JPH10219104A - Nylon resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which is markedly inhibited from generating monomers and oligomers when thermally melted and is suitable for producing extrusion molded items by adding an org. glycidyl ester or ether to a nylon resin. SOLUTION: This compsn. is prepd. by compounding a nylon resin with an org. glycidyl ester represented by formula I or an org. glycidyl ether represented by formula II (wherein R1 and R2 are each an org. group). The org. ester or ether is used in an amt. of 0.01-20wt.% of the resin. Usually, the ester or ether is compounded in an amt. of 0.1-10mol based on 1mol of the total terminal groups of the resin before being compounded. The addition of the ester or ether blocks terminal carboxyl and/or amino groups of the resin. Pref. the sum of the concns. of carboxyl and amino groups of the resin after being compounded is 5×10<-5> mol/g or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nylon resin molded article having excellent mechanical properties, heat resistance and surface appearance, and a resin composition for providing the same. Also, the present invention relates to a nylon resin molded article which generates a small amount of monomers and oligomers during melt heating and can be continuously molded for a long time, and a resin composition for providing the same.

[0002]

2. Description of the Related Art Nylon resin has excellent mechanical properties,
Utilizing moldability, heat resistance, toughness, chemical resistance, wear resistance, etc., injection molded products in the field of automobiles and machine parts,
Widely used as extruded products. Also toughness,
Films and sheets, utilizing transparency and oxygen barrier properties
It is also widely used as extruded products such as pipes and tubes.

In recent years, a problem in the field of nylon resin molded articles is that monomers and oligomers generated during melting and heating accumulate on a die and a casting drum over time, causing scratches on the surface of the molded article. This impairs the appearance of the product, or mixes into the product to form foreign matter. For that purpose, stop the process regularly,
There is a problem that it is necessary to clean the casting drum and the like. This problem has been demanded to be solved in the field of extruded products, particularly in the field of extruding films and sheets in which surface appearance is important.

A method generally used to suppress the generation of monomers and oligomers during melting and heating is to completely remove the monomers and oligomers by thoroughly washing the nylon resin after the polymerization of the nylon resin. However, even in this method, when equilibrium exists between the chain polymer and the monomer or oligomer such as nylon 6, there is a problem that the monomer and oligomer are always regenerated when melted during molding. In order to suppress the generation of monomers and oligomers during melting and heating, it is effective to block the terminal carboxyl group and terminal amino group.
An end blocking method at the time of polymerization has been proposed (JP-A-8-23).
1711, JP-A-8-151442 and JP-A-8-81554). However, when the terminal of the nylon resin is blocked by addition at the time of polymerization of the monofunctional compound, it is actually impossible to set the terminal blocking rate to 100%. Therefore, the terminal blocking technology described in the above-mentioned publication is required. The terminal group concentration achieved by use does not significantly suppress the generation of monomers and oligomers during melting and heating.

[0005] Japanese Patent Application Laid-Open (JP-A) No. 6-145345 (objective: improvement of mechanical properties) and Japanese Patent Application Laid-Open No. 4-28727 (objective: improvement of retort resistance) JP-A-63-203
No. 29 (Purpose: Improvement of mechanical properties and moldability), JP-A-6
JP-A-2-15029 (object: improvement of transparency), JP-A-62-10136 (object: improvement of mechanical properties and moldability), JP-A-61-296030 (object: improvement of mechanical properties and moldability) And Japanese Patent Application Laid-Open No. 61-236828 (Object: Improvement of resistance to metal halides). The aim of the technology described in these publications is to suppress the generation of monomers and oligomers during melting and heating. Not that. In addition, the terminal blocking techniques described in these publications are disclosed in the above-mentioned Japanese Patent Application Laid-Open Nos.
There is no great difference from the technical contents described in JP-A-151442 and JP-A-8-81554. Therefore, even if the technology described in these publications is used, it is not possible to significantly suppress the generation of monomers and oligomers during melt heating. You can't.

On the other hand, for the purpose of blocking terminal carboxyl groups and terminal amino groups, a method of blending a specific organic glycidyl ester or organic glycidyl ether (Japanese Patent Application Laid-Open No. 2-105821), a method of preparing a specific organic monooxazoline compound. A blending method (Japanese Patent Application Laid-Open No. 2-151654) has been proposed, but there is no description about suppression of generation of monomers and oligomers during melt heating.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to suppress the generation of monomers and oligomers at the time of melting and heating, and if necessary, has excellent film forming properties and high transparency when forming a film. It is an object to provide a nylon resin composition which gives a film.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, when a specific organic glycidyl ester or organic glycidyl ether is added to a nylon resin, the glycidyl compound is converted to a nylon resin terminal. It has been found that the compound efficiently reacts with a carboxyl group or an amino group of the above, and as a result, generation of monomers and oligomers is remarkably suppressed at the time of melt molding, and a composition suitable for an extruded product is obtained.

That is, the present invention relates to (A) a nylon resin which is suitable for extrusion molding and film formation, (B) an organic glycidyl ester represented by the following general formula (I), or (II) And a nylon resin composition comprising an organic glycidyl ester represented by the formula (I): (A) Nylon resin, (B) an organic glycidyl ester represented by the following general formula (I), or (II)
A method for producing a nylon resin composition, comprising blending an organic glycidyl ester represented by the formula: ”.

Embedded image (Here, R1 and R2 each represent an organic group.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, “weight” means “mass”.

The nylon resin used in the present invention is a resin containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the main components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, lactams such as ε-aminocaprolactam and ω-laurolactam, Tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m -Xylylenediamine, p-xylylenediamine, bis (3-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, amino Such as ethylpiperazine Aliphatic, alicyclic, aromatic diamines and adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5 -Methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, naphthalenedicarboxylic acid (1,4-form, 1,5-form, 1,8-
, 2,3-body, 2,6-body, and 2,7-body), aliphatic, alicyclic, and aromatic dicarboxylic acids. In the present invention, these are derived from these raw materials. The nylon homopolymers or copolymers can each be used alone or in a mixture.

Specific examples of the polyamide resin used in the present invention include polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 6
6), polytetramethylene adipamide (nylon 4
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecamide (nylon 61
2), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66/6
T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66/6
I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6) and copolymers or mixtures thereof Of these, nylon 6, nylon 66, nylon 610, nylon 6/66 copolymer, nylon 6/12 copolymer and mixtures thereof are preferred, and nylon 6 and nylon 6/66 copolymer, nylon 6/66 are particularly preferred. 1
2 copolymers and mixtures thereof.

The degree of polymerization of these nylon resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 6.0, particularly 2.0 to 5 0.0 is preferred.

In the present invention, an organic glycidyl ester or an organic glycidyl ether (hereinafter referred to as an organic glycidyl compound) is compounded. By mixing with the nylon resin, all or a part thereof can efficiently react with the terminal group of the nylon resin, and a polyamide resin composition suitable for extrusion molding can be obtained. In the present invention, the organic glycidyl compound reacts and disappears, and even if only the nylon resin is used, it is referred to as a nylon resin composition.

The general formula R1 constituting the organic glycidyl ester used in the present invention preferably has 1 to 30 carbon atoms. As a result, the preferred number of carbon atoms in the molecule is 4 to 31, more preferably 6 to 31. Is a glycidyl ester of a monocarboxylic acid. The monocarboxylic acid is selected from linear aliphatic monocarboxylic acids, or aliphatic monocarboxylic acids having side chains, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids, having an unsaturated bond. It doesn't matter. Specific examples include butyric acid, isobutyric acid, valeric acid, isovaleric acid, t-butyl acetic acid, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), Decanoic acid (capric acid), undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, eicosanoic acid (arachinic acid), docosanoic acid (behenic acid), tricosanoic acid , Hexacosanoic acid (serotinic acid), heptacosanoic acid (carboseric acid), octacosanoic acid (montanic acid), triacontanic acid (mericic acid), docosic acid (behenolic acid), 12,13-diketobehenic acid, behenoxylic acid, oleic acid, Eicosenoic acid, behenic acid, erucic acid, tetradecane-4,7-dienoic acid, Hexane carboxylic acid, benzoic acid, methylbenzoic acid (o-, m
-, P-form), t-butylbenzoic acid (o-, m-, p-
Isomer), ethylbenzoic acid (o-, m-, p-isomer), 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 9-
Anthracenecarboxylic acid and the like can be mentioned.

The general formula R2 constituting the organic glycidyl ether used in the present invention preferably has 1 to 30 carbon atoms. As a result, the preferred number of carbon atoms in the molecule is 3 to 30, preferably 6 carbon atoms. ~ 30 monoalcohols or glycidyl ethers of phenol. The monoalcohol is selected from a linear aliphatic monoalcohol, an aliphatic monoalcohol having a side chain, and an alicyclic monoalcohol, and may have an unsaturated bond. Specific examples of monoalcohol and phenol include propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octanol. Decanol, nonadecanol, eicosanol, docosanol,
Tricosanol, tetracosanol, hexacosanol, heptacosanol, octacosanol, triacontanol (above, linear, branched), oleyl alcohol, behenyl alcohol, phenol, cresol (o
-, M-, p-), biphenol (o-, m-, p-)
Body), 1-naphthol, 2-naphthol and the like.

Among the above organic glycidyl esters and organic glycidyl ethers (hereinafter collectively referred to as organic glycidyl compounds), the following formulas (A-1) to (A-
Glycidyl compounds as shown in 3) and (B-1) to (B-6) are preferable, and the glycidyl compound of (B-6) is particularly preferably used.

[0018]

Embedded image The amount of the organic glycidyl compound to be added can be changed according to the desired degree of blocking of the terminal groups of the nylon resin, ie, the carboxyl group and the amino group. Naturally, the amount of the terminal group of the nylon resin becomes smaller as the degree of polymerization becomes higher. Therefore, as the degree of polymerization becomes higher, a higher terminal blocking ratio can be achieved with a smaller amount of addition. Usually 0.1 to 10 times mol, preferably 0.1 to 5 times the total terminal group amount of the nylon resin before compounding.
The organic glycidyl compound is added in a molar amount of, more preferably, 0.3 to 3 times by mole. In terms of weight, the total amount of the organic glycidyl compound is 0.1 to 10 parts by weight, preferably 0.25 to 8 parts by weight, and more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the nylon resin. Then, the carboxyl group and / or the amino group of the terminal group of the nylon resin are blocked by the organic glycidyl compound. The concentration of carboxyl groups and amino groups of the polyamide resin in the nylon resin composition is 5 × 10
It is preferable to be ^-5 mol / g or less. More preferably, it is 4 × 10 ⁻⁵ mol / g or less, especially 3 × 10 ⁻⁵ mol / g.
The following is preferred.

If the amount of the organic glycidyl compound of the present invention is too small, the effect of the present invention is hardly obtained. If the amount is too large, unreacted organic glycidyl compound bleeds on the surface of a molded article such as a film or the like, Deposits tend to form defects on the film surface. However, when preparing a master pellet containing a large amount of the organic glycidyl compound and mixing it with a pellet containing a small amount of the organic glycidyl compound or not being mixed, the amount of the organic glycidyl compound in the master pellet may be large. Absent.
In that case, when the mixture of the nylon resin composition finally obtained is viewed as a whole, the same effect of the invention is provided if the mixture is specified by the present invention.

The method for producing the nylon resin composition of the present invention is not limited to a specific method, but usually a method of melt-kneading at a temperature not lower than the melting point of the nylon resin is usually used. A commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, and the like, in which a mixture obtained by dry-blending a molten nylon resin, an organic glycidyl compound, and additives as necessary using a Henschel mixer, a ribbon blender, or the like. And a method in which the mixture is kneaded at 200 to 350 ° C. depending on the melting point of the nylon resin, or a method in which the mixture is directly charged into a hopper of an extruder and melt-kneaded, and the like are suitable. Alternatively, a master pellet containing a large amount of additives may be prepared and blended with a pellet containing no additive to form a nylon resin composition, which may be supplied to a molding machine hopper.

Further, the nylon resin composition of the present invention may contain other additives such as talc, kaolin, organic phosphorus compounds, polyether ether ketone, etc. at the time of melt-kneading or melt-forming as long as their properties are not impaired. Crystal nucleating agents, coloring inhibitors such as hypophosphites, antioxidants such as hindered phenols and hindered amines, heat stabilizers, lubricants, UV inhibitors, coloring agents and the like can be added. The nylon resin composition of the present invention is preferably used for extrusion molding, particularly for forming a film.

[0022]

The present invention will be described more specifically with reference to the following examples. In addition, the blending ratios shown in Examples and Comparative Examples are all parts by weight.

Various physical properties were measured as follows.

[Relative viscosity] 1 g / 100 in 98% sulfuric acid
Measured at a mL concentration and 25 ° C. [Terminal group concentration] COOH (carboxyl group): The nylon resin composition was dissolved in benzyl alcohol, phenolphthalein was added as an indicator, and the mixture was titrated with an N / 50N KOH ethanol solution.

NH2 (amino group): After dissolving the nylon resin composition in anhydrous benzyl alcohol and reacting by adding salicylaldehyde, phenolphthalein is used as an indicator in an N / 50N sodium methoxide / anhydrous methanol solution. It was titrated.

[Tensile Properties] A sample having a width of 10 mm and a length of 50 mm was cut out, and the tensile properties were measured.

[Oxygen Permeability Coefficient] The obtained film was measured at 30 ° C. using a double gas permeability measuring apparatus.

[Haze] The obtained film was measured using an integrating sphere type light transmittance measuring apparatus. The smaller the value, the higher the transparency.

[Amount of Monomer and Oligomer] Initial: A pellet of the polyamide resin composition was pulverized to 24 mesh or less, and 10 g of the pellet was subjected to Soxhlet extraction with 200 mL of methanol for 6 hours. The obtained methanol solution was subjected to GC
The amount of the monomer (caprolactam) was determined by analysis using the internal standard method (internal standard: naphthalene). The residue was concentrated to dryness using a rotary evaporator, and the residue was vacuum-dried at 80 ° C. for 8 hours. After drying, the weight was measured, and this was defined as the amount of oligomer.

The GC analysis conditions are as follows. J & W Sc
entific capillary column DW-1 (3
0m), column temperature 200 ° C, injection temperature 2
50 ° C, detector temperature 250 ° C.

After heating: 25 g of the ground sample was sealed in a glass ampoule under vacuum and immersed in a 280 ° C. oil bath for 30 minutes. After allowing the ampoule to cool to room temperature, the ampoule was cracked to take out the nylon resin. After grinding the nylon resin with a sample mill, 10 g of the ground sample is
L for 6 hours. The obtained methanol solution was analyzed as described above, and the amounts of monomers and oligomers were measured.

[Die mark generation time at the time of melt film formation] The time from continuous film formation at 260 ° C. until the start of the formation of a die mark can be visually confirmed. Examples 1 to 6 Melt kneading of an organic glycidyl compound and a nylon resin having ηr = 4.40 in which all of the terminal groups are amino groups or carboxyl groups was performed using a 30 mmφ twin screw extruder. A nylon 6 resin having a relative viscosity of 4.40 and an organic glycidyl compound shown in Table 1 were blended to obtain a cylinder temperature of 250.
The mixture was fed to an extruder at 200 ° C. and a screw rotation speed of 200 rpm to perform melt-kneading. The extruded gut was cooled and then pelletized with a pelletizer to obtain a polyamide resin composition. After the pellet was vacuum-dried at 80 ° C. for 8 hours, the amount of terminal groups and the amount of monomers and oligomers were measured. Table 1 shows the results. Subsequently, after extruding from a T-die at 260 ° C. using a single screw extruder of 35 mmφ, L / D = 29, full flight screw, a 40 μm film is formed while continuously being taken off by a casting drum having a surface temperature of 120 ° C. did. Table 1 shows the measurement results of the physical properties of the obtained film.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

Example 7 Example 5 except that a nylon resin having ηr = 3.40 was used.
Was performed in the same manner as described above. Table 2 shows the results of various analyzes and measurements.

Example 8 Nylon 6 with ηr = 3.20 / Nylon 66 = 85/1
5 copolymers and an organic glycidyl compound (B-6)
Melt kneading was performed using a mφ twin screw extruder under the conditions of a cylinder temperature of 230 ° C. and a screw rotation speed of 200 rpm. After the extrusion gut was cooled, it was pelletized with a pelletizer. After the pellet was vacuum-dried at 80 ° C. for 8 hours, the amount of terminal groups and the amount of monomers and oligomers were measured. Table 1 shows the results. Subsequently, after extruding from a T-die at 230 ° C. using a single screw extruder of 35 mmφ, L / D = 29, full flight screw, a 40 μm film is formed while continuously being taken off by a casting drum having a surface temperature of 120 ° C. did. Table 2 shows the measurement results of the physical properties of the obtained film.

Example 9 An unstretched film having a thickness of 150 μm was formed under the same composition and conditions as in Example 1. This sheet was stretched three times in the machine direction at a film temperature of 50 ° C. by a roll-type longitudinal stretching machine, and the longitudinally stretched film was guided to a tenter-type transverse stretching machine and stretched 3.5 times at 70 ° C. Thereafter, a heat setting treatment was performed at a film temperature of 210 ° C. to obtain a biaxially stretched film having a thickness of 15 μm. Physical properties of the obtained film were measured.

Example 10 Master pellets containing a large amount of the glycidyl ether of (B-6) (nylon 6 / (B-6) = 100 parts /
6.33 parts) was prepared in advance, and 20 parts of the master pellets were mixed with nylon 6 resin pellets 8 having ηr = 4.40.
Pellets were blended into 00 parts, and the mixture was directly supplied to a hopper of a melt film forming machine to form a film. Table 2 shows the results.

Comparative Examples 1 and 2 Example 1 except that no organic glycidyl compound was added.
In the same manner as in Example 7, melt extrusion was performed, and film formation and physical property measurement were performed. Table 3 shows the results.

Comparative Example 3 A 2-liter stainless steel autoclave was charged with 700 g of ε-caprolactam, 14 g of water, 0.126 g of acetic acid, and 0.208 g of cyclohexylamine. The temperature was raised, and the initial polymerization was performed under pressure for 1.5 hours. Next, the pressure in the vessel was returned to the atmospheric pressure, and the reaction was carried out at normal pressure for 2.5 hours.
Subsequently, the pressure was reduced to 50 torr and the reaction was carried out for 2 hours.
4.40 nylon resin was obtained. The obtained resin was melt-extruded in the same manner as in Example 1, and the film was formed and evaluated. Table 3 shows the results.

As is evident from Table 1, the film obtained by adding the organic glycidyl compound of the present invention to form a melt film has excellent mechanical strength, haze and oxygen permeability regardless of stretching. In addition, the monomer when melted and heated,
It can be seen that the amount of oligomers generated is small, so that die marks are hardly generated for a long time. In the prior art end blocking at the time of polymerization is insufficient end blocking,
A large amount of monomers and oligomers are generated, and die marks during film formation are easily generated in a short time.

[0043]

As described above, the molded article of the present invention has excellent strength and oxygen barrier properties, and has a small amount of monomers and oligomers generated during melting and heating. This makes it possible to reduce the occurrence of scratches and foreign substances, and particularly to enable long-term continuous stable operation of extruded products.

Claims (11)

[Claims] An extruded nylon resin composition comprising (A) a nylon resin and (B) an organic glycidyl ester represented by the following general formula (I) or (II): Stuff. Embedded image (Where R1 and R2 each represent an organic group). 2. The nylon resin composition according to claim 1, wherein the proportion of the organic glycidyl ester and / or the organic glycidyl ester is 0.01 to 20 parts by weight based on 100 parts by weight of the nylon resin (A). 3. The nylon resin composition according to claim 1, wherein the ratio of the number of molecules of the organic glycidyl ester and the organic glycidyl ester to the total terminal group amount of the (A) nylon resin is 0.1 to 10 moles. Stuff. 4. The sum of the carboxyl group and amino group concentrations of the nylon resin in the nylon resin composition after compounding is 5 × 1.
0 ^-5 mol / g or less is claim 1 either nylon resin composition. Stuff. 5. The nylon resin composition according to claim 1, which is for a film. 6. The nylon resin is nylon 6, nylon 6.
The nylon resin molded product according to any one of claims 1 to 5, which is at least one selected from a copolymerized nylon containing as a main component and a nylon mixture containing nylon 6 as a main component. 7. An extruded nylon comprising (A) a nylon resin and (B) an organic glycidyl ester represented by the following general formula (I) or (II): A method for producing a resin composition. Embedded image (Where R1 and R2 each represent an organic group). 8. The method for producing a nylon resin composition according to claim 7, wherein the ratio of the organic glycidyl ester and / or the organic glycidyl ester is 0.01 to 20 parts by weight with respect to 100 parts by weight of the nylon resin (A). 9. The nylon resin composition according to claim 7, wherein the ratio of the number of molecules of the organic glycidyl ester and the organic glycidyl ester to the total terminal group amount of the nylon resin is 0.1 to 10 times mol. Method of manufacturing a product. . 10. The sum of the carboxyl group and amino group concentration of the nylon resin in the nylon resin composition after compounding is 5 ×.
The method for producing a nylon resin composition according to any one of claims 7 to 9, wherein the amount is ^10-5 mol / g or less. 11. A film formed by molding the nylon resin composition according to claim 5.