JP3086798B2 - Heat resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin composition having excellent workability, thermal stability and impact resistance.

[0002]

2. Description of the Related Art Post-chlorinated polyvinyl chloride resin (hereinafter referred to as CP)
VC) is known as a useful industrial material due to its properties such as higher heat deformation temperature and higher rigidity than ordinary polyvinyl chloride resin. However, CPVC has poor thermal fluidity during processing, resulting in poor productivity, thermal degradation and yellowing of resin easily occurring, flat surface smoothness of molded products, and it is difficult to obtain transparent molded products. Therefore, its use is limited. The disadvantage of such a CPVC is essentially due to the close proximity of the thermal fluidization temperature and the thermal decomposition temperature. As a means for remedying this drawback, a method has been proposed in which various polymers are blended to lower the heat flow temperature and improve processability. For example, Japanese Patent Publication No. 45-35177 discloses blending a methyl methacrylate polymer as a method of improving the processability by lowering the heat flow temperature of CPVC and improving the thermal stability. . This method is effective in improving the surface smoothness of a molded article without lowering the heat deformation temperature of CPVC. However, this method has a drawback that the lubricity on the metal surface is lost with an increase in the blend ratio of the methyl methacrylate polymer, and the stickiness occurs, making it difficult to continuously mold for a long time. I have.

[0003] Therefore, as a result of various studies on the improvement of the processability of CPVC, it has been found that by blending a polyester-based thermoplastic resin comprising a polyester hard segment and a polyether and / or polylactone soft segment with CPVC, the thermal fluidity of CPVC is improved. It has been found that both the heat stability and the thermal stability are improved.

However, even when such a polyester-based thermoplastic resin is used, it is not always satisfactory in terms of its physical properties.

[0005]

Accordingly, as a result of intensive studies to improve the above-mentioned drawbacks of the CPVC, the modifier and the mixed system thereof, the polyester hard segment in the polyester (hard segment) -polyether copolymer has A polyethylene terephthalate-polyether copolymer composed of ethylene terephthalate units is not compatible with CPVC, exists as a dispersed particle phase in a CPVC matrix, and a polyester (hard segment) -polylactone copolymer is compatible with CPVC. It was found that by using both copolymers in combination, the particle size of the dispersed particle phase could be controlled and the above-mentioned problems could be improved, and the present invention was reached.

[0006]

The present invention relates to (A) 100 parts of a post-chlorinated polyvinyl chloride resin (parts by weight, hereinafter the same).
And (B) a polyethylene terephthalate-polyether copolymer comprising a polyethylene terephthalate segment and a polyether segment, the weight ratio of both being 70/30 to 30/70, and (C) a polytetramethylene terephthalate segment. A polylactone segment, the weight ratio of which is 80/20 to 5/9
5 comprising a polytetramethylene terephthalate-polylactone copolymer, wherein the total blending amount of the polyethylene terephthalate-polyether copolymer (B) and the polytetramethylene terephthalate-polylactone copolymer (C) is 0.5 to 40 parts by weight, and the weight ratio of component (B) / component (C) is 99.5 / 0.5.
The present invention relates to a heat-resistant resin composition having a ratio of 5 to 30/70.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The heat-resistant resin composition of the present invention comprises:
(A) a post-chlorinated polyvinyl chloride resin, (B) a polyethylene terephthalate segment and a polyether segment, and the weight ratio of both is 70/30 to 30/70.
And a polytetramethylene terephthalate-polylactone copolymer comprising (C) a polytetramethylene terephthalate segment and a polylactone segment, wherein the weight ratio of both is 80/20 to 5/95. A heat-resistant resin composition comprising:

The above-mentioned CPVC is obtained by chlorinating a polyvinyl chloride resin obtained by an ordinary polymerization method such as a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method. Any method such as a chlorination method, a gas-phase photochlorination method, and a chlorination method using a radical-generating substance can be employed, but the chlorine content is 60 to 69% (% by weight, the same applies hereinafter) and the specific viscosity ( It is important that ηspC = 4 g / l nitrobenzene, 30 ° C.) is 0.15 to 0.35. If the chlorine content is less than 60%, it is difficult to maintain a sufficient heat distortion temperature level as a heat-resistant resin,
If the chlorine content exceeds 69%, the thermal stability is reduced, and thermal decomposition is liable to occur, and the color changes to a dark reddish brown during thermal fluidization. Further, when the specific viscosity is less than 0.15, the impact resistance is lowered, and when it exceeds 0.35, the transparency is lowered.

The polyethylene terephthalate-polyether copolymer used as the component (B) in the present invention comprises a polyethylene terephthalate segment and a polyether segment, and the polyethylene terephthalate segment / polyether segment has a weight ratio of 70%.
/ 30-30 / 70, preferably 60 / 40-4
0/60. When the ratio exceeds 70/30, the melting point exceeds 230 ° C., and it becomes difficult to mix with CPVC. On the other hand, when the ratio is less than 30/70, the transparency of the composition comprising the matrix resin CPVC and the polyester-based thermoplastic resin is undesirably reduced.

The polyester-based thermoplastic resin is a combination of the polyethylene terephthalate-polyether copolymer and the polytetramethylene terephthalate-polylactone copolymer described below in the composition of the present invention.

The polyethylene terephthalate segment is a segment containing about 70% or more, preferably about 80% or more of ethylene terephthalate units, and contains other ester units of about 30% or less, preferably about 20% or less. May be copolymerized.

Specific examples of the polyether as a source of the polyether segment include polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a copolymer of ethylene oxide and propylene oxide. .

The molecular weight of the polyether segment is:
It is preferably about 400 to 8000, and 600 to 6
More preferably, it is about 000.

The method for producing the component (B) is not particularly limited, and any method can be adopted. For example, dimethyl terephthalate, ethylene glycol and polyether may be subjected to a polycondensation reaction via transesterification in the presence of a catalyst, or a polyethylene terephthalate oligomer and a polyether may be subjected to a polycondensation reaction in the presence of a catalyst. Is also good. They may also be continuous polymerization processes.

The polytetramethylene terephthalate-polylactone copolymer used as the component (C) in the present invention comprises a polytetramethylene terephthalate segment and a polylactone segment, and the polytetramethylene terephthalate segment / polylactone segment is contained in a weight ratio. 80/20 to 5/95, preferably 70
/ 30 to 10/90, more preferably 60/40 to 2
0/80. When the ratio exceeds 80/20, the impact strength and the transparency of the composition comprising CPVC and the polyester-based thermoplastic resin are lower than that of CPVC alone, and 5 /
When it is less than 95, the heat distortion temperature of the mixture of CPVC and the polyester-based thermoplastic resin is lower than that of CPVC alone.

As the polyester hard segment of the component (C) in the present invention, a polytetramethylene terephthalate segment is used. In this case, the polyethylene terephthalate-polyether copolymer is used, though not so much as the polyethylene terephthalate segment. It has good compatibility with the polymer, and is preferable from the viewpoint of controlling the dispersed particle size (the average particle size is several μm or less and the particle size distribution is made uniform).

Examples of the lactone as a source of the polylactone segment include ε-caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, trimethyl-ε-caprolactone, β-propiolactone, bivalolactone, and α-valero. Lactone, enanthractone, caprylolactone, etc. are listed. Among them, ε-caprolactone has the highest compatibility with CPVC, the dispersion particle size is controlled, the impact resistance is improved, and it is economically available. preferable. Further, a polylactone segment in which two or more kinds of the lactones are used in combination may be used.

The method for producing the component (C) is not particularly limited, and any method can be employed. For example, polytetramethylene terephthalate is dissolved in a lactone monomer or both are melted and transesterification is performed in the presence of a catalyst. It may be a continuous polymerization reaction.

The component (B) and the component (C) may be blended with the component (A) as the two types of components as described above, but the component (B) and the component (C) may form a segment. The copolymer or a mixture of the copolymer and the component (B) or (C) may be mixed.

The mixing ratio of each component in the composition of the present invention is as follows:
Component (B) and component (C) (polyester thermoplastic resin) are preferably 0.5 to 40 parts, more preferably 1 to 30 parts, and particularly preferably 2 to 20 parts, per 100 parts of component (A). When the amount of the polyester-based thermoplastic resin is less than 0.5 part, the effect of improving processability and thermal stability is not so much obtained, and when it exceeds 40 parts, the heat deformation temperature and the transparency are compared with those of CPVC alone. And it gets pretty bad.

The proportion of the component (B) and the component (C) in the polyester-based thermoplastic resin is such that the component (B) is 99.
It is preferably from 5 to 30%, more preferably from 95 to 40%.
It is preferably 0%, more preferably 5 to 60%. If the proportion of the component (B) is less than 30%, the heat distortion temperature is lower than that of CPVC alone, and if it exceeds 99.5%, it becomes difficult to control the dispersed particle size, the effect of improving the impact resistance is reduced, and the transparency is reduced. Sex is not enough.

The method of mixing the components when preparing the composition of the present invention is not particularly limited, and the components may be mixed simultaneously, or some of the components may be mixed first, and the remaining components may be mixed. May be mixed. Among the mixing methods,
In the method of mixing the component (A) with the component (B) and the component (C) previously mixed, the heat history of the component (A) is reduced, and the effect of the combined use of the component (C) tends to appear. It is preferable from the point of view.

For the purpose of the present invention, the melting point of the polyester-based thermoplastic resin (mixture of the components (B) and (C)) is 23 to facilitate mixing with the component (A).
The temperature is desirably 0 ° C. or lower.

The composition of the present invention comprises CPVC as the sea portion,
It is mainly a composition having a sea-island structure in which the component (B) exists as an almost spherical island portion, and it is unknown what form the component (C) exists. By having this, the sea-island structure is easily obtained.

It is generally not preferred that the island portion (mainly the component (B)) has a directional property such as an elongated shape or an elliptical shape, and a shape close to a sphere does not give directionality to physical properties. Therefore, it is preferable.

Further, when the island portion is nearly spherical, the average particle diameter is preferably several μm or less, but is generally 0.0 μm or less.
It is preferably in the range of 1 to 5 μm, and 0.03 to 3 μm.
More preferably, it is in the range of m. However, the average particle size can be appropriately selected according to the composition, application, required physical properties, and the like. Also, it is generally preferable that the particle size distribution is narrow,
There may be two or more peaks in the particle size distribution, and a broad distribution is acceptable.

Next, when preparing a polyester-based thermoplastic resin, a mixture of the component (B) and the component (C) is first prepared, and then the component (A) is mixed.
A method for preparing a mixture of the component (B) and the component (C) will be described.

The method is not particularly limited, and any method can be adopted. Specifically, there is a method of synthesizing the components (B) and (C) and then mixing them using an extruder.

A mixture of the component (B) and the component (C),
The mixing with the component (A) may be performed, for example, by mixing each component in a powdery state and / or in a granular form using a V-type blender or a Henschel mixer under any conditions. If necessary, kneading may be performed using a roll mill or an extruder.

On the other hand, when the composition of the present invention is prepared by mixing all of the components (A) to (C) at a time, for example, each component is in a powder state in a V-blender or a Henschel mixer. May be mixed under arbitrary conditions. If necessary, kneading may be performed using a roll mill or an extruder. The mixture thus obtained is supplied to a processing machine such as a calender roll, an extruder or an injection molding machine to obtain a desired molded product.

The composition of the present invention is suitably used for sheets, plates, pipes, etc., which require heat resistance and chemical resistance.

The composition of the present invention may contain, if necessary, conventionally used heat stabilizers, lubricants, pigments, impact strength improvers, and other fillers.

[0033]

EXAMPLES Hereinafter, the effects of the present invention will be described using examples, but the present invention is not limited only to these.

The melting points and viscosities in the Production Examples were measured under the following conditions. Melting point (° C): Differential scanning calorimeter (D manufactured by PerkinElmer)
SC7) at a heating rate of 20 ° C./min. Intrinsic viscosity (dl / g): phenol / 1,1,2,2-
Measured at a concentration of 0.5 g / dl and a temperature of 25 ° C. using a tetrachloroethane = 1/1 (weight ratio) solution as a solvent.

Production Example 1 [Production of polyethylene terephthalate-polyether copolymer (hereinafter referred to as copolymer (B))] 100 parts of dimethyl terephthalate, 27 parts of ethylene glycol, and 95 parts of polyethylene glycol (molecular weight: 1540) are usually used as raw materials. By the method, a polyethylene terephthalate-polyethylene glycol copolymer containing 50% of polyethylene glycol was obtained. This copolymer had a melting point of 200 ° C. and an intrinsic viscosity of 1.2 dl.

Production Example 2 [Production of Polyester (Hard Segment) -Polylactone Copolymers (C-1) and (C-2)] Copolymer (C-
1): 40 parts of polyethylene terephthalate and 60 parts of ε-caprolactone were reacted by a conventional method to obtain a polyethylene terephthalate-polyε-caprolactone copolymer. This copolymer has a melting point of 210 ° C. and an intrinsic viscosity of 1.3.
dl / g.

Copolymer (C-2): Polytetramethylene terephthalate-polyε-caprolactone copolymer was obtained by reacting 60 parts of polytetramethylene terephthalate and 40 parts of ε-caprolactone by a conventional method. The melting point of this copolymer was 200 ° C.

Example 1 and Reference Examples 1-2 [Production of polyester-based thermoplastic resin] The ratio of the copolymer (B) to the copolymer (C-1) or (C-2) shown in Table 1. , A polyester-based thermoplastic resin was produced using an extruder and granulated. The melting point of these copolymers is 20
The range was 0-210 ° C.

[Production and Measurement of the Heat-Resistant Resin Composition of the Present Invention] CPVC used heat-resistant Kanevinyl H717 (chlorine content: about 67%) manufactured by Kaneka Chemical Co., Ltd. A plastic resin was blended, the composition was made as shown in Table 1, kneaded and granulated using an extruder, and then pressed to prepare a test piece, which was subjected to the following measurements.

Evaluation of fluidity: using a capillary rheometer manufactured by Toyo Seiki Co., Ltd.

[0041]

(Equation 1)

The melt viscosity was measured at 200 ° C. to evaluate the fluidity. Thermal stability evaluation: Coloring of the sample after kneading was visually evaluated. Izod impact value (notched, 23 ° C): ASTM
According to D-256. Vicat softening point: according to JIS K-7206.

Comparative Examples 1 to 4 As comparative examples, the same treatment as in the example was performed for four examples of the formulations shown in Table 1, and the same measurement as in the example was performed on the obtained test pieces.

[0044]

[Table 1]

As can be seen from Table 1, Examples 1 and Reference Examples 1 to 1 in which a polyester thermoplastic resin comprising the copolymer (B) and the copolymer (C-1) or (C-2) were blended with CPVC. Composition 2 has a lower melt viscosity and better fluidity and thermal stability than Comparative Example 1 in which no copolymer was added to CPVC. In addition, impact resistance has been improved,
It can be seen that the decrease in the heat distortion temperature is small.

The CPVC and copolymer (B) shown in Comparative Examples 2 and 4 were compared with the compositions of the above Examples and Reference Examples.
The composition comprising only CPVC or the copolymer (C-1) is inferior in any of melt viscosity, impact resistance, heat stability, heat deformation temperature and the like.

In Comparative Example 2, in the mixed state of the copolymer (B) in CPVC, a wide dispersed particle diameter of 0.01 to 10 μm was observed, and whiskers and ellipses were observed. . In contrast, in Example 1, most of the dispersed particles had a spherical or elliptical shape in the range of 0.05 to 2 μm.

Further, in Comparative Example 3 where the total amount of the copolymers (B) and (C-1) with respect to the amount of CPVC was too large, the Vicat softening point was greatly reduced and the polymer was inferior. Recognize.

[0049]

According to the present invention, the composition obtained is CPV.
When the polyester-based thermoplastic resin is not added to C, the melt viscosity, fluidity, thermal stability, impact resistance, etc., are almost the same as those of the conventional CPVC-improved composition, with almost no loss in heat deformation temperature and transparency. It is excellent in that it is very useful as a material for molding sheets, plates, pipes, pipe joints and the like.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 27/24 C08L 67/04-67/07

Claims (2)

(57) [Claims] (A) Post-chlorinated polyvinyl chloride resin 1
(B) a polyethylene terephthalate-polyether copolymer comprising (B) a polyethylene terephthalate segment and a polyether segment in a weight ratio of 70/30 to 30/70, and (C)
It is composed of a polytetramethylene terephthalate segment and a polylactone segment, and the weight ratio of both is 80/2.
0-5 / 95 of a polytetramethylene terephthalate-polylactone copolymer, wherein a component (B) is a polyethylene terephthalate-polyether copolymer and a component (C) is a polytetramethylene terephthalate-polylactone copolymer. The total compounding amount is 0.5 to 40 parts by weight, and (B) component / (C) component is 99.
A heat-resistant resin composition having a ratio of 5 / 0.5 to 30/70. 2. The post-chlorinated polyvinyl chloride resin as the component (A) contains 60 to 69% by weight of chlorine, and has a specific viscosity (η spC = 4 g / l nitrobenzene, 30 ° C.) of 0.15 to 0.15. The heat-resistant resin composition according to claim 1, which is 0.35.