JP4194078B2 - Impact-resistant polyester resin sheet - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an impact-resistant polyester resin sheet.
[0002]
[Prior art]
Polyester resin sheets are used for decorative sheets and food container sheets as an alternative to vinyl chloride resin sheets because they can be heat-processed such as vacuum forming and membrane forming. In some cases, amorphous polyester may be used alone for the polyester-based resin sheet. However, when higher impact resistance is required, butadiene rubber-based impact modifier known as MBS resin or acrylic is used. Add rubber impact modifier. Conventionally, it is known to add the above-mentioned butadiene rubber-based impact modifier or acrylic rubber-based impact modifier in order to improve the impact resistance of a polyester resin (see, for example, Patent Document 1). ) As a modification method of the amorphous polyester resin, the above butadiene rubber impact modifier or acrylic rubber impact modifier is used to improve molding processability or to increase high temperature embossability. Addition is also known (see, for example, Patent Document 2 and Patent Document 3).
[0003]
[Patent Document 1]
JP-A-52-74652 (page 1-9)
[Patent Document 2]
Japanese Patent Laid-Open No. 2001-214044 (page 1-6)
[Patent Document 3]
JP 2001-247753 A (page 1-8)
[0004]
However, since the butadiene rubber impact modifier lowers the weather resistance of the polyester resin sheet, it is preferable to use an acrylic rubber impact modifier if it is necessary to consider the weather resistance as well as the impact resistance. However, the particles of the acrylic rubber-based impact resistance improving agent are liable to cause secondary agglomeration and have a disadvantage that a desired reinforcing effect cannot be obtained.
[0005]
[Problems to be solved by the invention]
The present invention has been made for the purpose of providing a polyester resin sheet that eliminates the conventional problems as described above, does not deteriorate weather resistance, and has excellent impact resistance. .
[0006]
[Means for Solving the Problems]
As a result of diligent research, the present inventors have found that the above-mentioned problems can be achieved by blending an amorphous polyester-based resin with a glycidyl methacrylate copolymer together with an acrylic rubber-based impact modifier, and completed the present invention. .
That is, the gist of the present invention is as follows.
A polyester system mainly composed of an amorphous polyester composed of a dicarboxylic acid component composed of terephthalic acid and a diol component composed of 20 to 35 mol% 1,4-cyclohexanedimethanol and 65 to 80 mol% ethylene glycol. Impact-resistant polyester formed by molding a resin composition comprising 1 to 25 parts by weight of an acrylic rubber impact modifier and 0.5 to 5 parts by weight of a glycidyl methacrylate copolymer with respect to 100 parts by weight of the resin. Resin sheet, and
A polyester system mainly composed of an amorphous polyester composed of a dicarboxylic acid component composed of terephthalic acid and a diol component composed of 20 to 35 mol% 1,4-cyclohexanedimethanol and 65 to 80 mol% ethylene glycol. 0.5 to 25 parts by weight of an acrylic rubber impact modifier, 0.5 to 5 parts by weight of a glycidyl methacrylate copolymer, and 0.5 to 10 parts by weight of an acrylic polymer processing aid with respect to 100 parts by weight of the resin And an impact-resistant polyester resin sheet formed by molding a resin composition containing 1 to 3 parts by weight of a lubricant.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
The amorphous polyester used as the main resin component of the impact-resistant polyester resin sheet of the present invention is a dicarboxylic acid component composed of terephthalic acid, 20-35 mol% 1,4-cyclohexanedimethanol, and 65-80. It is a polyester composed of a diol component composed of mol% ethylene glycol, and is commercially available from Eastman Chemical Company under trade names such as “PETG GN071”, “PETG 6763”, “Provista” and the like.
In the polyester resin sheet of the present invention, crystalline, low crystalline and other amorphous polyesters can be blended in addition to the above amorphous polyester. Specific examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PETI, PBTI, and the like. The blending ratio of the amorphous polyester in the mixture of these polyesters is in the range of 60 to 100% by weight, preferably 80 to 100% by weight.
When the blending ratio of the amorphous polyester is less than 60% by weight, the impact resistance, sheet formability, secondary processability, and the like of the sheet are lowered, and a desired sheet cannot be obtained.
[0008]
The acrylic rubber impact modifier blended in the polyester resin of the present invention is composed of a methyl methacrylate, a core made of an acrylic rubber obtained by polymerizing an acrylic ester such as butyl acrylate and a small amount of a crosslinkable monomer, Two-layer rubber particles having a shell portion formed by graft polymerization of vinyl monomers such as acrylonitrile and styrene, such as “HIA-80” (Kureha Chemical Industry Co., Ltd.), “Acryloid KM-330” Resins that are commercially available under trade names such as (Rohm and Haas), “Metablene W-300A”, and “Metablene W-530” (Mitsubishi Rayon) are preferably used.
This acrylic rubber-based impact resistance improver is 1 to 25 parts by weight (0.5 to 25 parts by weight when used in combination with an acrylic processing aid), preferably 1 with respect to 100 parts by weight of the polyester resin. Used in the range of 5 to 20 parts by weight. When the addition amount of the acrylic rubber polymer is less than 1 part by weight, the effect of improving the impact resistance is insufficient, and the melt viscosity of the resin composition during the sheet molding process is increased to increase the heat gelation state. The effect of facilitating the transfer of the sheet, increasing the quantitative supply accuracy to the calendar roll, and improving the thickness accuracy of the sheet cannot be obtained. Moreover, since the surface property of a sheet | seat will be impaired on the contrary when the addition amount exceeds 25 weight part, it is unpreferable.
[0009]
The glycidyl methacrylate copolymer blended with the acrylic resin impact modifier in the polyester resin of the present invention is a functional methacrylate copolymer having an epoxy group in the side chain, and is usually glycidyl methacrylate and other glycidyl methacrylate copolymers. It is obtained by copolymerizing with a vinyl monomer. Other vinyl monomers copolymerized with glycidyl methacrylate include styrene derivatives such as styrene and vinyltoluene, (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate, (meth) acrylic acid, Examples include acrylonitrile, ethylene, vinyl chloride, vinyl acetate, and vinylidene chloride.
Specific examples of these glycidyl methacrylate copolymers include “ARUFON” manufactured by Toagosei Co., Ltd., “Modiper A-4200” manufactured by NOF Corporation, “Bond First 7M” manufactured by Sumitomo Chemical Co., Ltd., and the like.
Moreover, the said glycidyl methacrylate copolymer is mix | blended in the ratio of 0.5-5 weight part with respect to 100 weight part of polyester-type resin. If the amount is less than 0.5 part by weight, the impact resistance of the polyester resin sheet is not sufficiently improved, and if the amount exceeds 5 parts by weight, no further impact resistance improvement effect can be expected.
[0010]
Lubricants blended with the above polyester resins include hydrocarbon lubricants such as paraffin wax and olefin wax, higher fatty acid lubricants such as stearic acid, metal soap lubricants such as calcium stearate, and ester lubricants such as montanic acid wax. These can be used, and these can be used alone or in admixture of two or more.
If the amount of these lubricants is too small, when calendering or extrusion molding into a sheet shape, the melted polyester tends to stick to the calender roll, etc., conversely, if too much, the blowout to the surface of the sheet will increase and printability will increase. Is damaged. Therefore, in this invention, it is good to mix | blend a lubricant with 0.5-3 weight part with respect to 100 weight part of polyester-type resin, Preferably it is 1-2.5 weight part.
[0011]
Furthermore, acrylic processing aids blended in the present invention are acrylic acid esters such as methyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, A copolymer having a weight average molecular weight of 1,000,000 to 5,000,000 based on methacrylic acid esters such as ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate is preferred. Examples thereof include “Metablene P-551” and “Metablene P-530A” manufactured by Mitsubishi Rayon Co., Ltd., “Kane Ace PA-30” and “Kane Ace PA-100” manufactured by Kaneka Corporation.
The blending ratio of these acrylic processing aids is 0.5 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 1 to 6 parts by weight with respect to 100 parts by weight of the polyester resin. can do. If this amount is too small, there will be no effect of imparting lubricity to the polyester or increasing the melt viscosity, and processing to obtain a thin and uniform surface will be difficult. This is undesirable because it causes turbulent flow in the bank of rolls and impairs the surface properties of the sheet.
[0012]
Furthermore, in the present invention, various additives conventionally added, for example, pigments, hindered amine light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic and organic fillers, and compatibility. Resins and the like can be blended.
[0013]
The polyester resin sheet of the present invention comprises a polyester resin based on the above amorphous polyester, an acrylic rubber impact modifier and a glycidyl methacrylate copolymer, and, if necessary, a lubricant or an acrylic processing aid. Further, the various additives as described above are blended at respective doses, kneaded to adjust the raw materials, and then manufactured by a normal calendering method or extrusion method.
[0014]
【Example】
Next, the content of the present invention will be described in more detail with reference to examples.
[0015]
Example 1
10 parts by weight of an acrylic rubber impact modifier (trade name “Metablene W-300A” manufactured by Mitsubishi Rayon Co., Ltd.) with respect to 100 parts by weight of amorphous polyester (trade name “PETG GN071” manufactured by Eastman Chemical Co., Ltd.) , 4 parts by weight of a glycidyl methacrylate copolymer (trade name “ARUFON UG4070-2” manufactured by Toa Gosei Co., Ltd.), 1.5 parts by weight of a lubricant (montanic acid wax, manufactured by Clariant Japan, trade name “G431L”) and phenolic A polyester resin sheet having a thickness of 0.1 mm was produced at 175 ° C. by blending 1 part by weight of an antioxidant and using a normal calendering method. Calendar workability and sheet thickness accuracy were good. The impact strength of the obtained sheet was 11.5 kJ / m, and the secondary aggregation of the acrylic rubber polymer was not observed by observation with a transmission electron microscope, indicating a good dispersion state.
[0016]
Example 2
For 100 parts by weight of amorphous polyester (trade name “PETG GN071” manufactured by Eastman Chemical Co., Ltd.), 15 parts by weight of acrylic rubber impact modifier (“HIA-80” manufactured by Kureha Chemical Industry Co., Ltd.) and glycidyl methacrylate Polymer (4 parts by weight of “Bond First 7M” manufactured by Sumitomo Chemical Co., Ltd.) and 1 part by weight of a phenolic antioxidant were prepared, pellets were made using a twin screw extruder, and then thickened using a single screw extruder. A polyester resin sheet having a thickness of 0.1 mm was prepared, and the resulting sheet had an impact strength of 12.2 kJ / m, and no secondary aggregation of the acrylic rubber polymer was observed by observation with a transmission electron microscope. It showed a good dispersion state.
[0017]
Example 3
Instead of 100 parts by weight of the amorphous polyester of Example 2, 85 parts by weight of amorphous polyester (“PETG GN071”), crystalline polyester (trade name “600FP”, polybutylene terephthalate resin, manufactured by Polyplastics Co., Ltd.) A polyester resin sheet having a thickness of 0.1 mm was prepared in the same manner as in Example 2 except that the amount was 15 parts by weight. The impact strength of the obtained sheet was 13.4 kJ / m, and secondary aggregation of the acrylic rubber polymer was not observed by observation with a transmission electron microscope, indicating a good dispersion state.
[0018]
Comparative Example A polyester resin sheet having a thickness of 0.1 mm was produced in the same manner as in Example 2 except that no glycidyl methacrylate copolymer was blended. The resulting sheet had an impact strength of 2.3 kJ / m, and secondary aggregation of the acrylic rubber polymer was observed by observation with a transmission electron microscope.
[0019]
【The invention's effect】
According to the present invention, since the acrylic rubber polymer is blended to improve the impact resistance of the polyester resin sheet mainly composed of amorphous polyester, the sheet is compared with the case of using the diene rubber polymer. The weather resistance of the acrylic rubber-based impact modifier particles can be well dispersed by adding a glycidyl methacrylate copolymer, and the impact resistance can be reduced due to poor dispersion. An impact-resistant polyester resin sheet having excellent weather resistance is obtained.

Claims (3)

A polyester system mainly composed of an amorphous polyester composed of a dicarboxylic acid component composed of terephthalic acid, a diol component composed of 20 to 35 mol% 1,4-cyclohexanedimethanol and 65 to 80 mol% ethylene glycol. Impact-resistant polyester formed by molding a resin composition in which 1 to 25 parts by weight of an acrylic rubber impact modifier and 0.5 to 5 parts by weight of a glycidyl methacrylate copolymer are blended with 100 parts by weight of a resin Resin sheet. A polyester system mainly composed of an amorphous polyester composed of a dicarboxylic acid component composed of terephthalic acid, a diol component composed of 20 to 35 mol% 1,4-cyclohexanedimethanol and 65 to 80 mol% ethylene glycol. 0.5 to 25 parts by weight of an acrylic rubber impact modifier, 0.5 to 5 parts by weight of a glycidyl methacrylate copolymer, and 0.5 to 10 parts by weight of an acrylic polymer processing aid with respect to 100 parts by weight of the resin And an impact-resistant polyester-based resin sheet formed by molding a resin composition comprising 1 to 3 parts by weight of a lubricant. The impact-resistant polyester resin sheet according to claim 1 or 2, wherein the glycidyl methacrylate copolymer is a copolymer of glycidyl methacrylate and another vinyl monomer.