JPS59219365A - Polyester amide copolymer resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides filler-filled and
The present invention relates to a reinforced polyesteramide copolymer resin composition. More specifically, it is a novel filler-filled and reinforced polynisderamide copolymer composition that exhibits excellent moldability when molded at low mold temperatures of 100°C or less and provides molded products with improved mechanical strength. Regarding.

Polyethylene terephthalate (hereinafter referred to as PET) has excellent heat resistance, chemical resistance, mechanical properties, electrical properties, etc., and is used in many industrial products as fibers, films, etc. In particular, P reinforced with inorganic fillers such as glass fiber
Since ET has significantly improved thermal and mechanical properties, it has been widely used in engineering plastics and the like in recent years.

However, when it is intended to use fiber-reinforced PETi in injection molding applications, it is known that there are major molding and physical property disadvantages due to the crystallization behavior of PET. That is, since PET has a low crystallization rate at low temperatures, when injection molding is performed at a mold temperature of 130° C. or lower, for example, it is difficult to obtain a molded product with good crystallization, and only a molded product with poor surface hardness can be obtained. Moreover, if the obtained molded article is used at a temperature higher than the second-order transition point, crystallization will proceed, resulting in poor shape stability. In addition, surface roughness occurs due to non-uniform crystallization within the mold, and this poses many problems as a resin for injection molding. Furthermore, some methods are used to mold the mold at a mold temperature of around 50°C to obtain a molded product with almost no crystallization of PET, and then heat-treat it, but this method is only inefficient. However, it has drawbacks such as crystallization during heat treatment, resulting in volumetric shrinkage and deformation of the molded product. Therefore P
ET molding is usually performed using a special molding machine that can obtain a mold temperature of 130°C or higher, but such molding machines are not common, so the mold temperature 9
There has been a desire for a PET resin that can be molded favorably using a molding machine at 0 to 110°C or lower.

In order to solve the above problems, various methods have been proposed to improve the crystallization rate of PET at low temperatures. Japanese Patent Publication No. 47-3027 proposes a method of mixing gypsum or talc and polyalkylene glycol diether with polyester, but the PET obtained by this method has improved moldability compared to ordinary PET. Although the improvement effect is insufficient, 1
It is difficult to mold using a mold at 00°C or lower.In addition, in Japanese Patent Application Laid-open No. 158452/1989, sthorium or potassium salts of long-chain aliphatic carboxylic acids or pendant carboxyl groups are Sodium or potassium salts and aromatic carboxylic acid esters of organic polymers with '! A method of mixing it into 1PET has been proposed. With this method, it is possible to mold using a mold with a temperature of 100°C or less, but additives tend to evaporate during molding, which not only often causes white smoke to be generated and deteriorates the working conditions, but also makes molding difficult. It also has the disadvantage of deteriorating the surface gloss of objects. Various other methods have been proposed, but none of them f'L
However, the effect of improving moldability was not sufficient.

The present inventors have developed an additive that has a low-temperature crystallization promoting effect that allows PET crystallization to proceed sufficiently even at a mold temperature of 100°C or less, and that does not have the above-mentioned drawbacks. As a result of various studies to obtain this, we found that a polyesteramide copolymer made by modifying PET with a polyamide oligomer having a specific structure, reinforced or filled, with a carbon number of 7 to 25
The object can be achieved by the combined use of a sodium salt or potassium salt of a carboxylic acid, or a sodium or potassium salt of a polymer having a carboxyl group, and a polyalkylene glycol compound. Reached.

That is, the present invention provides (^) 0.05 to 205 to 20 parts by weight of a polyamide plotter consisting of amide units represented by the following general formula (1) (f(a, R2 represents hydrogen or a methyl group)
A polyester block consisting of ester units represented by the following general formula (II) (representing an integer of 99.95 to 805 to 80 parts by weight to 4) and having a solid viscosity of 0.5 or more. and the above-mentioned polyamide plotter is made of 100 parts by weight of a polyester amide copolymer having an average continuous repeating number of amide units of 2 to 40 (B) Reinforcement 1fc is a filler material 10 to 140 parts by weight 0 Carbon number 7 to 25 0.05 to 20 M parts of the sodium salt or potassium salt of carboxylic acid, or the sodium salt or potassium salt of a polymer containing a carboxyl group, and (0 general formula RIO-f R20 + nM (/ζ dashi R1
, R1' represents H or a lower alkyl group, and Rz represents an alkylene group having 2 to 4 carbon atoms. 1, and n is an integer greater than or equal to 5. ) is a polyesteramide-based copolymer composition composed of 0.1 to 10 parts by weight of polyalkylene glycol.

In the present invention, the polyester block constituting the polyesteramide copolymer is an aromatic polyester obtained from terephthalic acid or its ester-forming derivative and a linear aliphatic diol having 2 to 4 carbon atoms, and includes polyethylene terephthalate, polypropylene terephthalate, etc. , polybutylene terephthalate. Among these, polyethylene terephthalate is preferred because molded products with particularly high strength and high modulus of elasticity can be obtained, and the mole percentage of the diol component can be replaced with other dicarboxylic acids or diols. It may be something like that.

Such dicarboxylic acids include inctaric acid, orthophthalic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, succinic acid, adipic acid, sebacic acid,
Examples of diols such as dodecanedioic acid, neopentyl glycol, 1,4-cyclohexanediol, 1,
Examples include 4-cyclohexane dimetatool, diethylene glycol, polyethylene glycol, and the like.

In the present invention, in the amide unit constituting the polyamide block, the dicarboxylic acid component is in7thalic acid, orthophthalic acid, or terephthalic acid. and,
It is preferable that at least 30 moles of the dicarboxylic acid component consist of inphthalic acid and/or orthophthalic acid because the copolymerization reaction described below can be carried out very easily. Further, the diamine component is piperazine or a ring-substituted derivative thereof. Examples of ring-substituted derivatives of piperazine include methylpiperazine and trans-2,5-dimethylpiperazine. Less than 40 moles of the dicarboxylic acid component constituting the amide unit of Cholera can be replaced by other dicarboxylic acids such as succinic acid, succinic acid and adipic acid. In addition, less than 10 moles of the diamine component may be substituted with other diamines, e.g.
enylene diamine, m-phenylene diamine, p-phenylene diamine, 2.4-) lyene diamine, 2.6-
1 luenediamine, 3.4-1 luenediamine, 1.5
-1-phthylenediamine, 1,8-naphthylenediamine, p,p'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenylsulfone, 4,4-diaminodiphenylsulfone, iso7-tali It may be replaced with aromatic diamines such as tsukudihydrazide and terephthalic dihydrazide, alicyclic diamines such as 1,4-cyclohexanediamine, and aliphatic diamines such as hexamethylene diamine.

In the present invention, it is necessary that the polyamide block has an average number of continuous repeats of amide units of 2 or more. If the average number of continuous repetitions is less than 2, the effect will not be sufficiently expressed, and a copolymer with a high crystallization rate at low temperatures and in a mold cannot be obtained. The upper limit is not particularly strictly defined, but if it exceeds 40, it becomes difficult to copolymerize with polyester, so it is undesirable.For polyester blocks, there is no particular limit to the average continuous repeating number, but 20 About 500 is preferable.

The polyesteramide copolymer used in the present invention must be composed of 0.05 to 20 weight φ of polyamide block and 99.95 to 80 weight % of polynisdel block. The amount of polyamide block is 0.
If the amount is less than 0.05% by weight, the effect will not be sufficiently expressed.

At 0.05% by weight or more, the effect becomes noticeable, especially at 0.05% by weight or more.
．． At 1 weight φ or more, copolymers having substantially the same low-temperature crystallization rate can be obtained even if the copolymerization amount changes. As described above, a major feature of the present invention is that sufficient effects can be obtained even with a small amount of polyamide block. Furthermore, if the amount of polyamide blocks exceeds 20 wt. 1 ik%, the polycondensation reaction will be difficult to proceed, making it impossible to obtain a copolymer with a high degree of capping, which is not preferable. Therefore, the copolymerization ratio of the polyamide block is suitably in the range of 0.05 to 20% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.2 to 5% by weight.
There are two people in charge of weight.

The polyesteramide copolymer used in the present invention is phenol/tetrachloroethane (1/l) at 25°C.
It is necessary that the intrinsic viscosity measured in the volume ratio is 0.5 or more. If the intrinsic viscosity is less than 0.5, a product with sufficient performance over the next month cannot be obtained. There is no particular limit on the upper limit, but if the hard-shouldered viscosity is 2.0 or higher, it will be difficult to manufacture for practical purposes.

The polyester amide thread copolymer used in the present invention can be produced by the method described below. Namely, the polyester precursor represented by formula (III) 0 1 HO (-CH2%0 -CQC-0(LCH2 island OH(I
II) (n represents an integer of 2 to 4) Alternatively, a polyamide oligomer (R1, R2fd hydrogen or methyl group) having an average degree of polymerization of 2 to 4o and having repeating units represented by formula (I) is added to the low polycondensate. It is produced by dissolving the compound (represented in Table 1) and then carrying out a polycondensation reaction. The polyester precursor represented by the formula (I[l) or its low polycondensate is produced by esterifying or transesterifying a raw material for producing polyester, that is, terephthalic acid or its ester-forming derivative, and an aliphatic diol. can do. The esterification reaction or the transesterification reaction can be carried out under conditions normally employed in the production of polyester. By adding and mixing the polyamide oligomer into the melt of the obtained polyester precursor or its low polycondensate, the polyamide oligomer is easily dissolved. Note that the low polycondensates mentioned here refer to those with an intrinsic viscosity of 0.2 or less.
Yeah. In addition, the polyester precursor or its low polycondensate has a repeating unit represented by the formula 0(1), which may contain terephthalic acid as a raw material, its ester-forming derivative, or an aliphatic diol. The molecular chain terminals of the polyamide oligomer are preferably mostly carboxyl groups or ester-forming groups derived from carboxyl groups in terms of reactivity and solubility with the polyester precursor. Examples of the ester-forming group derived from a carboxyl group include methyl ester, ethyl ester, lower alkyl ester of hydroxyethyl ester, and ester of phenol or phenol derivatives.

Furthermore, when 70 moles or more of the dicarphonic acid component constituting the polyamide oligomer is terephthalic acid,
It is necessary that a phenol derivative residue represented by the following formula (IV) is bonded to at least 50'% of the two molecular chain ends, and the average degree of unity of the polyamide oligomer is in the range of 2 to 5. It is necessary.

If the above-mentioned group is not bonded to the molecular chain end or the bonding ratio is less than 50%, copolymerization with polyester becomes difficult. Furthermore, if the average degree of polymerization of the oligomer exceeds 5, copolymerization with polyester by melt polycondensation becomes difficult, so it is necessary to employ a special method as described below. That is, the polyamide oligomer is dimethylacetamide, dimethylformamide, N
- Uniformly mix a solution of methylpyrrolidone, hexamethylphosphoramide, etc. and a solution of polyalkylene terephthalate or its oligomer dissolved in a solvent such as dimethyl sulfoxide. A uniformly mixed solidified product of polyamide oligomer and polyalkylene terephthalate or its oligomer is precipitated. After separating the solvent from this precipitate, solid phase polycondensation is performed to obtain copolymer f:.

In the group represented by the above formula (1), either R3 or & must be an alkyl group having 3 to 5 carbon atoms, and the bonding of such a substituent will cause the formation of the polyamide oligomer. The solubility is improved and the dissolution into the polyester precursor becomes nJ-capable. Examples of the alkyl group having 3 to 5 carbon atoms include n-propyl group, 1so-propyl group, n-butyl group, is.

-butyl group, tert-butyl group, n-pentyl group, l-pentyl group, etc.
Most preferred is the tert-butyl group. & is hydrogen, lower alkyl group or lower alkoxy group.

If at least 30 molar parts of the polyamide oligomer component are phthalic acid and/or orthophthalic acid, the above-mentioned restrictions apply.
This is advantageous in the production of copolymers because it is sufficient that most of the molecular chain ends are carboxyl groups or ester-forming groups derived from carboxyl groups.

The N m4 synthesis reaction carried out after dissolving the polyamide oligomer in the polyester precursor or its low polycondensate can be carried out under the same conditions as for ordinary polyester polycondensation. That is, the reaction is carried out under reduced pressure at a temperature slightly higher than the melting point of polyester using an antimony compound, titanium compound, germanium compound, or zinc compound as a catalyst.

Further, depending on the case, all methods such as solid phase polymerization may be combined. The polycondensation reaction causes polycondensation of polyester and condensation reaction of polyester and polyamide oligomer to obtain the polyesteramide block comonomer of the present invention. Since most of the added polyamide oligomer is copolymerized with the polyester without any decomposition reaction, a copolymer of any composition can be obtained by adjusting the addition of polyamide oligomer: t. Therefore, the amount of polyamide oligomer added is 100 parts by weight of polyester (the amount of polyester obtained when the polyester precursor is polymerized alone).
It is appropriate to use the amount in the range of 0.05 to 25 parts by weight. Further, the average number of consecutive repeats of amide units in the polyamide blocks in the copolymer approximately corresponds to the average degree of polymerization of the polyamide oligomer used.

The polyamide oligomer can be synthesized by mixing an aromatic dicarboxylic acid chloride selected from terephthalic acid, isophthalic acid and orthophthalic acid with piperazine or a ring-substituted derivative thereof and reacting the mixture.

The reaction is preferably carried out in an appropriate solvent, and examples of the solvent include halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane, and benzene, 11-hexane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and hexamethylphosphorol. Examples include amides and mixed solvents thereof.

It is preferable to add a tertiary amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, N-ethylpiperidine, N-ethylmorpholine, etc. to these solvents in order to facilitate the reaction. In addition, monovalent or divalent lower aliphatic alcohol,
Phenol or monovalent or divalent phenol derivatives coexist, or aromatic dicarboxylic acid chloride monoesters (monovalent or divalent lower aliphatic alcohols, esters with phenol or monovalent or divalent phenol derivatives, etc.) (preferably) coexist, it is possible to obtain a polyamide oligomer having -8' ester linkage at the terminal, and by appropriately selecting the i used, the degree of polymerization of the obtained polyamide oligomer can be controlled. It's convenient. In addition, when 70 moles or more of the dicarboxylic acid component of the polyamide oligomer is terephthalic acid, a phenol derivative represented by the general formula or a monoester of the derivative and terephthalic acid chloride is used to form the terminal of the molecular chain of the polyamide oligomer. 50φ or more, as described above.
ζ A group represented by general formula (IV) is bonded.

The polyamide oligomer production reaction proceeds rapidly at the same time as the raw materials are mixed, and a polyamide oligomer is obtained. The reaction temperature is preferably lower than room temperature, and suitably around 0°C.

The above aromatic dicarboxylic acid chloride monoester is
It is obtained by reacting aromatic dicarboxylic acid chloride with alcohol or phenol. During the reaction, in order for the esterification reaction to proceed smoothly,
Triethylamine, tri-n-propylamine%1l-
Tertiary amines such as n-butylamine, N-ethylpiperidine, N-ethylmorpholine, etc. may be added. The obtained aromatic dicarboxylic acid chloride monoester can be purified and used, but the reaction product can also be used directly. In this case, add more aromatic dicarboxylic acid chloride to the reaction product, or use an excess of aromatic dicarboxylic acid chloride from the beginning. l: This is convenient because it can be subjected to a reaction with a ring-substituted derivative thereof. The amount of aromatic dicarboxylic acid chloride and aromatic dicarboxylic acid chloride monoester used is 0% of aromatic dicarboxylic acid chloride monoester per mol of aromatic dicarboxylic acid chloride.
．． It is preferable to use it in a range of 1 to 2.0 mol. Generally, the larger the amount of aromatic dicarboxylic acid chloride monoester used, the lower the degree of polymerization obtained.
The smaller the amount used, the higher the degree of polymerization can be obtained. Since the reaction is almost quantitative, the amounts of aromatic dicarboxylic acid chloride and piperazine or their ring-substituted derivatives are as follows:
It is preferable that the amount of one COα group and the amine group in the entire reaction system including the aromatic dicarboxylic acid chloride is approximately equal.

Whether or not the desired polyesteramide block copolymer has been obtained by the reaction between the polyester and the polyamide oligomer can be confirmed, for example, by the method described below. That is, the obtained polymer was dissolved in a mixed solvent of phenol/tetrachloroethane, n-hebutane, which is a non-solvent for the polymer, was added until the solution showed clear turbidity, and then centrifuged to form the solution into two layers. After separation, the lower thick layer is taken out and poured into a large amount of methanol to precipitate the polymer. If unreacted polyamide oligomer remains, it is removed by this operation. Next, the infrared absorption spectrum of the precipitated polymer was measured.
If absorption based on =O stretching vibration appears, it can be confirmed that the polyamide is copolymerized. Further, the copolymer composition can be determined from the nitrogen content determined by elemental analysis. Furthermore, the average number of continuous repeats of amide units can be indirectly predicted from the degree of polymerization of the polyamide oligomer used as a raw material, but can also be determined directly from high-resolution NMR spectrum analysis of the obtained polymer. Furthermore, the fact that amide units are copolymerized in a block form in the polymer is confirmed by the fact that there is almost no decrease in the melting point due to copolymerization and that a phase-separated structure is observed when the polymer melt is observed under a microscope. .

Reinforcing or filling materials used in the invention (includes talc, clay, kaolin, mica, asbestos,
Silicates such as wollastonite and calcium silicate, silica,
Inorganic fillers such as gypsum and graphite, and glass fibers,
Examples include fibrous reinforcing agents such as carbon fiber, graphite fiber, metal carbide fiber, metal nitride fiber, aramid fiber, and phenol resin fiber. These reinforcing or filling materials may be used alone or in combination of two or more. Further, these may be used as they are, or may be used after surface treatment or sizing agent treatment. Among the above-mentioned reinforcing or filling substances, glass fibers or a combination of glass fibers and mica are preferred because they significantly improve the heat resistance and mechanical properties of the molded product. Reinforcing or filling substance (average usage amount is JO~1 for 100 parts by weight of polyesteramide copolymer (A))
A 40-layer lid is suitable. If it is less than 10 parts by weight, sufficient effects cannot be obtained, and if it exceeds 140 parts by weight, the fluidity of the system becomes poor and molding becomes difficult.

Examples of the sodium salt or potassium salt of a carboxylic acid having 7 to 25 carbon atoms, or the sodium salt or potassium salt (C) of a polymer containing a carboxyl group used in the present invention include stearic acid, pelargonic acid, behenic acid, etc. Copolymerization of olefins such as ethylene/methacrylic acid copolymers, ethylene/acrylic acid copolymers, etc. with acrylic acid or methacrylic acid, sodium or potassium salts of 1, styrene/maleic anhydride copolymers, etc. Examples include sodium or potassium salts of co-M combinations of aromatic olefins and maleic anhydride, such as superimposed bodies. Among these, sodium salts of polymers containing carboxyl groups or potassium 9
Salt is preferably used because it causes less decrease in the viscosity of the polyester resin during molding. In addition, in the above copolymer,
Olefin reed or aromatic olefin is a copolymer of 50~
98:! It is preferable to use a polymer that accounts for 80 to 980 to 98 parts by weight, and a particularly preferable polymer is a sodium salt of an ethylene/methacrylic acid copolymer. The amount of component (q) used is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on ~100 parts by weight of the polyesteramide copolymer (20 parts by weight). If it exceeds the amount, the mechanical properties of the molded product will deteriorate, and if it is less than 0.05 part by weight, the effect of improving moldability will be insufficient.

The general formula used in the present invention is the formula % (&, &' represent H or a lower alkyl group, and brain represents an alkylene group having 2 to 4 carbon atoms. Also, n is an integer of 5 or more.) The polyalkylene glycols represented include polyethylene glycol, polypropylene glycol, polydetramethylene glycol and their mono- or dialkyl ethers (e.g. monomethyl or dimethyl needle, monoethyl diethyl ether, monoglobil or dipropyl ether, motuptyl). (Dibuterethyl, etc.) can be mentioned. In the present invention, it is preferable that the polyalkylene glycol has alkyl ether at both ends, since the solid viscosity of the polyesteramide copolymer is less likely to decrease during molding.

When using a monoalkyl ether in which only one end is etherified or a polyalkylene glycol in which both ends are hydroxyl groups, the intrinsic viscosity of the polyesteramide copolymer during molding will decrease significantly. , component 0 requires the use of a polyesteramide copolymer with a high degree of polymerization (the average degree of polymerization n must be 5 or more; if it is less than 5, component 0 will stand out on the surface of the molded product) The appropriate amount of O component 0, which is undesirable because it causes a darkening, is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the polyesteramide copolymer (5). If the amount is more than 10 parts by weight, the rigidity of the molded product will decrease, and if it is less than 0.1 part by weight, the effect of improving moldability will be insufficient, so it is unsuitable.

Since the composition of the present invention has a high crystallization rate even at relatively low temperatures,
Even when molding is performed at a mold temperature of approximately 00° C., a molded product that is uniformly and highly crystallized to the surface layer and has excellent surface gloss can be obtained with a short mold residence time. The molded product obtained has excellent dimensional stability and shape stability even at high temperatures, exhibits extremely low warpage and excellent heat resistance a.

In the composition of the present invention, in addition to the above-mentioned components, additives commonly used in polyester resins, such as colorants,
It can contain a mold release agent, an antioxidant, an ultraviolet stabilizer, a flame retardant, and the like.

The composition of the present invention is produced by mixing each component by any known means. For example, the polyesteramide copolymer is mixed with the components (Bl, (C), (L)) in any suitable mixer or rotating machine, and the mixture is melt extruded, or the polyesteramide copolymer is polymerized. In the final stage of molten resin, components (to), (C),
It is also possible to mix (In) and extrude it as it is.Also, the components (C1, (II
It is also possible to adopt a method of melt-kneading and then blending component Φ), or conversely, a method of melt-kneading component 0.0 into a polyesteramide copolymer containing component (B).

The composition of the present invention does not require any special molding method or reaction conditions, and can be molded under the same conditions as those used for molding ordinary thermoplastic resins.Reference Example 1 [Synthesis of polyamide oligomer] Attach a dropping funnel, nitrogen gas introduction tube, reflux device, and stirrer to a 300d four-eye flask, 15
Q+aA! of methylene chloride, and 0.048 mol of anhydrous bibenzine and 0.04 mol of catechol were added at room temperature under a nitrogen gas stream.
012 mol, triethylamine 10+dt dissolved. Methylene chloride solution 501de in which 0.030 mol of terephthaloyl chloride and 0.030 mol of inphthaloyl chloride were dissolved
It is added dropwise into the reaction vessel at room temperature over a period of 30 minutes, and the reaction is allowed to proceed for an additional 30 minutes at room temperature.

Thereafter, methylene chloride was removed by distillation, the resulting residue was sufficiently washed with gold water, and then vacuum dried to obtain a polyamide oligomer.

In the proton NMR spectrum of this oligomer,
δ=8. The absorption of phenyl protons adjacent to carboxylic acid or carboxylic acid ester appearing near Oppm and δ-7. The number average degree of polymerization of the polyamide oligomer was determined from the intensity ratio with other phenyl proton absorptions appearing in the region from Qppm to δ-s and oppm, and found that n=3.0.

Reference Example 2 [Synthesis of bis-β hydroxyethyl tere-7 tallate (BHET)] Dimethyl terephthalate 2 was placed in a 500d three-meter flask.
04F, ethylene glycol 1502, and calcium acetate 0.33f were heated to 180°C under a stream of bonbon gas, and the reaction was continued for 4 hours to obtain BHET gold.

Reference example 3 [Synthesis of polyesteramide copolymer] 2
00m/BHET 38 obtained in Reference Example 2 by attaching a nitrogen gas introduction tube, an air cooling tube, and a stirrer to a Mitsuro flask.
f, triphenyl phosphate 4■, antimony trioxide 1
01η Gold pot is heated in a 220° C. oil bath under a nitrogen gas stream to melt BHET'i. In this state, reference example 1
The powdered polyamide oligomer obtained in step 1 was added in an amount of 0.5% by weight based on BHET, and stirred for 10 minutes. The oligomer B) dissolved in LET and became a colorless and transparent melt. Then, while keeping the oil bath temperature at 220°C, the system was gradually depressurized to 5 + maHg.Then, the oil bath temperature was raised to a total of 280°C, the system was depressurized to 0.5 mrHg or less, and the system was depressurized to 5 + maHg. Polyesteramide copolymer was obtained by proceeding the polymerization for 2 hours under 0 phenol, tetrachloroethane (1:1 v
The intrinsic viscosity ([η]) determined at 25°C in
It was 89.

The following experiment was conducted to confirm that the obtained polymer was a copolymer of polyester and polyamide. A solution was prepared, n-hebutane was added to this solution until the solution showed clear turbidity (approximately 19 cm), and the mixture was centrifuged, and the entire lower layer of the liquid separated into two layers was collected. The collected liquid was poured into a large amount of methanol to precipitate the polymer, dried separately, and the infrared absorption spectrum was measured.Also, polyethylene terephthalate homopolymer 0.189 and polyamide oligomer 0.020f f 20 ml The sample was dissolved in a phenol/tetrachloroethane mixed solvent and subjected to all the same treatments to measure the infrared absorption spectrum.

In the polymer obtained in this example, an absorption based on the C=O stretching vibration of hyperazinamide is observed at 1630 crn, whereas infrared absorption spectra of polyethylene terephthalate homopolymer or a mixture of polyethylene terephthalate and polyamide oligomer are observed. No such absorption is observed.

Therefore, it was confirmed that polyamide was copolymerized in the polymer obtained by reacting with the polyamide oligomer IBHET.

Furthermore, when the polymer was melted at 280°C and observed under a 200x optical microscope, no phase-separated structure was observed for the homopolymer of polyethylene terephthalate, and a fine-particle phase-separated structure was observed for the polymer obtained in this example. ;I didn't see it. This indicates that the obtained polymer is a block copolymer. It is confirmed that the obtained polymer is a block copolymer since another experiment in which the polyamide block content ff: was changed and the melting point of the polymer did not drop at all. will be explained more specifically. All parts in the examples are by weight unless otherwise specified.

Example 1 100 parts of the polyesteramide copolymer obtained in Reference Example 3 (intrinsic viscosity 0.89), 8 parts of sodium salt of ethylene/methacrylic acid copolymer (Su-Rin 1707, manufactured by Mitsui Polychemical Co., Ltd.) , polyethylene glycol dimethyl ether (average molecular weight of polyethylene glycol part 100
0) 3 parts, glass fiber (Nittobo Co., Ltd. eS3PE47s
, focused chopped strands, cut length 3 m) 5
0 part was premixed and then put into the hopper of a 4Ofmφ extruder (f3VSE-40-28 type manufactured by Osaka Seiki Kogyo Co., Ltd.), and the cylinder temperature was 250-275-275-275℃.
An extruded pellet was obtained by melt-kneading at an adapter temperature of 265°C and a die temperature of 265°C. The extrusion was carried out smoothly and a well-dispersed pellet of glass fibers was obtained.

After drying the obtained pellet under reduced pressure at 120°C for 15 hours, the injection molding machine (Niroku Uncle Berg Co., Ltd. 1V- A test piece was molded using a mold 15-75. It showed good moldability despite being molded using a low-temperature mold.

Table 1 shows the surface smoothness of the molded piece and the crystallinity of the polyesteramide copolymer on the surface (measured by X-ray analysis).

Comparative Example 1 A composition was obtained and molded in exactly the same manner as in Example 1, except that a homopolymer of polyethylene terephthalate (intrinsic viscosity: 0.85) was used instead of the polyesteramide copolymer.

Despite being molded in a low-temperature mold, it showed good moldability and excellent surface smoothness, but in terms of surface crystallinity, Example 1 using a polyesteramide copolymer was superior. Ta.

Example 2 In Example 1, sodium stearate A (1
A molding was performed under the same conditions as in Example 1, except that 7 parts of . The surface smoothness and crystallinity of the molded product obtained are shown in Table 1.

Example 3 Molding was carried out under the same conditions as in Example 1, except that in Example 1, a polyesteramide yarn copolymer with an intrinsic viscosity of 101 was used.2, and polyethylene glycol (average molecular weight 1000) was used in part a instead of polyethylene glycol dimethyl ether. I did this. Table 1 shows the physical properties of the molded product obtained. When polyethylene glycol that does not have dialkyl ether at both ends is used, the intrinsic viscosity of the polyester polyamide copolymer decreases significantly.
Example 4 All molding was carried out under the same conditions as in Example 1 except that 50 parts of mica was used instead of glass fiber. Table 1 shows the physical properties of the molded product obtained.

Table 1 Comparative Example 2 Molding was carried out under the same conditions as in Example 1 except that the amount of polyethylene glycol dimethyl ether in Example I was changed to -eo, 09 parts. It lacked sex.

Comparative Example 3 Example 1 except that the amount of thorium salt of the ethylene/methacrylic acid copolymer was changed to 0.04 parts.
Molding was carried out under the same conditions. Similar to Comparative Example 2, irregularities were observed on the surface of the molded product.

Comparative Example 4 Molding was carried out under the same conditions as in Example 1 except that the amount of polyethylene glycol dimethyl ether was changed to 11 parts. The fluidity of the resin during molding was good, and the surface smoothness of the molded product was also good, but the rigidity was poor due to the large amount of plasticizer blended.

Example 5 Molding was carried out under the same conditions as in Example 1 except that 3 parts of polyethylene glycol dimethyl ether having an average molecular weight of 400 in the polyethylene glycol portion was used. The surface smoothness and crystallinity of the molded product are shown as 1.

As explained above for each fruit/male side, even when the composition of the present invention is injection molded using a mold at a low temperature of 1.00°C or less, the crystallinity of the resin on the surface progresses and the surface smoothness is improved. 〇 Patent applicant: RiRa Co., Ltd. Representative patent attorney: Ken Honda

Claims (1)

[Scope of Claims] (1) (~0.05 to 20% by weight of a polyamide block consisting of amide units represented by the following general formula (1)), and (hh, R2 represents hydrogen or methyl group) the following general formula: 99.95 to 80% by weight of polyester block consisting of ester units represented by (I[) (n is 2 to 80% by weight)
(representing an integer of 4) is a random type block copolymer having an intrinsic viscosity of 0.5 or more, and the polyamide block is a polyesteramide having an average continuous repeating number of amide units of 2 to 40. System copolymer 100 parts by weight (B) Reinforcement or filler substance 10 to 140 parts by weight (
q Sodium salt or potassium salt of a carboxylic acid having 7 to 25 carbon atoms, or sodium salt or potassium salt of a polymer containing a carboxyl group 0.05 to 20 parts by weight and 0 General formula RtO+&O+-n&' (Tomodashi R1, R1 ' represents H or a lower alkyl group, and s represents an alkylene group having 2 to 4 carbon atoms.
n is an integer of 5 or more. ) A polyesteramide copolymer resin composition comprising 0.1 to 10 parts by weight of a polyalkylene glycol represented by: (2) Claim 1 in which component 0 is a sodium salt or potassium salt of a polymer containing a carboxyl group.
Compositions as described in Section. (8) The composition according to claim 1, wherein R1 and side of component 0 are lower alkyl groups. Component (5) of the composition according to claim 1, wherein at least 30 moles of the dicarboxylic acid residues constituting the entire polyamide block in component (4) are isophthalic acid and/or orthophthalic acid residues. In ~, the average number of consecutive repeats of amide units in the polyamide block is 2
5. The composition according to claim 5, wherein the composition is .about.5. (The composition according to claim 1, wherein 30 molar or more of the dicarboxylic acid residues constituting the entire polyamide block in the gradient is isophthalic acid residues, and the remainder is terephthalic acid residues. The composition according to claim 1, wherein the content of polyamide blocks in component (A) is 0.1 to 5% by weight. 2% by weight of the composition according to claim 1. (9) The composition according to claim 1, wherein the diamine residue of the polyamide block in component (8) is a piperazine residue. (10) The composition according to claim 1, wherein n of the diol residue of the polyester block in component (f) is 2.