JPS59193955A - Molding resin composition - Google Patents

Abstract

PURPOSE:A composition obtained by incorporating polyethylene terephthalate with a crystal nucleating agent and a specific ether compound, and capable of giving molded articles having improved surface gloss and reduced heat shrinkage in a mold at low temperatures with improved moldability without causing volatilization in a mold at high temperatures. CONSTITUTION:A molding resin composition obtained by incorporating (A) 100pts.wt. polyethylene terephthalate with (B) 0.05-10ptw.wt. crystal nucleating agent, and (C) 0.1-10pts.wt. ether compound expressed by the formula (R is H or monofunctional aliphatic hydrocarbon; Ar is monofunctional hydrocarbon; n is an integer >=1). A polyamide having preferably >=2 amide-forming groups linked through amide or hydrazide bonds without decomposing nor melting at <=270 deg.C or talc, etc. may be used as the component (B). A compound expressed by the formula (n is 1-10, preferably 1-6; R is 1-20C monofunctional aliphatic hydrocarbon; Ar is phenyl or benzyl) is used as the component (C).

Description

Detailed Description of the Invention Technical Field The present invention relates to an ester resin composition, and more specifically, it relates to an ester resin composition, and more specifically, by blending a special ether compound into polyethylene terephthalate together with a crystal nucleating agent, the composition can be easily stabilized during molding, drying, etc. During heating operation or high temperature 1
The present invention relates to a molding resin composition that contains few components that volatilize when used in a rectangular atmosphere, and that provides a molded product with good heat shrinkage and surface gloss even when molded at a low mold temperature.

Conventional technology-4 is that polyethylene terephthalate has a slow crystallization rate, so when injection molding is performed at a normal mold temperature of 70 to 120°C, an avatar-like pattern occurs on the surface of the obtained molded product. They exhibited a dull and rough appearance, had poor shape stability and a high heat shrinkage rate, and were not satisfactory in terms of other physical properties. For this reason, conventionally, ethylene terephthalate molding has been carried out by using a special high-temperature mold to maintain the temperature above 150°C, but such high mold temperatures require a significantly longer molding cycle. This has become a major negative factor in terms of production.

Therefore, in order to promote the crystallization of polyethylene terephthalate and improve the above-mentioned drawbacks, for example, a crystal nucleating agent consisting of inorganic particles, of which talc is a typical example, is used.
A method of increasing the crystallization rate by blending approximately 2% by weight (Japanese Patent Publication No. 7542/1983), or a method of blending an alkali metal salt of an organic carboxylic acid (Japanese Patent Publication No. 48/4097), etc. is proposed. However, in these methods, only the crystal nucleating agent added is sufficient. The effect of increasing the crystallization rate of polyethylene terephthalate is not sufficient, so when these compositions are used as molding phase additives, the mold temperature is not much different from that of conventional molds, and it is necessary to increase the mold temperature to a high temperature of 130 to 140 °C or more. There is a need to.

In addition, we have so far developed a composition (% 158452
Publication No. 2) has also been proposed.

However, although the crystallization of polyethylene prephthalate is considerably promoted by such a formulation,
When a molding material made of this composition is injection molded, a so-called mold deposit is observed in which a precipitate is generated in the mold cavity, and furthermore, because the low-molecular organic plasticizer used here is volatile, If gas is generated when polyethylene terephthalate is mixed, or when the resulting mixed product is dried or molded, or if the molded product is used in a high-temperature atmosphere for a long time, low-molecular organic plastics may occur. There are many problems such as dimensional changes in the molded product due to the gradual extraction of the agent. As a result of intensive research to overcome these drawbacks, it was discovered that polyethylene terephthalate combined with a crystal nucleating agent and a special ether compound in a certain proportion could achieve the seven objectives.Based on this knowledge, the present invention was developed. It was completed.

That is, the present invention includes (A) 100 parts by weight of polyethylene terephthalate, and (B) 0.05 to ILM of a crystal nucleating agent.

and (C) an ether compound represented by the general formula (wherein R is hydrogen or a -valent aliphatic hydrocarbon group, Ar is a monovalent hydrocarbon group, and n is an integer of 1 or more) 0 , 1 to 10 parts by weight.

Examples of polyethylene terephthalate used as component (A) of the present invention include ethylene terephthalate homopolymers, copolymers containing at least 70 moles of ethylene terephthalate repeating levels, and mixtures with other polyesters in equivalent amounts. Among these, those having an intrinsic viscosity of 0.4 or more as determined at 35° C. in a mixed solvent containing phenol and tetrachloroethane in a weight ratio of 6 to 4 are preferred.

As the crystal nucleating agent used as component (B) of the present invention, conventionally known useful compounds (Plastics, Age
r Nov.

92 (198], ) ), for example, mica, aluminum calcium/licade, inorganic powders such as metal oxides, sodium stearate, sodium benzoate, sodium monomethyl terephthalate, ethylene and acrylic acid. or methacrylate A; - sodium salt of copolymer with acid, sodium salt of copolymer of styrene and maleic anhydride, sodium salt of organic carboxylic acid, etc., but preferably -tL<i- t, (i)
Polyamides having at least two hydranamide bonds or hydranopa bonds, or both, which do not melt or decompose at temperatures below 270°C, (II) having the general formula (in which M and M' are the same); - or different 7 groups (1) metal, 0 and p are 1 or 2), and aromatic oxysulfonic acid metal salts represented by: The above may be used in combination. The items that freeze particularly well are listed above (
1) and (II). These preferred crystal nucleating agents have a synergistic effect with component (C) that causes crystallization of component (A), when the &IJ ethylene terephthalate is cooled from the molten state in the mold, without requiring a long induction period. Crystallization is promoted precisely, or, for example, when organic sodium carboxylate is used as a crystal nucleating agent, a smooth effect such as less deterioration of polyethylene terephthalate is produced.

Here, the polyamides of (I) have the general formula % () () () () () () () ) (In the formula, Ar1, Ar2 and Ar5 are divalent hydrocarbon groups, Ar4 and Ar5 is a monovalent hydrocarbon group) is a polyamide in which at least two types of amide-forming groups represented by amide bond or hydrazide bond or both are linked, the amide bond and the amide bond in the molecule of the polyamide. The polyamide has a sum of the number of hydrazide bonds of 2 or more and does not melt or decompose at a temperature of 270°C or lower, preferably 300°C or lower. Among these, those of general formula (IV), (V), (Vl
), (vIl), and G[X) are selected from among the amide-forming groups represented by i''I-2s or more connected by an amide bond.

Here, as Ar1, for example, -CH2Cf(2-1, etc.) is suitable, and as Ar4 and Ar5, examples can be mentioned, but among these, the preferable ones are Ar1, Ar2 and Ar3 are both divalent aromatic hydrocarbon groups, and both Ar4 and Ar5 are monovalent aromatic hydrocarbon groups, and these are believed to have an effect as a crystal nucleating agent as well as from the viewpoint of thermal stability. There is.

These polyamides may be homopolymers, random copolymers, block copolymers, or may be block copolymers or graft copolymers with other polymers, but they must not melt or decompose at temperatures below 270°C. It is especially preferable that melting or decomposition does not occur at a temperature of 300° C. or lower. The sum of the number of amide bonds and the number of hydrazide bonds in the twisted z IJ theamide molecule is over 2μ, and there is no particular restriction on the upper limit. However, since these NII amides are used as crystal nucleating agents, they need to be dispersed in an extremely fine state in the polyethylene terephthalate component (A). A method of melt blending, a method of precipitating a solution of the polyamide together with a coprecipitant to facilitate dispersion, and blending with polyethylene terephthalate;
Alternatively, a method such as solution blending of a solution of polyamides and a solution of polyethylene terephthalate as component (A) is used, but for oligoamides having 2 to 6 amide bonds in the polyamide molecule, strong mixing a! Use of a machine is advantageous because direct melt blending is possible. As a method for such melt blending, it is preferable to use a mixer in which two or more screw IJs rotate in the same or different directions, or a single screw extruder in which screws reciprocate back and forth as they rotate. It's small.

Next, typical examples of the polyamides include -NH combination Co-1 CH6CH6 a? Specific examples of IJ theamides and oligoamides in which the sum of the number of amide bonds and hydranod bonds in the molecule is 2 to 6 are: 0QcoNr+◎C0NH@C0N)I-@--NHC
O-@-NHCO@, ◎-CONH@-NHco◎C0NH◎-Nl(CO@
-CONi-1@-NHCO-@◎NI-rco goco
Nr■◎NncoG-co+5rGN14CO<(3)
-co+i1%◎薊联C於＠0◎■0 etc.

Examples of aromatic oxysulfonic acid metal salts represented by the general formula (n) or CIII) include nonodium p-phenolsulfonate, disodium 2-naph)-5-sulfonate, and disodium p-phenolsulfonate, 2--) - Phthol-8 = disodium sulfonate, resorcin-4,6-nosulfonic acid tetrasodium, 2,3-naphthalesonol-6
-Sodium sulfonate' and the like.

These compounds can be added to the polyethylene terephthalate component (A) and can be carried out at any stage of the esterification reaction, transesterification reaction, or polycondensation reaction in the polyethylene terephthalate manufacturing process (7,
Depending on your exact wishes, j? Although it is possible to blend the compound after the completion of the polycondensation of 11 ethylene terephthalate, it is generally better to blend it before the completion of the polycondensation of the polyethylene terephthalate because the crystallization rate of the obtained polyester composition increases.

The formulation i of the crystal nucleating agent used as the unknown component (B) is:
(A) If the amount exceeds 0.05 to 103 parts by weight per 100 parts by weight of polyethylene terephthalate (component (A)), the melt viscosity of the resulting composition may increase and it may also cause mold deposits. It is not preferable for molding, and if it is less than 0.05 parts by weight, no effect of accelerating the crystallization rate is observed.

The ether compound used as component (C) of the present invention is represented by the general formula (I), in which R is hydrogen or a -valent aliphatic hydrocarbon group, such as methyl group, ethyl group, propyl group, butyl group. group, pentyl group, hexyl group, heptyl group,
Examples include octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, and octadecyl group, and preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms.

Ar in the general formula (I) is a monovalent hydrocarbon group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, Aliphatic groups such as hexadecyl group, cyclohexyl group, nclohexyl group, aliphatic groups such as noclohexylethyl group, aromatic rings such as benol group, phenylethyl group, naphthylmethyl group, phenyl group, naphthyl group, etc. A group having an aromatic ring is preferred, and a phenyl group or a benyl group is particularly preferred.

In general formula (I), n is an integer of 1 or more, preferably 1
-10, particularly preferably 1-6.

The value of n, RI''i, and the ease of synthesis of the ether compound can be selected, but in particular, the control of compatibility with polyethylene terephthalate as component (A), and the crystal nucleating agent as component (B) can be selected. It is advantageous to make a selection in such a way as to effectively exhibit synergistic effects.

Examples of the ether compound used as component (C) of the present invention include C6H13C6H13c6tt, 5 1 1 1, and the like.

These ether compounds are conveniently synthesized by a conventionally known method by reacting a condensate obtained from Group 1-1 and formaldehyde with ArX (provided that X u CL , Br or I). be. Alternatively, it is also possible to obtain a mixture of different types of ArXt or a mixture of different types of ArXt by reacting them sequentially. The ether compound thus obtained preferably has a melting point of 150°C or lower.

The amount of the ether compound used as the component (C) of the present invention is 100% of the polyethylene terephthalate of the component (A).
0.1 to 10 parts by weight, preferably 1 to 8 parts by weight
Parts by weight range. If this amount is less than 0.1 part by weight, it will be difficult to obtain a molded product with excellent gloss! 2) On the other hand, if the amount exceeds 10 parts by weight, it may cause undesirable problems in molding processing such as the occurrence of mold deposit knots.

The uninvented compositions and products can be prepared by a known method, for example, by adding all the crystal nucleating agent (B) to the polymerization of polyethylene terephthalate (A). It can be prepared by a method of condensing or triblending the component (C) with the ether compound using an extruder, or by simultaneously extruding all the components (HCJJ condensing).

In addition, the composition of the present invention may contain various auxiliary additives, such as reinforcing photoresist, antioxidant, ultraviolet absorber, lubricant, pre-release agent, flame retardant, and antistatic agent, depending on the purpose and purpose. , a coloring agent, etc. can be added.

Among the above-mentioned auxiliary additives, reinforcing photonic agents include carbon fibers such as fibrous organic and inorganic substances such as aramid fibers, glass fibers, carbon fibers, and asbestos '4Jl fibers, or non-P! , 7t of fibrous inorganic substances are mentioned.
Ll Among these, glass fiber is preferable.

In addition, the blending amount of this reinforcing photonic agent is 5 to 150 parts per 100 parts of component (A) polyethylene terephthalate.
The range of weight parts is preferable; if the amount is less than 5 weight parts, it will not provide sufficient shape stability, while if it exceeds 150 weight parts, the brittleness will increase and the practical I111i value will decrease. do.

The ψ,,l-1 product of the present invention thus obtained is:
Of course, when molding with a vorticity mold, 100℃
It exhibits excellent formability even when molded using nearby low-temperature molds, and it also provides molded products with good surface gloss, low heat shrinkage, and good shape stability. The composition contains few components that volatize over time and has excellent thermal stability.

As described above, the resin composition of the present invention can be molded in a low temperature range, which was not possible with conventional polyethylene terephthalate, and can contain volatile components even during the production, drying, or molding of this composition. Labor 1 because there is almost no
#I It is also excellent in terms of hygiene, and in combination with 1.1 = mechanical properties, heat resistance, chemical resistance, etc. inherent to recycled ethylene terephthalate, it is extremely useful as an industrial resin.
It can also be used as a material for films and textiles.

The present invention will be explained in more detail with reference to the following iC examples for actual Miiii, but it goes without saying that the present invention is not limited to these examples.

Example 1 (a) Production of blended resin 100 parts by weight of polyethylene terephthalate, 1 part by weight of Merck (manufactured by Nippon Merck Co., Ltd., MS type) as a crystal nucleating agent, and 4 parts by weight of an ether compound having the following structure were mixed in a rotary drum blender. Thereafter, the mixture was put into a double-screw extruder, and melt-kneaded with 45M parts of glass fibers having a length of 3cm at a cylinder temperature of 1i260-280-280°C to form pellets. The obtained pellets were dried at 150°C for 5 hours. The ratio of each component and the solution viscosity of the crosslinking resin are determined as follows.
Shown in the table.

The solution viscosity of the kneaded resin is determined at 35°C in a 6:4 mixed solvent of phenol and detrachloroethane, and is ηsp/
It is expressed as c.

(b) Molding and evaluation (b) The mixture obtained in (a) was coated with an injection molding machine (
Using KC-201)'i manufactured by Kawaguchi Tekko Co., Ltd., test specimens were prepared at various mold temperatures using a molding cycle of 25 seconds and an appropriate injection pressure at a temperature of 270-280-280°C. (ASTMI dumbbell test piece) was molded and various evaluations were performed. The results are shown in Table 2.

In addition, each evaluation was performed as follows.

Mold deposit; Judgment was made by observing the mold surface after 30 consecutive shots.

Mold releasability; It was expressed as the drop rate due to protrusion from the mold.

The center of the surface gloss dumbbell specimen was measured at a 201 current angle according to ASTM D 528.

Heating shrinkage rate: Length dimension of dumbbell test piece 'fIf: Lo, length dimension after heat treatment at 120°C for 15 hours in air open is Ll
It was calculated using the following formula.

Tensile strength: Measured based on ASTM D638.

Amount of volatilization: A dumbbell test piece was crushed, and the powder that passed through a 100-meter sieve was evaporated at 150°C using an infrared moisture meter.
After heating for a time, the weight ωo1 before heating and the weight ω1 after heating were measured, and the weight change rate was determined by the following formula.

Comparative Example 1 For comparison, an experiment similar to Example 1 was conducted without using a crystal nucleating agent and an ether compound, and it was found that when the mold temperature during molding was 110°C, the molded product was insufficiently crystallized. Due to the rough surface, it was difficult to release the dumbbell from its rough shape, so when it was removed too quickly, the dumbbell became deformed. In order to obtain an excellent molded product, it was necessary to raise the mold temperature to around 160°C.For this reason, Example 1 was used for Hibiki 1, in which Merck was used as the crystal nucleating agent and no ether compound was used. A similar experiment was conducted.The proportions of each component are shown in Table 1, and the evaluation results are shown in Table 2.

In this case as well, at a mold temperature of 110°C, only a molded product with no surface gloss and poor mold release was obtained.

Comparative Example 2 For comparison, an experiment similar to Example 1 was conducted using the same ether compound as in Example 1 without using a crystal nucleating agent. The proportions of each component are shown in Table 1, and the results of each evaluation are shown in Table 2.

Comparative Example 3 The same experiment b'A as in Example 1 was carried out except that in place of the ether compound in Example 1, a known Nisder compound dimethylolpropanobensoate was used. The percentages of each component are shown in Table 1, and the evaluation results are shown in Table 2.

In this case, it can be seen that volatilization during heating; 6- is large and practicality is poor.

Example 2 The same experiment as in Example 1 was conducted using disodium p-phenolsulfonate as a crystal nucleating agent. That is,
100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, and 1 part by weight of disodium p-phenolsulfonate were polymerized using manganese acetate and antimony oxide as catalysts to synthesize polyethylene terephthalate containing a crystal nucleating agent. For this polyethylene terephthalate, a resin compounded as shown in Table 3 was prepared and evaluated in the same manner as in Example 1. The results are shown in the fourth layer.

As in Example 1, the heat shrinkage rate was small even when molded in a mold at 80°C, and the amount of volatilization during heating was small, and a molded product with good surface gloss was obtained in a mold at 110°C. .

Comparative Examples 4 and 5 Example 2 for the case where the known ester compound dimethylolpropane dibenzoate was used instead of the ether compound in Example 2 (Comparative Example 4) and the case where diphenyl terephthalate was used (Comparative Example 5) A similar experiment was conducted. The proportions of each component are shown in Table 3, and the results of each evaluation are shown in Table 4.

It can be seen that in both cases, the amount of volatilization during heating is large.

An experiment similar to Example 2 was carried out by varying the amount of ether compound. Table 3 shows the proportions of each component, and Table 4 shows the evaluation results.

When the amount of the ether compound was 8 parts by weight (Example 3), good surface gloss was obtained, whereas when the amount was 20 parts by weight (Comparative Example 6), mold deposits were observed, and in addition, when heated The amount of volatilization also increases, which is undesirable.

Furthermore, with a blending amount of 0.05 parts by weight (Comparative Example 7), sufficient surface gloss was not obtained and mold release properties were also poor.

Examples 4 and 5 In Example 2, the amount of nonatrilam p-phenolsulfonate added was changed during the polymerization of polyethylene terephthalate, and the il of the ether compound to be blended was changed. The proportions of each component are shown in Table 3, and the results of each evaluation are shown in Table 4.

Below is a blank Example 6 (a) For a solution containing 10 parts by weight of poly-p-phenylene terephthalamide (crystal nucleating agent) obtained by solution polymerizing terephthalic acid dichloride and p-phenylenediamine in N-methylpyrrolidone, Polybutylene terephthalate adibate (abbreviated as PBTAD, terephthalic acid: adipic acid/butylene glycol molar ratio = 60: 40/100
) A solution of N-methylpyrrolidone in which 25 parts by weight was dissolved was blended, and then co-precipitated in a methanol-water mixed solution.

After filtering this and washing with methanol and water,
It was vacuum dried at ℃ for 5 hours. The resulting co-precipitate contains poly-
Contains about 30% p-phenylene terephthalamide. 3.5 parts by weight of this coprecipitate and other compounding agents were blended in the proportions shown in Table 5, melt-mixed with polyethylene terephthalate in the same manner as in Example 1, pelletized, and evaluated.

The results of each evaluation are shown in Table 6.

Example 7 An experiment similar to Example 6 was carried out using the crystal nucleating agent of component (B) and the crystal nucleating agent of component (C).
) The experiment was carried out by changing the ether compound of the component. In addition, in Example 6, polybutylene terephthalate adipate was added as a coprecipitant after polyamide as a crystal nucleating agent was synthesized by a polycondensation reaction, but this also consisted of polybutylene terephthalate anovate polytetramethylene glycol copolymer (
The experiment was carried out by changing the molar ratio of terephthalic acid:adipic acid/butylene glycol:polytetramethylene glycol=70:30/85:15, abbreviated as PBA-PTG. Table 5 shows the proportions of each component, and Table 6 shows the evaluation results.

An experiment similar to Example 6 was carried out using an oligomer of poly-p-phenylene terephthalamide in place of poly-p-phenylene terephthalamide in Example flJ6. Table 7 shows the proportions of each component, and Table 8 shows the evaluation results.

The oligomer of poly-p-phenylene terephthalamide used here is oligoamide-1 oligoamide-
1 is a reaction between 1 mole of terephthalic acid cyclolide and 2 moles of aniline in hexamethylphosphoramide solvent, which is sweet.
Oligoamide-2 contains 1 mole of terephthalic acid chloride and p
- Synthesis was carried out by reacting with 2 moles of phenylene diamine and then reacting with 2 moles of benzoyl chloride. Oligoamide-3 was reacted with equimolar p-nitrobenzoic acid and p-nitroaniline in a trimethylacetamide solvent, and reduced using 20 parts by weight of stannous chloride, 30 parts by volume of 36-dihydrochloric acid, and 50 parts by volume of ethanol. The diamino compound was prepared by reacting it with benzoic acid chloride in a hexamethylphosphoramide bath agent.

Comparative Example 8 VC was conducted in the same manner as in Example 8, except that the amount of oligoamide-1 was changed to 20 parts by weight. Table 7 shows the proportions of each component, and Table 8 shows the evaluation results.

In this case, it is not preferable because mold 7''' knots are likely to occur.

Below the aftermill

Claims (1)

[Claims] 1. (A) R/ethylene terephthalate 100i
i part, (B) 0.05 to 10 parts by weight of crystal nucleating agent, and (C
) General (wherein R is hydrogen or a -valent aliphatic hydrocarbon group,
A molding resin composition comprising 0.1 to 10 parts by weight of an ether compound represented by Ar11-1 (monovalent hydrocarbon group, n is an integer of 1 or more). 2. Component (C) has n in the above general formula from 1 to 10.
Claim 1 is an ether compound in which R is an aliphatic hydrocarbon group having a valence of 1 to 200 carbon atoms, and Ar is a phenyl group or a benyl group.
Compositions as described in Section. 3 (6) The components are (1) linked by at least two amide bonds or hydranode bonds, or both; and
714' lyamide film that does not melt or decompose at temperatures below 70°C; (ii) general formula (wherein M and M' are the same or different alkali metals;
0 and p are 1 or 2), and (l
li) The composition according to claim @1 or 2, which is any one of Merck's products or for children aged 2 years and 11 years or older. Component 4 (B) is a polyamide of (1), and the polyamide has the general formula % (wherein Ar4, Ar2 and Ar3 are divalent hydrocarbon groups,
Ar4 and Ar5 are monovalent hydrocarbon groups) At least two selected from among the amide-forming groups represented by Ar4 and Ar5 are monovalent hydrocarbon groups are connected by an amide bond.
Compositions as described in Section. 5. The composition according to claim 4, wherein Ar1, Ar2 and Ary of the amide forming groups are divalent aromatic hydrocarbon groups, and Ar4 and Ar5 are monovalent aromatic hydrocarbon groups. 6. The composition according to claim 3, wherein component (B) is an aromatic oxysulfonic acid metal salt represented by the general formula (11).