JP2005154712A - Amorphous polyester resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new amorphous polyester resin excellent in transparency and which realizes the improvement of rigidity, and to provide a method for producing the same. <P>SOLUTION: The amorphous polyester resin containing an ester polymer, a crystallization inhibitory monomer and inorganic oxide fine particles is obtained by dispersing the inorganic oxide fine particles in a prescribed monomer to form the fine particles-containing monomer, then performing the polymerization reaction in the presence of the fine particles-containing monomer and the crystallization inhibitory monomer to form the polyester. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an amorphous polyester resin having transparency, low linear expansion and high rigidity, and a method for producing the same.

  Examples of transparent resins that can be used for optical applications such as organic glass and plastic lenses include methacrylic resins, polycarbonate resins, styrene resins, and epoxy resins. Organic glass has superior impact resistance, light weight, and moldability compared to inorganic glass, and methacrylic resin, in particular, has high light transmittance, low light scattering, excellent transparency, and high weather resistance. In order to be superior, its use and usage are also increasing.

  However, considering the application of the organic glass to actual products, the above-mentioned various properties such as impact resistance are not sufficient, and various research and development have been conducted to improve these properties. For example, in Japanese Patent Laid-Open No. 11-343349, for the purpose of improving rigidity, a resin made of a transparent resin in which fine amorphous silica having a diameter equal to or smaller than the visible light wavelength is blended with a transparent amorphous organic polymer. A window is disclosed.

  In the process of forming a transparent amorphous polymer, the resin is obtained by adding silica fine particles dispersed in a solvent to obtain a reaction system, and then adding a coagulant solvent to the reaction system to precipitate. Thus, an amorphous transparent resin containing the silica fine particles and the polymer is obtained. The polymer can be produced through a polymerization reaction such as suspension polymerization, solution polymerization, emulsion polymerization or bulk polymerization, and methyl methacrylate or the like is used as a monomer constituting the polymer.

  Japanese Patent Laid-Open No. 6-316045 discloses a laminated sheet consisting of three layers of a (meth) acrylic resin sheet, a thermoplastic polyurethane sheet, and a polycarbonate sheet on both sides of the (meth) acrylic resin sheet. ) Synthesis in which a laminated film on which an acrylic resin film and a polycarbonate film are attached is laminated so that the (meth) acrylic resin sheet of the laminated sheet and the (meth) acrylic resin film of the laminated film are in contact with each other. A resin safety glass is disclosed.

  Thereby, the adhesiveness of each layer in the safety glass can be improved, and devitrification of the (meth) acrylic resin sheet and distortion of the transmission image can be prevented at a high temperature of the hot press method. Furthermore, when the safety glass receives a strong impact, the internal (meth) acrylic resin portion can be prevented from being broken and scattered by the impact.

  Furthermore, JP-A-6-71826 comprises a layer made of a copolymer of a specific glutarimide and methyl methacrylate or a methacrylic resin, and a layer made of a transparent polymer having impact resistance to polycarbonate or the like. A vehicular glazing material is disclosed in which a hardened surface film is formed directly or via a primer layer on the surface of a laminated structure.

  However, since conventional organic glass and the above-described resin have lower rigidity than inorganic glass, the thickness thereof is increased when applied to a large-sized product requiring a certain degree of rigidity, such as a front window of a vehicle, for example. This is necessary, and results in contrary to weight reduction. On the other hand, when a filler such as glass fiber is added to increase the rigidity, the transparency is lowered and it is difficult to ensure visibility.

  In addition, organic glass has the advantages of being lighter and more flexible in molding than inorganic materials, but its rigidity is low due to its low modulus of elasticity, resulting in a return of residual stress during molding at high temperatures, resulting in warping and reduced appearance quality. Or the surface is easily damaged due to low hardness. On the other hand, the above-mentioned resins are used for small parts such as automobile headlamps and sunroofs that have relatively low rigidity and are easy to surface-treat. There is nothing that can be done.

  On the other hand, for automotive exterior resin parts and interior resin parts other than window glass, from the aspect of impact resistance such as cracking against impact, fuel consumption, etc., deterioration of appearance quality such as warping and narrowing of gaps due to return of residual stress at high temperature At present, demands for improving physical properties such as weight reduction of parts and cost reduction are increasing. In order to meet these demands for improving physical properties, conventionally, improvement by layering has been studied in addition to the use of a single resin. It is considered that high value-added products can be produced at low cost by stacking, and cost reduction can be achieved by reducing the number of parts by integral molding with peripheral parts.

  However, in the laminate described in JP-A-6-316045, three types of transparent resins are laminated to improve impact resistance. However, in order to maintain transparency, thermal expansion at high temperatures is suppressed in the resin. When a filler or the like is not blended and applied to an interior / exterior part of an automobile, appearance quality such as unevenness due to extension of the part and warp due to expansion may be deteriorated at high temperatures in summer.

  Also, in the above Japanese Patent Laid-Open No. 6-71826, an example of a resin window in which (meth) acrylic resin, polycarbonate resin or the like is laminated is disclosed, but a filler that suppresses thermal expansion in order to maintain the transparency of the resin. Therefore, it is difficult to sufficiently suppress thermal expansion. Further, in order to maintain transparency, it is not possible to add a filler for improving the rigidity such as glass fiber, and if it is attempted to improve the rigidity, it is necessary to increase the plate thickness, resulting in an increase in weight, which is contrary to the weight reduction.

  Further, in JP-A-11-343349, since the silica fine particles are dispersed in an organic solvent different from the monomer that is a polymer raw material that is the main component of the resin, the silica fine particles are uniformly distributed in the finally obtained resin. Moreover, it is difficult to mix with good yield, and it is difficult to ensure transparency and improve rigidity.

  The present invention has been made in view of the above problems of the prior art, and is a novel non-transparent organic glass that can be applied to various products in place of the conventional inorganic glass and has excellent transparency and can improve rigidity. A crystalline polyester resin and a method for producing the same are provided.

In order to solve the above problems, the present invention provides:
The present invention relates to an amorphous polyester resin comprising an ester polymer, a crystal inhibition monomer composed of at least one of glycols and dibasic acids, and inorganic oxide fine particles.

The present invention also provides:
A step of dispersing inorganic oxide fine particles in a predetermined monomer to form a fine particle-containing monomer;
Performing a polymerization reaction in the presence of a crystal-inhibiting monomer composed of at least one of the fine particle-containing monomer and glycols and dibasic acid to form an ester polymer;
It is related with the manufacturing method of the amorphous polyester resin characterized by comprising.
Furthermore, the present invention comprises a step of dispersing inorganic oxide fine particles in a predetermined monomer to form a fine particle-containing monomer, and a step of previously forming an ester polymer, and further comprising the ester polymer and the fine particle-containing monomer. And a step of polymerizing after mixing the crystal-inhibiting monomer, and a method for producing an amorphous polyester resin.

  According to the present invention, a fine particle-containing monomer in which inorganic oxide fine particles are dispersed in a predetermined monomer is prepared, and an ester polymer is formed by performing a polymerization reaction in the presence of the fine particle-containing monomer and the crystal inhibition monomer. ing. At this time, the fine particle-containing monomer constitutes the ester polymer through the polymerization reaction, but the crystal-inhibiting monomer inhibits crystallization of the ester polymer through the polymerization process. As a result, the finally obtained polyester resin becomes amorphous and exhibits sufficiently high transparency.

  Further, since the inorganic oxide fine particles are dispersed in the monomer which is a constituent material of the ester polymer, the inorganic oxide fine particles are uniformly dispersed in the ester polymer through the polymerization reaction. Therefore, the mechanical strength such as rigidity of the polyester resin can be improved by the filling effect of the inorganic oxide fine particles.

  In the present invention, the inorganic oxide fine particles can be dispersed in all kinds of constituent monomers constituting the ester polymer, or can be dispersed in one or more constituent monomers. Although not specified in the above-described production method, in the latter case, if necessary, one or more monomers are prepared as constituent raw materials in addition to the monomer in which the inorganic oxide fine particles are dispersed. Moreover, it can also be made to disperse | distribute in the said crystal | crystallization inhibition monomer in addition to the said monomer as needed.

  In the present invention, “amorphous” means a state in which the heat of crystal fusion measured by a scanning scanning calorimeter is 50% or less of that of a homoester polymer.

  Further, “transparent” in the present invention is defined as a haze value of a sample having a thickness of 2 mm of 5% or less.

  As described above, according to the present invention, a novel amorphous polyester resin excellent in mechanical properties such as transparency and rigidity can be provided. Therefore, it can be widely applied as an organic glass applicable to various products in place of the conventional inorganic glass.

Details of the present invention, as well as other features and advantages, are described in detail below.
The polyester resin in the present invention needs to be amorphous. In general, in order to improve the strength and rigidity of organic glass, high-strength and rigid molecules can be used in consideration of the molecular structure of the polymer constituting the resin. However, when the crystallinity of the resin is increased, there is one aspect that the transparency is lowered. Therefore, in the present invention, the target polyester resin is made amorphous.

  In the present invention, in order to make the polyester resin finally obtained amorphous, a crystal-inhibiting monomer is used in the process of producing the polyester resin. When the polyester resin is produced through a polymerization process from a predetermined monomer, the polymerization is carried out in the crystal-inhibiting monomer, whereby the crystallization of the ester polymer constituting the polyester resin is inhibited, and the polyester resin is amorphous. It becomes.

  In the present invention, in order to make the polyester resin amorphous, the crystal inhibition monomer is composed of at least one of glycols and dibasic acids. Thereby, the polyester resin can be made amorphous efficiently.

  In addition, when manufacturing pellets or products from resin powder, the pellets and the product can be made transparent by controlling molding conditions and the like, but fillers such as inorganic oxide fine particles are used as in the present invention. If included, crystallization proceeds with the filler as a core, and the polyester resin finally obtained may crystallize. Therefore, in the present invention, as described above, the crystal inhibition monomer is used as an essential element.

  The crystallization-inhibiting monomer preferably contains at least one glycol of 1,4-cyclohexanedimethanol and neopentyl glycol. Moreover, it is preferable to contain at least one dibasic acid of isophthalic acid and 2,6-naphthalenedicarboxylic acid. Thereby, the polyester resin finally obtained can be sufficiently amorphized without depending on the content of the inorganic oxide fine particles.

  Further, the content ratio of the crystal-inhibiting monomer in the amorphous polyester resin can be appropriately selected in consideration of the mechanical strength such as rigidity and the degree of transparency required for the resin, preferably The blending ratio in the amorphous polyester resin is 1 mol% to 25 mol%, more preferably 5 mol% to 25 mol%. This blending ratio can be identified by a pyrolysis gas chromatography method or the like.

  The amorphous polyester resin of the present invention contains an ester polymer as a main component, that is, a skeletal component, the type of which is obtained through a polycondensation reaction of a polybasic acid and a polyhydric alcohol, an alkyd polymer, an unsaturated ester. Well-known things, such as a polymer and a maleic acid polymer, can be illustrated. However, in the present invention, an unsaturated ester polymer, particularly polyethylene terephthalate can be preferably used.

  Polyethylene terephthalate has good compatibility with the above-mentioned crystal-inhibiting monomer and can sufficiently amorphize the finally obtained polyester resin without greatly depending on production conditions. In addition, polyethylene terephthalate has excellent mechanical strength among ester polymers, and can sufficiently improve mechanical properties such as rigidity of the finally obtained amorphous polyester resin.

  The amorphous polyester resin of the present invention contains inorganic oxide fine particles. The inorganic oxide fine particles function as a filler for the amorphous polyester resin as in the conventional case. The reason why the inorganic oxide fine particles are used as the filler is that the inorganic oxide fine particles are uniformly dispersed in the crystal-inhibiting monomer due to the production method of the present invention described below. As a result of conducting the polymerization reaction in the presence, the inorganic oxide fine particles are uniformly dispersed in the ester polymer without agglomeration, and the mechanical properties of the amorphous polyester resin finally obtained are not impaired. This is because the mechanical strength can be improved.

  The kind of the inorganic oxide fine particles is not particularly limited, but is preferably silica particles. Since the silica particles have a silanol group on the surface thereof, the affinity with the above-described crystal-inhibiting monomer is increased due to the silanol group. Therefore, the silica particles are stably present in the crystallization-inhibiting monomer, and are stably present in the amorphous polyethylene resin as the final product. Therefore, the uniform dispersion of the silica particles in the amorphous polyethylene resin is stably secured, and the transparency and mechanical strength can be sufficiently secured.

  Further, the average diameter of the inorganic oxide fine particles is preferably 5 nm to 100 nm, and more preferably 5 nm to 20 nm. When the average diameter of the inorganic oxide fine particles exceeds 100 nm, near the lower limit wavelength of visible light wavelength, that is, near 380 nm, the light transmittance of the amorphous polyester resin decreases, and the transparency may not be sufficiently secured. is there. In addition, when the average diameter of the inorganic oxide fine particles is less than 5 nm, not only is it difficult to obtain the market, but agglomeration occurs due to poor peptization, and the transparency of the amorphous polyester resin cannot be sufficiently secured. There is.

  Furthermore, the content of the inorganic oxide fine particles in the amorphous polyester resin is preferably 1% by weight to 50% by weight, and more preferably 1% by weight to 10% by weight. When the content of the inorganic oxide fine particles exceeds 50% by weight, the inorganic oxide fine particles are aggregated in the amorphous polyester resin, and the transparency of the amorphous polyester resin may not be sufficiently secured. is there. On the other hand, when the content of the inorganic oxide fine particles is less than 1% by weight, the effect as a filler cannot be obtained, and the mechanical strength such as rigidity of the amorphous polyester resin cannot be sufficiently improved. There is.

  Next, the manufacturing method of the amorphous polyester resin of the present invention described above will be described. First, the inorganic oxide fine particles are uniformly dispersed in a monomer constituting a later ester polymer to obtain a fine particle-containing monomer. Specifically, an aqueous solution containing the inorganic oxide is prepared by, for example, a water glass method, and then the solvent is replaced with a monomer liquid such as ethylene glycol. Examples of commercially available products include EG-ST manufactured by Nissan Chemical Industries, Ltd.

  Next, the crystal-inhibiting monomer and other monomers constituting the polymer are charged into the solution, and a reaction intermediate (when terephthalic acid and ethylene glycol are present at a predetermined temperature, for example, 180 to 220 ° C., under a pressurized atmosphere. Bishydroxyethylene terephthalate is prepared), and then polymerized by heating to a predetermined temperature, for example, 200 ° C. to 280 ° C. in a reduced-pressure atmosphere, whereby crystallization is inhibited by the crystal-inhibiting monomer, and An amorphous polyester resin in which the inorganic oxide fine particles are stably and uniformly dispersed can be obtained. As the catalyst, germanium dioxide or the like can be used.

  Alternatively, an ester polymer is prepared in advance, and then the solution and the crystal inhibition monomer are added and polymerized, whereby the crystallization is inhibited by the crystal inhibition monomer, and the inorganic oxide fine particles are stable. In addition, a non-quality polyester resin that is uniformly dispersed can be obtained.

  Here, when the weight average molecular weight of the finally obtained amorphous polyester is in the range of 20000 to 25000, the range of 5000 to 10,000 is the standard, and in the range of 25000 to 30000, the ester polymer is generally in the range of 10,000 to 15000. For example, in the case of polyethylene terephthalate, this ester polymer is terephthalic acid and ethylene glycol at 200 to 250 ° C. and 0.2 to 0.3 MPa, and bishydroxyethylene terephthalate is also used as a starting material at 200 to 250 ° C., It can be produced under the condition of 0.2 to 0.3 MPa.

  Next, the polymerization after mixing the solution and the crystal-inhibiting monomer is performed at 200 to 280 ° C. under a reduced pressure atmosphere, whereby the non-quality polyester resin can be obtained.

  By adding to the polymerization system what does not participate in the polymerization, the polymerization reaction tends to be somewhat inhibited. By preparing the above-mentioned ester polymerization holiday in advance and then introducing the solution and the crystal-inhibiting monomer for polymerization, inhibition of this polymerization reaction is greatly improved. The technique described in claims 12 to 14 is this removal, and a polymer having a sufficiently high molecular weight can be obtained even if inorganic oxide fine particles are added.

  In the preparation of the intermediate, since the glycol monomer is required to be twice or more equivalent to that of the dibasic acid, it is necessary to add the glycol monomer as many times as appropriate. Since this glycol monomer is recovered after completion of the polymerization reaction, there is no particular limitation, but ethylene glycol is preferred from the viewpoint of low cost. In the examples and comparative examples described later, the glycol monomer was actually added so as to be twice the equivalent of the dibasic acid, but since it was recovered after polymerization, in the text and in the table, the monomer incorporated into the polymer Only for convenience.

  As described above, the inorganic oxide fine particles may be dispersed in all the monomers instead of being dispersed in one or more monomers selected from the monomers constituting the ester polymer. Moreover, a commercially available thing can be used for the fine particle containing monomer mentioned above. Moreover, it can also be made to disperse | distribute in the said crystal | crystallization inhibition monomer in addition to the said monomer as needed.

The invention is illustrated by the following examples and comparative examples. The flexural modulus, linear expansion coefficient, and light transmittance were measured by the following methods.
Flexural modulus Measured with an autograph (DCS-10T, manufactured by Shimadzu Corporation).
Linear expansion coefficient It measured with the thermomechanical measuring apparatus (TMA120C Seiko Electronics Co., Ltd.).
Light transmittance Measured with a haze meter (manufactured by Murakami Color Research Laboratory, HM-65 Co., Ltd.).
DSC
It was measured with an inspection scanning calorimeter (DSC2920TA Instruments Inc.).
Intrinsic Viscosity The obtained polymer was dissolved in phenol / tetrachloroethane = 60/40 (volume ratio), and after the solvent-soluble component was dried, the solid content was 30 ° C. phenol / tetrachloroethane = 60/40 ( Volume ratio) Measured by dissolving in a solvent.

(Example 1)
A terephthalic acid monomer, an ethylene glycol monomer containing 20% by weight of silica particles having a particle size of 15 nm, and a neopentyl glycol monomer are mixed at a molar ratio of 50: 49: 1, and a reaction intermediate is produced under a pressure of 180 ° C. Then, polymerization was performed using a germanium dioxide catalyst and trimethyl phosphate under reduced pressure at 230 ° C. to obtain a colorless and transparent resin. Further, it was confirmed by an inspection scanning calorimeter (DSC) that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.4 GPa, the linear expansion coefficient was 3.5 × 10 ⁻⁵ / ° C., the haze value was 1.5%, and the intrinsic viscosity of the solvent-soluble component was 0.51 dl / g. The results are shown in Table 1.

(Example 2)
Example 1 except that the silica particle-containing ethylene glycol had a silica particle content of 30% by weight and the mixing ratio of the terephthalic acid monomer, the silica particle-containing ethylene glycol monomer, and the neopentyl glycol monomer was 50: 49: 1. Polymerization was performed in the same manner to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 4.3 GPa, the linear expansion coefficient was 3.8 × 10 ⁻⁵ / ° C., the haze value was 1.4%, and the intrinsic viscosity of the solvent-soluble component was 0.49 dl / g. The results are shown in Table 1.

(Example 3)
Example 1 except that the silica particles-containing ethylene glycol had an average diameter of 5 nm and the mixing ratio of the terephthalic acid monomer, the silica particles-containing ethylene glycol monomer, and the neopentyl glycol monomer was 50:40:10. Polymerization was performed in the same manner to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.4 GPa, the linear expansion coefficient was 4.1 × 10 ⁻⁵ / ° C., the haze value was 1.4%, and the intrinsic viscosity of the solvent-soluble component was 0.51 dl / g. The results are shown in Table 1.

Example 4
Polymerization was carried out in the same manner as in Example 3 except that the silica particles-containing ethylene glycol had an average diameter of silica particles of 100 nm to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 3.1 GPa, the linear expansion coefficient was 3.9 × 10 ⁻⁵ / ° C., the haze value was 1.3%, and the intrinsic viscosity of the solvent-soluble component was 0.52 dl / g. The results are shown in Table 1.

(Example 5)
Example 1 except that the silica particle-containing ethylene glycol had a silica particle content of 5% by weight and the mixing ratio of the terephthalic acid monomer, the silica particle-containing ethylene glycol monomer, and the neopentyl glycol monomer was 50:40:10. Polymerization was performed in the same manner to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 1.9 GPa, the linear expansion coefficient was 6.5 × 10 ⁻⁵ / ° C., the haze value was 1.6%, and the intrinsic viscosity of the solvent-soluble component was 0.51 dl / g. The results are shown in Table 1.

(Example 6)
A terephthalic acid monomer, an ethylene glycol monomer containing 75% by weight of silica particles having a particle size of 15 nm, and a neopentyl glycol monomer containing 75% by weight of silica particles having a particle size of 15 nm were mixed in a molar ratio of 50:40:10. After preparing a reaction intermediate under a pressure of 180 ° C., polymerization was performed using a germanium dioxide catalyst and trimethyl phosphate under a reduced pressure of 230 ° C. to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 4.5 GPa, the linear expansion coefficient was 3.5 × 10 ⁻⁵ / ° C., the haze value was 1.9%, and the intrinsic viscosity of the solvent-soluble component was 0.51 dl / g. The results are shown in Table 1.

(Example 7)
Polymerization was performed in the same manner as in Example 1 except that the mixing ratio of the terephthalic acid monomer, the silica particle-containing ethylene glycol monomer, and the neopentyl glycol monomer was set to 50:40:10 to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.4 GPa, the linear expansion coefficient was 3.5 × 10 ⁻⁵ / ° C., the haze value was 1.2%, and the intrinsic viscosity of the solvent-soluble component was 0.49 dl / g. The results are shown in Table 1.

(Example 8)
1,4-cyclohexanedimethanol monomer was used instead of neopentyl glycol monomer, and the mixing ratio of terephthalic acid monomer, silica particle-containing ethylene glycol monomer, and 1,4-cyclohexanedimethanol monomer was 50:40:10. Except for the above, polymerization was carried out in the same manner as in Example 1 to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.3 GPa, the coefficient of linear expansion was 3.5 × 10 ⁻⁵ / ° C., the haze value was 1.2%, and the intrinsic viscosity of the solvent-soluble component was 0.51 dl / g. The results are shown in Table 1.

Example 9
Example 1 except that isophthalic acid monomer was used instead of neopentyl glycol monomer and the mixing ratio of terephthalic acid monomer, silica particle-containing ethylene glycol monomer, and isophthalic acid monomer was 50:40:10. Polymerization was performed to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.3 GPa, the linear expansion coefficient was 4.8 × 10 ⁻⁵ / ° C., the haze value was 1.5%, and the intrinsic viscosity of the solvent-soluble component was 0.50 dl / g. The results are shown in Table 1.

(Example 10)
Instead of neopentyl glycol monomer, 2,6-naphthalenedicarboxylic acid monomer was used, and the mixing ratio of terephthalic acid monomer, silica particle-containing ethylene glycol monomer, and 2,6-naphthalenedicarboxylic acid monomer was 40:50:10. Except for the above, polymerization was carried out in the same manner as in Example 1 to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.9 GPa, the linear expansion coefficient was 5.3 × 10 ⁻⁵ / ° C., the haze value was 2.2%, and the intrinsic viscosity of the solvent-soluble component was 0.51 dl / g. The results are shown in Table 1.

(Example 11)
Example except that silica particle-containing propylene glycol monomer was used instead of silica particle-containing ethylene glycol monomer, and the mixing ratio of terephthalic acid monomer, silica particle-containing propylene glycol monomer, and neopentyl glycol was 50:40:10 Polymerization was carried out in the same manner as in 1 to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.3 GPa, the coefficient of linear expansion was 6.4 × 10 ⁻⁵ / ° C., and the haze value was 1.5%. The results are shown in Table 1.

(Example 12)
By heating a terephthalic acid monomer and an ethylene glycol monomer at 250 ° C. and 0.3 MPa, a polyethylene terephthalate having a weight average molecular weight of 5000 is obtained, and an ethylene glycol monomer solution containing 20% by weight of silica particles having a particle size of 15 nm, isophthalic acid Were mixed at a molar ratio of 1: 100: 100 and polymerized using a germanium dioxide catalyst and trimethyl phosphate under reduced pressure at 280 ° C. to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 3.3 GPa, the linear expansion coefficient was 3.7 × 10 ⁻⁵ / ° C., the haze value was 1, 3%, and the intrinsic viscosity of the solvent-soluble component was 0.58 dl / g. . The results are shown in Table 2.

(Example 13)
By heating the terephthalic acid monomer and the ethylene glycol monomer at 250 ° C. and 0.3 MPa, a polyethylene terephthalate having a weight average molecular cliff of 5000 is obtained, and an ethylene glycol monomer solution containing 2.0% by weight of silica particles having a particle size of 15 nm. , Neopentyl glycol and terephthalic acid were mixed at a molar ratio of 1: 50: 50: 100 and polymerized using a germanium dioxide catalyst and trimethyl phosphate under reduced pressure at 280 ° C. to obtain a colorless and transparent resin. . Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 3.2 GPa, the linear expansion coefficient was 3.8 × 10 ⁻⁵ / ° C., the haze value was 1.3%, and the intrinsic viscosity of the solvent-soluble component was 0.59 dl / g. . The results are shown in the last 2.

(Example 14)
By heating pishydroxyethylene terephthalate at 250 ° C. and 0.3 MPa, polyethylene terephthalate having a weight average molecular weight of 5000 is obtained, and an ethylene glycol monomer solution containing 20% by weight of silica particles having a particle size of 1.511 nm and isophthalic acid are obtained. The mixture was mixed at a molar ratio of 1: 100: 100, and mixed under reduced pressure of 280 ° C. using a germanium dioxide catalyst and trimethyl phosphate to obtain a colorless and transparent resin. Moreover, it was confirmed by DSC that the resin was amorphous. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 3.5 GPa, the linear expansion coefficient was 4.1 × 10 ”5 / ° C., the haze value was 1.2%, and the intrinsic viscosity of the solvent-soluble component was 0.57 dl / g. . The results are shown in Table 2.

(Comparative example)
A terephthalic acid monomer and ethylene glycol containing 20% by weight of silica particles having a particle size of 15 nm were mixed at a molar ratio of 50:50 to prepare a reaction intermediate under a pressure of 180 ° C., and then a reduced pressure of 280 ° C. Polymerization with a germanium dioxide catalyst and trimethyl phosphate gave a whiteish resin. Moreover, it was confirmed by DSC that the resin was crystalline. A test piece was prepared by injection molding and then subjected to a test. The flexural modulus at room temperature was 2.6 GPa, the linear expansion coefficient was 4.3 × 10 ⁻⁵ / ° C., the haze value was 13.0%, and the intrinsic viscosity of the solvent-soluble component was 0.51 dl / g. The results are shown in Table 1.

  As mentioned above, it turns out that the amorphous polyester resin of this invention shows a high value with respect to a bending elastic modulus, a linear expansion coefficient, and light transmittance from an Example and a comparative example.

  As described above, the present invention has been described in detail based on the embodiments of the present invention with specific examples. However, the present invention is not limited to the above contents, and all modifications and changes are made without departing from the scope of the present invention. It can be changed.

  For example, the amorphous polyester resin of the present invention may optionally contain an antioxidant and a heat stabilizer (for example, including hindered phenol, hydroquinone, thioether, phosphites, and their substitution products and combinations thereof), UV absorbers (eg resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants, mold release agents (eg silicone resin, montanic acid and salts thereof, stearic acid and salts thereof, stearyl alcohol, stearylamide, etc.), dyes (eg nitrocin) Etc.), colorants including face departments (for example, cadmium sulfide, phthalocyanine, etc.), additive additives (for example, silicone oil), crystal nucleating agents (for example, talc, kaolin, etc.), etc. Can do.

  The amorphous polyester resin of the present invention can be molded into a desired shape and applied to any application. In particular, from the viewpoint of utilizing transparency, high rigidity, and low linear expansion, it can be applied to molded products such as parts around automobile windows as organic glass replacing inorganic glass.

Claims (14)

  An amorphous polyester resin comprising an ester polymer, a crystal inhibition monomer composed of at least one of glycols and dibasic acids, and inorganic oxide fine particles.   The amorphous polyester resin according to claim 1, wherein the content of the crystal-inhibiting monomer is 1 mol% to 25 mol%.   The amorphous polyester resin according to claim 1 or 2, wherein the crystal-inhibiting monomer contains at least one of 1,4-cyclohexanedimethanol and neopentyl glycol.   The amorphous polyester resin according to any one of claims 1 to 3, wherein the crystal-inhibiting monomer contains at least one dibasic acid of isophthalic acid and 2,6-naphthalenedicarboxylic acid.   The amorphous polyester resin according to any one of claims 1 to 4, wherein the ester polymer is polyethylene terephthalate.   The amorphous polyester resin according to claim 1, wherein the inorganic oxide fine particles have an average particle diameter of 5 nm to 100 nm.   The amorphous polyester resin according to claim 1, wherein the content of the inorganic oxide fine particles is 1% by weight to 50% by weight.   The amorphous polyester resin according to claim 1, wherein the inorganic oxide fine particles are silica particles.   A molded body comprising the amorphous polyester resin according to any one of claims 1 to 8. A method for producing an amorphous polyester resin according to any one of claims 1 to 8,
A step of dispersing inorganic oxide fine particles in a predetermined monomer to form a fine particle-containing monomer;
Performing a polymerization reaction in the presence of a crystal-inhibiting monomer composed of at least one of the fine particle-containing monomer and glycols and dibasic acid to form an ester polymer;
A process for producing an amorphous polyester resin, comprising:   The method for producing an amorphous polyester resin according to claim 10, wherein the polymerization reaction is performed using monomers of terephthalic acid and ethylene glycol to form polyethylene terephthalate as the ester polymer. A method for producing an amorphous polyester according to any one of claims 1 to 8,
Comprising a step of dispersing inorganic oxide fine particles in a predetermined monomer to form a fine particle-containing monomer, and a step of producing an ester polymer,
Furthermore, the manufacturing method of the amorphous polyester resin obtained from the process of superposing | polymerizing after mixing the said ester polymer, the said fine particle containing monomer, and a crystal | crystallization inhibition monomer.   The method for producing an amorphous polyester resin according to claim 12, wherein the ester polymer is obtained from terephthalic acid and ethylene glycol.   The method for producing an amorphous polyester resin according to claim 12, wherein the ester polymer is obtained from bishydroxyethylene terephthalate.