JP2001064496A - Resin composition and its molding process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polyester resin composition enabling the improvement of its processing property and its calendaring process by incorporating a specific polyolefin resin and/or a montanoic acid wax in it for reducing its melt adhesivity. SOLUTION: This objective composition is obtained by incorporating (A) a thermoplastic polyester resin, (B) (i) a polyolefin resin obtained by grafting a side chain with a different monomer form that constituting its main chain and/or (ii) a montanoic acid wax. As the component A, a polyethylene terephthalate resin (as an amorphous polyethylene terephthalate copolymer), etc., can be cited. As the component (i), a low-density polyethylene resin grafted with a polymethyl methacrylate or a polyacrylonitrile-styrene copolymer can be cited. As the component (ii), the montanoic acid (ester wax), etc., can be cited.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to improve the workability by reducing the adhesiveness of a thermoplastic resin having a remarkable adhesion to a metal surface of a processing machine at the time of heating and melting, and to facilitate cleaning after processing. is there. In particular, it enables calender roll processing of amorphous polyethylene terephthalate resin having strong melt adhesion.

[0002]

2. Description of the Related Art A typical polyethylene terephthalate resin of a thermoplastic polyester resin (hereinafter referred to as PET).
Is formed by heating and melting, but in this processing, since the adhesion to the metal surface of the processing machine is severe, the fluidity is poor in extrusion processing, and the discharge amount is hardly increased. In addition, even when cleaning the processing machine after the processing is completed, it is necessary to allow a large amount of cleaning resin to flow for a long time due to poor peelability of the adhered resin. In particular, copolymer non-crystalline polyethylene terephthalate resin (hereinafter referred to as A-PET) has strong melt adhesion and is extremely difficult to mold. With respect to A-PET, it has been strongly required in recent years to produce sheets and films by calender roll processing, but the calender rolls are so strongly adhered that calender roll processing cannot be performed. The use of various lubricants has been studied to solve this drawback, but no suitable lubricant has been found.

[0003]

SUMMARY OF THE INVENTION Accordingly, the present invention
An object of the present invention is to provide a method for reducing the melt adhesion of ET, A-PET, etc., improving workability, and enabling calender roll processing.

[0004]

That is, the inventors of the present invention have conducted intensive studies and found that the invention described in the claims is effective in solving the above-mentioned problems. It is.

[0005] The invention of claim 1 is a thermoplastic polyester resin composition containing a polyolefin resin obtained by graft-polymerizing a side chain of a monomer different from a monomer constituting the main chain and / or a montanic acid wax.

According to a second aspect of the present invention, the graft-polymerized polyolefin resin is obtained by graft-polymerizing a low-density polyethylene resin obtained by graft-polymerizing polystyrene, a low-density polyethylene resin obtained by graft-polymerizing polymethyl methacrylate, or a polyacrylonitrile-styrene copolymer. A resin selected from the group consisting of a low-density polyethylene resin, a polypropylene resin obtained by graft polymerization of polystyrene, a polypropylene resin obtained by graft polymerization of polymethyl methacrylate, and a polypropylene resin obtained by graft polymerization of a polyacrylonitrile styrene copolymer. The resin composition as described in the above.

According to a third aspect of the present invention, the thermoplastic polyester resin is a single resin or a plurality of resins selected from a polyethylene terephthalate resin, an amorphous polyethylene terephthalate resin which is a copolymer of polyethylene terephthalate, and a polybutylene terephthalate resin. The resin composition according to claim 1.

A fourth aspect of the present invention is a method for molding and processing a resin composition containing a thermoplastic polyester resin, wherein a polyolefin resin having a side chain graft-polymerized with a monomer different from the monomer constituting the main chain in the resin composition And / or a method for processing a thermoplastic polyester resin using a resin composition containing a montanic acid wax.

According to a fifth aspect of the present invention, there is provided the molding method according to the fourth aspect, wherein the graft-polymerized polyolefin resin is the second aspect.

The invention according to claim 6 is the method according to claim 4 or 5, wherein the method is calender roll processing.

In summary, the present invention relates to a method for reducing the melt adhesion of a thermoplastic polyester resin by incorporating a graft-polymerized polyolefin resin and / or montanic acid wax. is there.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The typical and best modes of the embodiment of the present invention are specifically shown in the examples described later. This will be described in detail below.

Examples of the polyolefin resin obtained by graft-polymerizing a side chain of a monomer different from the monomer constituting the main chain (hereinafter abbreviated as grafted polyolefin resin) include a low-density polyethylene resin obtained by graft-polymerizing polystyrene and a graft-polymerized polymethyl methacrylate. Low-density polyethylene resin (hereinafter LDPE-g-PMMA)
), A low-density polyethylene resin grafted with a polyacrylonitrile-styrene copolymer (hereinafter referred to as LD
PE-g-AS), a polypropylene resin obtained by graft-polymerization of polystyrene, a polypropylene resin obtained by graft-polymerization of polymethyl methacrylate, and a polypropylene resin obtained by graft-polymerization of polyacrylonitrile styrene. By kneading the polyester resin, the tackiness of the thermoplastic polyester resin at the time of heating and melting can be reduced. In particular, LDPE-g-PMMA and LDPE-g-A
S is useful because it has good compatibility with the thermoplastic polyester resin and has a good effect of lowering the melt adhesion.

As the montanic acid wax, montanic acid itself, montanic acid ester wax and partially saponified ester wax of montanic acid are commercially available, all of which are useful.

Although the graft-polymerized polyolefin resin and the montanic acid wax each have an effect of lowering the tackiness of the thermoplastic polyester resin at the time of melting,
It is more preferable to use both companies together. The montanic acid wax is conventionally generally used as a lubricant, and when it is used by adding it to a thermoplastic polyester resin, it acts as a lubricant, and has an effect of delaying the gel time of the polyester resin. However, the use of a graft-polymerized polyolefin resin can shorten the gelation time delay of the polyester resin.

From the viewpoint of the graft-polymerized polyolefin resin, even if the amount of the graft-polymerized polyolefin resin is reduced, the tackiness of the thermoplastic polyester resin at the time of melting can be reduced. By reducing the amount of both added due to the synergistic effect of both, an effect of suppressing the effect on the physical properties of the thermoplastic polyester resin can be expected.

The addition amount of the graft-polymerized polyolefin resin and / or montanic acid wax is not particularly limited, but is determined within a range where the effects of the present invention are exhibited and the purpose of use of the thermoplastic polyester is not hindered. .

For example, if the processing method such as extrusion processing or calender roll processing, the necessary degree of decrease in tackiness at the time of melting, an allowable delay in gelation time, and the effect on the physical properties of the thermoplastic polyester resin are determined. Good. Addition of 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin is a target for use.

The method of adding the graft-polymerized polyolefin resin and / or montanic acid wax to the thermoplastic polyester resin may be a general method. That is, a method in which a graft-polymerized polyolefin resin and / or montanic acid wax is directly added to a thermoplastic polyester resin and kneaded, a master made of a thermoplastic polyester resin in which the graft-polymerized polyolefin resin and / or montanic acid wax is mixed at a high concentration. A method in which the batch is added to a thermoplastic polyester resin and kneaded, a method in which a polyolefin resin graft-polymerized as a vehicle for the colorant and / or a colorant containing montanic acid wax are added and kneaded.

As the thermoplastic polyester resin, there are PET, A-PET and polybutylene terephthalate resin.

The effect of reducing the adhesiveness of the grafted polyolefin resin and / or montanic acid wax thermoplastic resin upon melting is not only the thermoplastic polyester resin, but also the thermoplastic polyurethane resin, 6 nylon, 6, 6 nylon and the like. It is also effective for resins having polarity such as nylon resin.

[0022]

The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The following method was used to confirm the effect of lowering the tackiness of the thermoplastic polyester resin upon heating and melting.

A roller mixer (model R-60) (capacity: about 60 c) was added to Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd.
c) was set, and the temperature of each of the predetermined portions was set to 200 ° C. The resins and the like having the formulations shown in the examples and comparative examples were respectively charged into this mixer, and 10
Kneaded for minutes. Immediately thereafter, the mixer was disassembled, and the state of adhesion of the resin to each block constituting the container portion of the mixer was visually observed. In addition, the kneaded material attached to each block was scraped off with a metal spatula, and it was difficult to take out the mixture and the magnitude of the adhesiveness was determined. The time until the peak of the torque during kneading was measured and defined as the gel time.

As the thermoplastic polyester resin, Kodar PETG 6763 (hereinafter, referred to as PETG) manufactured by Eastman Kodak Co., Ltd., which is an A-PET having a remarkable adhesive property upon melting, was used.

In order to avoid the influence of hydrolysis due to moisture absorption of PETG, each sample used in the test was dried in a hot air dryer at 80 ° C. for 3 hours or more before use.

The following were specifically used for each sample. LDPE-g-PMMA: MODIPER A1200 manufactured by NOF Corporation LDPE-g-AS: MODIPER A manufactured by NOF Corporation
1400 Montanic acid partially saponified ester wax: Hoechst wax OP manufactured by Clariant Co., Ltd. Polyethylene wax: Epolen N10 GX-6 manufactured by Eastman Kodak Co., Ltd .: On the other hand, fatty acid ester release agent EP-525L manufactured by YAS Co., Ltd. Magnesium / Zinc organic composite release agent manufactured by Sakae Chemical Co., Ltd.

Examples 1 to 6 and Comparative Examples 1 to 4 The compositions shown in Tables 1 and 2 were mixed with a polyolefin resin grafted with a thermoplastic polyester and / or a montanic acid wax or other waxes, a release agent or the like. The mixture was kneaded, and then the kneaded product was evaluated for adhesiveness and the like.

Tables 1 and 2 also show the results of the adhesion state and the gelation time of the kneaded material. In the table, the cylinder block is the cylinder portion of the mixer vessel, and the end block is the portion that closes the cylinder end. The blade is a rotary wing that performs a rotary stirring operation in a cylinder.

PETG, which could not be peeled off from each block of the mixer at all, can be peeled off by adding a graft-polymerized polyolefin resin and / or montanic acid wax. Was done. In particular, after kneading 20 g of the kneaded material obtained in Example 6 with two rolls heated to 195 ° C. for 5 minutes, a sheet having a thickness of about 150 μm could be taken out. As a result, it has been found that a sheet or a film can be manufactured by calendering even if PETG is used.

[0031]

According to the present invention, it is possible to reduce the adhesiveness of a thermoplastic polyester resin when heated and melted, to improve the discharge rate at the time of extrusion and to shorten the cleaning time of a processing machine, Roll processing becomes possible.

[0032]

[Table 1]

[0033]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // B29K 67:00 B29L 7:00 F term (reference) 4F071 AA18X AA20X AA22X AA33X AA34X AA44X AA45 AA45X AA46 AA46X AA71 AA76 AA77 AF58 BA01 BB04 BC01 4F204 AA03 AA07 AA11 AA24 AA49 AG01 AM32 FA06 FB02 FF01 4J002 AE03Y BN03X BN05X CF041 CF061 CF071

Claims (6)

[Claims] 1. A thermoplastic polyester resin composition containing a polyolefin resin obtained by graft-polymerizing a side chain of a monomer different from a monomer constituting a main chain and / or a montanic acid wax. 2. A low-density polyethylene resin obtained by graft-polymerizing polystyrene, a low-density polyethylene resin obtained by graft-polymerizing polymethyl methacrylate, a low-density polyethylene resin obtained by graft-polymerizing a polyacrylonitrile-styrene copolymer, The resin composition according to claim 1, wherein the resin composition is a single resin or a plurality of resins selected from a polypropylene resin obtained by graft polymerization of polystyrene, a polypropylene resin obtained by graft polymerization of polymethyl methacrylate, and a polypropylene resin obtained by graft polymerization of a polyacrylonitrile styrene copolymer. . 3. The thermoplastic polyester resin is a single resin or a plurality of resins selected from a polyethylene terephthalate resin, an amorphous polyethylene terephthalate resin which is a copolymer of polyethylene terephthalate, and a polybutylene terephthalate resin. The resin composition as described in the above. 4. A method for molding and processing a resin composition containing a thermoplastic polyester resin, wherein a polyolefin resin and / or montanic acid obtained by graft-polymerizing a side chain of a monomer different from a monomer constituting a main chain in the resin composition. A method for forming and processing a thermoplastic polyester resin using a resin composition containing a wax. 5. The method according to claim 4, wherein the graft-polymerized polyolefin resin is the one according to claim 2. 6. The forming method according to claim 4, wherein the method is calender roll processing.