaks are integrated by The peak area obtained and the number of hydrogen atoms contained in each structure were calculated to obtain the terminal group content of the formula III in the polyamide resin.

(5) Thermal properties

The polyamide resin obtained in each of the examples and the comparative examples was accurately weighed 5 to 7 mg by a differential scanning calorimeter (DSC Q100) of TA Corporation, and started at 20 ° C at a heating rate of 20 ° C / min under a nitrogen atmosphere. The temperature is raised to a temperature 30 ° C higher than the temperature T0 of the endothermic peak appearing, and the temperature is kept at this temperature for 2 min, and then the temperature is lowered to 20 ° C at a temperature decreasing rate of 20 ° C / min, and the melting crystallization temperature Tc and the molten crystal 焓 ΔHc It is determined by this cooling curve: Tc is the temperature corresponding to the peak tip of the exothermic peak during the cooling process, and ΔHc is the peak area of the exothermic peak during the cooling process. After the above temperature drop, the temperature is raised again at a temperature increase rate of 20 ° C / min to a temperature 30 ° C higher than T0, and the melting point T _m and the melting enthalpy ΔH _{m are} determined by this secondary temperature rise curve: T _m is the endothermic heat during the second temperature rise The temperature corresponding to the peak tip of the peak, ΔH _m is the peak area of the endothermic peak during the second temperature rise.

(6) Molecular weight

2.5 mg of the polyamide resin obtained in each of the examples and the comparative examples was dissolved in 4 ml of hexafluoroisopropanol containing 0.005 N of sodium trifluoroacetate, and then filtered through a 0.45 μm filter to measure the number average molecular weight Mn and weight. The average molecular weight Mw, the measurement conditions are as follows

Pump: e-Alliance GPC system (made by Waters)

Detector: Differential detector Waters 2414 (manufactured by Waters)

Column: Shodex HFIP-806M (2) + HFIP-LG

Solvent: hexafluoroisopropanol (addition of 0.005N sodium trifluoroacetate)

Flow rate: 1ml/min

Sample injection amount: 0.1ml

Temperature: 30 ° C

Molecular weight correction: polymethyl methacrylate.

(7) Melt viscosity

The polyamide resin obtained in each of the examples and the comparative examples was dried in a vacuum oven at 80 ° C for 12 hours or more, and then formed into a film having a diameter of 25 mm by hot pressing with a laminator (film thickness: 0.7 mm). The melt viscosity was measured by the following method using a rotary rheometer (manufactured by Antonpaar, MCR302, φ25 parallel plate): the sample was melted at 260 ° C for 5 minutes, the parallel plate pitch was 0.5 mm, and the vibration mode was measured under a nitrogen atmosphere. The frequency was 0.5 to 6.88 Hz, and 50 points (0.5 minutes) and an amplitude of 1% were measured. The complex viscosity measurement at a frequency of 1.02 Hz was used as the melt viscosity.

(8) tensile modulus

According to the ASTM D638 standard test, the spline size is Type IV in ASTM D638, and the tensile modulus is tested by Shimadzu AG--IS 1KN. The test temperature is 23 ° C, the humidity is 50% RH, the tensile speed is 10 mm/min, and the clamp spacing is 60 mm. . The tensile modulus results are taken as the average of the five spline test results. The injection molding conditions for the spline are as follows:

Injection molding machine: ST10S2V (manufactured by NISSEI)

Injection temperature: 250 ° C (Examples 1 to 16, Comparative Examples 1 to 9, 12 to 17)

220 ° C (Comparative Examples 10, 11)

Mold temperature: 80 ° C (Examples 1 to 16, Comparative Examples 1 to 9, 12 to 17)

90 ° C (Comparative Examples 10, 11)

(9) Mould heat treatment of molded products

The molded spline used for the above tensile modulus test was placed in a constant temperature and humidity chamber at a temperature of 60 ° C and a relative humidity of 90% RH for 1000 hours.

(10) Melt retention stability

2 g of the polyamide resin obtained in each of the examples and the comparative examples was weighed into a test tube, and the system was replaced with nitrogen, and the polyamide resin in the test tube was rapidly heated to 260 ° C in a metal bath under a nitrogen stream and allowed to stand for 1 hour to be melted. The average molecular weight after the obtained melt retention was retained by GPC test.

(11) Joint injection molding

The metal piece was placed in a cavity, and after the mold was held for 1 minute, the melt of the thermoplastic resin composition was metered and injected into the mold. After the melt is cooled and solidified, the mold is opened to obtain a joined body.

Injection molding machine: ST10S2V (manufactured by NISSEI)

Screw temperature: 250 ° C

Mold temperature: 60, 120 ° C

(12) splicability

The bond between resin and metal is characterized by tensile shear strength. The test is tested according to ISO 19095. The spline size is the specified size in ISO 19095 shown in Figure 1. The joint area is 0.5 cm2. The Shimadzu AG-IS 1KN test is used. Tensile modulus, test temperature 23 ° C, humidity 50% RH, tensile speed 5 mm / min, clamp spacing 3 mm. The tensile shear strength results are taken as the average of the five spline test results.

The materials used in the examples and comparative examples are as follows:

Hexamethylenediamine: TCI

Sebacic acid: Hebei Kaide Biomaterial Co., Ltd.

Adipic acid: Alfa

Meta-xylylenediamine: TCI

Caprolactam: BASF

Polyether diamine: Huntsman

ED-600 (Mn=600),

ED-900 (Mn=900),

EDR-148 (Mn=148),

ED-2003 (Mn=2000),

XTJ-542 (Mn=1000),

RE-900 (Mn=900),

RT-1000 (Mn=1000)

Polyethylene glycol: Alfa (Mn=1000)

Stearic acid: TCI

Benzoic acid: TCI

Aluminum sheet A6061 (45mm*10mm*1.5mm) Kunshan Xinda Mould Co., Ltd.

Entrusted aluminum sheet processing company: Shenzhen Baoyuanjin Co., Ltd. (NMT processing);

Example 1

210.4 g hexamethylenediamine, 375.0 g azelaic acid, 25.9 g

ED-600 (Mn = 600) and 160 g of deionized water were placed in the reaction vessel, and the reaction vessel was sealed and replaced with nitrogen three times. Heating was started after the heater temperature of the reaction vessel was set to 180 ° C, and the heater temperature was set to 270 ° C after 2 hours. After the pressure in the reactor reached 1.75 MPa, the water vapor in the reactor was discharged through a bleed valve while maintaining the pressure in the vessel at 1.75 MPa until the temperature in the vessel was raised to 250 °C. When the temperature in the autoclave reached 250 ° C, the heater set temperature was lowered to 260 ° C, and the pressure in the autoclave was gradually decreased from 1.75 MPa to normal pressure within 1 hour (the temperature in the autoclave was 260 ° C when the pressure was reached). After the pressure was reduced to normal pressure, a nitrogen gas stream was introduced into the autoclave, and melt polymerization was carried out for 10 minutes under a nitrogen stream (up to a temperature of 263 ° C) to obtain a nylon 610 containing a polyether diamine block. The nylon 610 obtained by the above method had a relative viscosity of 1.73 and a melt viscosity of 16 Pa·s. The nylon 610 obtained by the above method is pelletized, placed in a Soxhlet extractor, and the unreacted polyether diamine is removed with methanol, and the content of the polyether diamine block is determined by nuclear magnetic resonance spectroscopy (1H-NMR). 5.1wt%. Other physical properties are shown in Table 1.

Examples 2 and 3, Comparative Examples 1-3

The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 1 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 1. The properties of the obtained nylon 610 are shown in Table 1.

Table 1

Example 1-3 Compared with Comparative Example 1, it can be seen that the melt viscosity of nylon 610 containing 5.1 wt% of the polyether diamine block is only the polyether diamine block-free nylon 610 having the same weight average molecular weight. The homopolymer has a melt viscosity of 8 to 9%, and there is no difference in crystallinity and mechanical properties. In addition, it can be seen from Comparative Example 2 that when the number average molecular weight of the polyether diamine block is less than 500, the crystallization temperature of the polyamide resin The degree, melting point and mechanical properties were all significantly decreased, while the number average molecular weight of the polyether diamine block in Comparative Example 3 was more than 1,500, and the melt viscosity decreased not significantly.

Examples 4-6, Comparative Examples 4 and 5

The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 2 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 2. The properties of the obtained nylon 610 are shown in Table 2.

Table 2

The decrease in melt viscosity of Example 2 and Examples 4-6 was more pronounced than Comparative Example 4 having a lower polyether diamine block content (0.1 wt%). Example 2 and Example 4-6 maintained the same crystallinity and mechanical properties as Comparative Example 1 as compared with Comparative Example 5 having a higher polyether diamine block content (20 wt%).

Comparative Example 6-8

The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 3 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 3. The properties of the obtained nylon 610 are shown in Table 3.

table 3

By comparing Example 2 and Comparative Example 6-8, the melt viscosity reduction effect of Example 2 was better than that of the polyether block containing other structures.

Example 7-10

The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 4 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 4. The properties of the obtained nylon 610 are shown in Table 4.

Table 4

Comparing Examples 7-10 with Example 2, it can be seen that when the non-reactive terminal group is contained, the Mw increase rate after melting retention is low, and the melt retention stability is good.

Example 11

500 g of caprolactam, 4.1 g of adipic acid, 25 g of JEFFAMINE ED-900 (Mn = 900), and 160 g of deionized water were placed in the reaction vessel, and the reaction vessel was sealed and replaced with nitrogen three times. Heating was started after the heater temperature of the reaction vessel was set to 290 °C. After the pressure in the reactor reached 1 MPa, the water vapor in the reactor was discharged through a bleed valve while maintaining the pressure in the vessel at 1 MPa until the temperature in the vessel was raised to 250 °C. When the temperature in the autoclave reached 250 ° C, the heater set temperature was lowered to 260 ° C, and the pressure in the autoclave was gradually reduced from 1 MPa to normal pressure within 1 hour (the temperature in the autoclave was 260 ° C when the pressure was reached). After the pressure was reduced to normal pressure, a nitrogen gas stream was introduced into the autoclave, and melt polymerization was carried out for 10 minutes under a nitrogen stream (up to a temperature of 263 ° C) to obtain a nylon 6 containing a polyether diamine block. The obtained nylon 6 was pelletized, placed in a Soxhlet extractor, and unreacted caprolactam and polyether diamine were removed by methanol, and the relative viscosity was 1.77, and the melt viscosity was 18 Pa·s. The content of the polyether diamine block was 5.6 wt% by nuclear magnetic resonance spectroscopy (1H-NMR). Other physical properties are shown in Table 5.

Examples 12 and 13, Comparative Example 9

The other operations were the same as in Example 11 except that the raw materials were changed as shown in Table 5 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 5. The properties of the obtained nylon 6 are shown in Table 5.

Example 14

261.2 g of hexamethylenediamine, 332.6 g of adipic acid, 25.9 g of JEFFAMINE ED-900 (Mn = 900), and 160 g of deionized water were placed in the reaction vessel, and the reaction vessel was sealed and replaced with nitrogen three times. Heating was started after the heater temperature of the reaction vessel was set to 180 ° C, and the heater temperature was set to 300 ° C after 2 hours. After the pressure in the reactor reached 1.75 MPa, the water vapor in the reactor was discharged through a bleed valve while maintaining the pressure in the vessel at 1.75 MPa until the temperature in the vessel was raised to 250 °C. When the temperature in the autoclave reached 250 ° C, the heater set temperature was lowered to 280 ° C, and the pressure in the autoclave was gradually reduced from 1.75 MPa to normal pressure within 1 hour (the temperature in the autoclave was 275 ° C when the pressure was reached). After the pressure was reduced to normal pressure, a nitrogen stream was introduced into the kettle, and melt polymerization was carried out for 10 minutes under a nitrogen stream (up to a temperature of 282 ° C) to obtain a nylon 66 containing a polyether diamine block. The nylon 66 obtained by the above method had a relative viscosity of 1.99 and a melt viscosity of 22 Pa·s. The nylon 66 obtained by the above method was pelletized, placed in a Soxhlet extractor, and the unreacted polyether diamine was removed with methanol, and the content of the polyether diamine block was determined by nuclear magnetic resonance spectroscopy (1H-NMR). 5.1wt%. Other physical properties are shown in Table 5.

Comparative Example 10

269.7 g of m-xylylenediamine, 404.5 g of sebacic acid, 18 g of JEFFAMINE ED-900 (Mn=900), 160 g of deionized water was added to the reaction vessel, and the reaction vessel was sealed and replaced with nitrogen three times. Heating was started after the heater temperature of the reaction vessel was set to 180 ° C, and the heater temperature was set to 240 ° C after 2 hours. After the pressure in the reactor reached 1.5 MPa, the water vapor in the reactor was discharged through a bleed valve while maintaining the pressure in the vessel at 1.5 MPa until the temperature in the vessel was raised to 220 °C. When the temperature in the autoclave reached 220 ° C, the heater set temperature was lowered to 230 ° C, and the pressure in the autoclave was gradually reduced from 1.5 MPa to normal pressure within 1 hour (the internal temperature was 230 ° C when the pressure was reached). The nylon MXD10 containing a polyether diamine block was obtained by dropping to atmospheric pressure. The nylon MXD10 obtained by the above method had a relative viscosity of 1.81 and a melt viscosity of 150 Pa·s. The nylon MXD10 obtained by the above method is pelletized, placed in a Soxhlet extractor, and the unreacted polyether diamine is removed with methanol, and the content of the polyether diamine block is determined by nuclear magnetic resonance spectroscopy (1H-NMR). 5.1wt%. Other physical properties are shown in Table 5.

Comparative Example 11

The other operations were the same as in Comparative Example 10 except that the raw materials were changed as shown in Table 5. The properties of the obtained nylon MXD10 are shown in Table 5.

Comparative Example 12

The other operations were the same as in Example 14 except that the raw materials were changed as shown in Table 5. The properties of the obtained nylon 66 are shown in Table 5.

table 5

In Examples 11-13, the melt viscosity was significantly lowered as compared with the nylon 6 homopolymer in Comparative Example 9. In Example 14, the melt viscosity was also significantly lowered as compared with the nylon 66 homopolymer in Comparative Example 12. By comparing Comparative Example 10 and Comparative Example 11, the semi-aromatic nylon MXD10 containing the polyether diamine block had a lower melt viscosity reduction effect in Comparative Example 10 than the corresponding semi-aromatic nylon homopolymer, and at the same time mechanically The performance is significantly reduced.

Example 15

The other operations were the same as in Example 11 except that the raw materials were changed as shown in Table 6 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 6. The properties of the obtained nylon 6 are shown in Table 6.

Example 16

The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 6 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 6. The properties of the obtained nylon 610 are shown in Table 6.

Comparative Example 13

3 kg of nylon 6, 30 g of JEFFAMINE ED-600 (Mn = 600) was dried and uniformly mixed. The mixture was transferred to a twin-screw extruder (TEX30α, Nippon Steel Works), and melt-kneaded at 250 ° C to obtain a nylon 6 composition. The nylon 6 composition was measured to have a melting point of 219 ° C, a weight average molecular weight Mw of 46,300, a melt viscosity of 45 Pa·s, and a tensile modulus of 2.2 GPa. Other physical properties are shown in Table 6.

Comparative Example 14

The other operations were the same as in Comparative Example 13, except that the raw materials were changed as shown in Table 6. The properties of the obtained nylon 610 composition are shown in Table 6.

Table 6

Melting of the polyamide resin composition obtained by melt-kneading in Comparative Example 13 and Comparative Example 14 The melt viscosity reduction effect was inferior to that of Example 15 and Example 16, and the precipitate was observed after moisture absorption treatment of the molded article, and no precipitation of precipitate was observed in either of Example 15 and Example 16. The unreacted polyether diamine in the polyamide resin composition of Comparative Example 13 and Comparative Example 14 was removed by methanol, and subjected to a nuclear magnetic resonance spectrum (1H-NMR) test to obtain a polyether diamine chemically bonded to the polyamide. The content was only 0.1% by weight, indicating that most of the polyether diamines in Comparative Example 13 and Comparative Example 14 existed in a state in which they were not chemically bonded to the polyamide.

Examples 17, 18, Comparative Examples 15-18

The other operations were the same as in Example 1 except that the raw materials were changed as shown in Table 7 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 7. The properties of the obtained nylon 610 are shown in Table 7.

Table 7

The polyether block structure in the product obtained in Comparative Examples 15-17 was combined with the end of the polyamide, and although the melt viscosity lowering effect was remarkable, the polymerization time required was long.

Example 19

The surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in a ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the measurement of the polyether diamine block obtained in Example 13. Nylon 6 and a nylon 6 melt were injected into the mold for a cooling time of 15 s, and the mold was opened to obtain a joined body having a screw temperature of 260 ° C and a mold temperature of 120 ° C. The joined body obtained by the above method was subjected to metal bonding performance test at a tensile speed of 5 mm/min in accordance with ISO 19095, and the results are shown in Table 8.

Example 20, 21, Comparative Example 19, 20

The performance of the resulting joined body was as shown in Table 8, except that the resin used for the injection molding or the mold temperature during the injection molding was changed as shown in Table 8.

Comparative Example 21

The surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in the ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the measurement of the commercial polyamide elastomer (PEBAX 5533SP01, manufactured by Arkema, melting After the viscosity of 42 Pa·s), the resin melt was injected into the mold for a cooling time of 15 s. The screw temperature was 260 ° C and the mold temperature was 120 ° C. At a mold temperature of 120 ° C, the polyamide elastomer cannot be solidified in a mold, and is deformed during demolding, so that a joined body cannot be obtained.

Comparative Example 22

Except that the mold temperature during the injection molding process was changed as shown in Table 8, the other operations were the same as in Comparative Example 21, and the joined body obtained by the above method was subjected to metal bonding performance test at a tensile speed of 5 mm/min according to ISO 19095. The results are shown in Table 8.

Table 8

*Shannon Armstrong, Benny Freeman, Anne Hiltner, Eric Baer. Polymer; 2012: 1383-1392.

Comparing Examples 19 to 21 with Comparative Examples 19 and 20, it can be seen that the polyamide 6 resin containing the polyether diamine block of Formula I has better adhesion to the metal than the polyether diamine of Formula I. Block of polyamide 6 resin. Further, in Examples 19 to 21, compared with Comparative Examples 21 and 22, the polyamide 6 resin containing the polyether diamine block represented by Formula I had better adhesion to the metal than the polyamide elastomer.

Claims (13)

1. A chain aliphatic polyamide resin containing a polyether diamine block, characterized in that the structure of the polyether diamine block is as shown in formula I,

   

   In the above formula I, a, b, and c are positive numbers, and R ₁ , R ₂ , and R ₃ are the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; The number average molecular weight of the segment is 500 or more and less than 1500 and the content of the polyether diamine block in the chain aliphatic polyamide resin is 0.5% by weight or more and 15% by weight or less based on the total weight of the chain aliphatic polyamide resin; When the chain aliphatic polyamide resin is formulated into a chain aliphatic polyamide resin solution having a concentration of 0.01 g/ml using 96 wt% sulfuric acid as a solvent, the relative viscosity ηr measured at 25 ° C is 1.1 or more and 4.0 or less.
2. The chain aliphatic polyamide resin according to claim 1, wherein in the formula I, 2 ≤ a + c ≤ 10, and 1.5 ≤ b ≤ 31, and R ₁ , R ₂ , and R _{3 are} simultaneously Is a methyl group.
3. The chain aliphatic polyamide resin according to claim 1, wherein the chain aliphatic polyamide resin contains no block other structure than the polyether diamine block.
4. The chain-shaped aliphatic polyamide resin according to claim 1, wherein the chain-like aliphatic polyamide resin has a total weight of the chain-like aliphatic polyamide resin of 0.005 mmol/g or more and 0.1 mmol/g or less. Terminal group of formula II

   -Y-(R ₄ -O) _m -R ₅ formula II;

   -Y- in the above formula II is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH (OH)-CH ₂ -, m is an integer of 2 or more and 100 or less, and R _{4 is the} same or different, and is an alkylene group having 2 or more and 10 or less carbon atoms, and R ₅ is 1 or more and 30 or less. The following alkyl groups.
5. The chain-shaped aliphatic polyamide resin according to claim 1, wherein the chain-like aliphatic polyamide resin has a total weight of the chain-like aliphatic polyamide resin of 0.005 mmol/g or more and 0.1 mmol/g or less. Terminal group of formula III

   -ZR ₆ type III;

   -Z- in the above formula III is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH (OH)-CH ₂ -, R ₆ is an alkyl group having 1 or more and 30 or less carbon atoms, an alkyl group substituted with an aryl group, an aryl group or an alkyl group substituted with an alkyl group.
6. The chain-like aliphatic polyamide resin according to any one of claims 1 to 5, wherein the chain-like aliphatic polyamide resin has a weight average molecular weight Mw of 10,000 or more as measured by gel permeation chromatography. And 400,000 or less.
7. The chain aliphatic polyamide resin according to any one of claims 1 to 5, wherein the chain aliphatic polyamide resin has a melting point of 215 ° C or higher.
8. The chain aliphatic polyamide resin according to any one of claims 1 to 5, wherein the chain aliphatic polyamide resin is an ISO19095 test strip at a tensile speed of 5 mm/min. The measured joint strength with metal aluminum was 10 MPa or more.
9. A method for preparing a chain aliphatic polyamide resin, which comprises polymerizing one or more of an aminocarboxylic acid, a lactam or a dibasic acid/diamine as a monomer to prepare a chain aliphatic polycondensation In the process of the amide resin, a polyether diamine as shown in Formula IV is added,

   

   In the above formula IV, d, e, and f are each a same or different positive number, and R ₇ , R ₈ , and R ₉ are each the same or different hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms; The polyether diamine has a molecular weight of 500 or more and less than 1,500 and the polyether diamine is added in an amount of 0.5% by weight or more and 15% by weight or less based on the total weight of the aminocarboxylic acid, lactam or dibasic acid/diamine monomer. .
10. The method for preparing a chain aliphatic polyamide resin according to claim 9, wherein d, e, and f in the formula IV satisfy 2 ≤ d + f ≤ 10, and 1.5 ≤ e ≤ 31, R ₇ , R ₈ and R _{9 are} simultaneously methyl.
11. The method for producing a chain aliphatic polyamide resin according to claim 9, wherein a compound represented by Formula V is further added

    U-(R ₁₀ -O) _n -R ₁₁ Formula V;

    In the above formula V, n is an integer of 2 or more and 100 or less, and R _{10 is the} same or different, and is an alkylene group having 2 or more and 10 or less carbon atoms, and R ₁₁ is an alkyl group having 1 or more and 30 or less carbon atoms. , U is NH ₂ -, HO-, HO-C(=O)-, O=C=NR ₁₂ -NH-C(=O)-O-, O=C=NR ₁₃ -NH-C(=O )-NH- or

    

    Here, R ₁₂ or R ₁₃ are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.
12. The method for producing a chain aliphatic polyamide resin according to claim 9, wherein a compound represented by formula VI is further added

    WR ₁₄ type VI;

    In the above formula VI, R ₁₄ is an alkyl group or an aryl-substituted alkyl group, an aryl group or an alkyl-substituted aryl group having 1 or more and 30 or less carbon atoms, and W- is NH ₂ -, HO-, HO-C (= O)-, O=C=NR ₁₅ -NH-C(=O)-O-, O=C=NR ₁₆ -NH-C(=O)-NH- or

    

    Here, R ₁₅ or R ₁₆ are the same or different alkylene groups having 1 or more and 20 or less carbon atoms.
13. A bonded body of a thermoplastic resin composition and a metal according to any one of claims 1 to 5, wherein the thermoplastic resin composition contains the chain-like aliphatic polyamide resin according to any one of claims 1 to 5.