JPH06107805A - Additive-containing resin molding and its production - Google Patents

Abstract

PURPOSE:To produce an additive-contg. polyester resin molding which hardly allows the additive containd therein to vaporize or disappear and hence long retains the properties of the additive. CONSTITUTION:An additive 6 having a carboxyl, hydroxyl, or amino group at its molecular end or having an ester group in its molecule is incorporated into a molding 50 by melt mixing a polyester resin 5 with an additive 6 e.g. on an extruder 1, thereby causing the transesterification between the additive 6 and the molecule of the resin 5 in a thermally molten state to bond the additive 6 to the molecule of the resin 5 via an ester bond, and molding the resin 5 into a desired shape.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention volatilizes various additives,
The present invention relates to a molded article made of a polyester resin contained so as not to disappear, and a method for producing the same.

[0002]

2. Description of the Related Art Polyester resins are excellent in strength and the like, but have a drawback that they are inferior in weather resistance. Therefore, when a polyester resin such as polycarbonate is melted and molded to manufacture roofing materials and other exterior building materials, an ultraviolet absorber is added to the resin to suppress deterioration of the resin due to ultraviolet rays and improve weather resistance. I am trying to

[0003]

However, even if a UV absorber which has been widely used in the past is added to a polyester resin such as polycarbonate, the UV absorber is likely to volatilize and disappear during melting and molding of the resin, There was a problem that it volatilizes and disappears even after molding. Therefore, conventional polyester-based resin molded articles containing an ultraviolet absorber are still unsatisfactory in terms of maintaining weather resistance for a long period of time.

Under these circumstances, studies have recently been conducted on high molecular weight ultraviolet absorbers that are difficult to volatilize, and, for example, ultraviolet absorbers composed of a copolymer of a benzophenone compound and an acrylic monomer have been developed. However, such a high molecular weight UV absorber may have poor compatibility with a polyester resin, and when added to a polycarbonate resin having good transparency, it causes a problem of transparency deterioration and coloring. There are cases.

In addition, a heat resistance improver, a flame retardant, and other additives may be contained in the polyester resin molded article depending on the intended use. However, if the additives are physically mixed, the additives are the same as above. However, there is a problem that it is difficult to maintain the performance of the additive for a long period of time because it volatilizes over time.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide an additive-containing polyester system capable of maintaining the performance of an additive for a long period of time with almost no volatilization or disappearance of the additive. It is to provide a resin molded product and a novel manufacturing method thereof.

[0007]

To achieve the above object, the additive-containing resin molded article of the present invention comprises an additive having a carboxyl group, a hydroxyl group or an amino group at the molecular end, or an ester in the molecule. An additive having a bond is contained, and the additive is ester-exchanged with a polymer molecule of a polyester resin to form an ester bond.

According to the production method of the present invention, an additive having a carboxyl group, a hydroxyl group or an amino group at the molecular end or an additive in the molecule is added before the polyester resin is heated and melted to be molded into a predetermined shape. It is characterized in that an additive having an ester bond is added to cause a transesterification reaction with polymer molecules of a polyester resin in a heat-melted state.

[0009]

The additive used in the present invention is a compound having a carboxyl group, a hydroxyl group or an amino group at the molecular end,
Or, since it is a compound having an ester bond in the molecule,
When the additive is added to the polyester-based resin before molding as in the production method of the present invention, most of the additive causes an ester exchange reaction at the ester bond portion of the polymer molecule of the polyester-based resin that is heated and melted, and the additive is It is immobilized by ester bond. Therefore, since the ester-bonded additive is contained and held in the resin molded product in a non-volatile manner, the resin molded product of the present invention can maintain the performance of the additive for a long period of time. The unreacted additive is mixed in the polymer molecule in a dispersed state.

[0010]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic explanatory view showing an embodiment of the production method of the present invention, illustrating the case of producing a plate-shaped molded product (resin plate) of a polyester resin containing an ultraviolet absorber as an additive. Is.

In FIG. 1, 1 is a melt extrusion molding machine, 1a
Is a resin charging hopper provided at the rear of the molding machine, 1b is an additive charging hopper provided in the middle of the molding machine, 1c is a screw built into the molding machine, 1d is molding gold provided at the tip of the molding machine. A mold 2, a pair of upper and lower cooling rolls, 3 a conveyor belt, and 4 a cutting machine.

According to this embodiment, the raw material polyester resin 5 dried by preheating is introduced into the molding machine 1 from the hopper 1a at the rear part of the molding machine, and the polyester resin 5 is melted at a temperature not lower than the melting temperature (but not the decomposition temperature). The following) is heated and melted, and kneaded with the screw 1c. Then, as the additive 6, an ultraviolet absorber having a carboxyl group, a hydroxyl group, or an amino group at the molecular end, or an ultraviolet absorber having an ester bond in the molecule is charged from the hopper 1b in the middle of the molding machine, and the screw 1c Is uniformly kneaded with the heat-melted polyester resin 5 and extruded into a plate shape from the mold 1d.

When the ultraviolet absorber is kneaded in this way, the ultraviolet absorber causes an ester exchange reaction at the ester bond portion in the polymer molecule of the polyester resin 5 to produce a polymer molecule in which the ultraviolet absorber is ester-bonded at the molecular end. . This transesterification reaction is based on the polyester resin 5
Is performed in a molten state.

A polyester resin molded product 50 extruded in a plate shape from the mold 1d is taken while being cooled by a pair of upper and lower cooling rolls 2 and 2, and is carried on a conveyor belt 3 to a cutting machine 4. Then, it is cut into a predetermined length.

The ultraviolet absorbent-containing polyester resin plate (molded product) produced by the above-mentioned method is a resin plate in which the ultraviolet absorber is immobilized by ester bond to the end of the polymer molecule of the polyester resin, and cannot be volatilized. As it is contained and retained in the product, it retains its excellent UV absorption ability for a long period of time,
Very good weather resistance.

As the raw material polyester resin 5, a thermoplastic polyester resin such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone or the like, which has a relatively high melting temperature and is prone to transesterification, is preferably used. To be done.

Further, the following benzophenone-based or benzotriazole-based UV absorbers are preferably used. That is, as an ultraviolet absorber having a carboxyl group at the molecular end, 2- (2'-hydroxy-5'-
Carboxyphenyl) benzotriazole, 2-hydroxybenzophenone-4-oxyacetic acid and the like are used, and as the ultraviolet absorber having a hydroxyl group at the molecular end, 2-hydroxy-4- (2'-hydroxyethoxy) benzophenone, 2,2 ′, 4,4 ′, 6,6′-hexahydroxybenzophenone, 2- (2 ′, 4′-dihydroxyphenyl) benzotriazole, 2-hydroxy-4-
(2'-hydroxyethoxy) benzotriazole, 2
-Hydroxy-5- (2'-hydroxyethyl) benzotriazole or the like is used, and as the ultraviolet absorber having an amino group at the molecular end, 2- (2'-hydroxy-3 '
-Amino-5'-t-butyl) benzotriazole and the like are used, and as the ultraviolet absorber having an ester bond in the molecule, 2-hydroxy-4- (2'-methacryloyloxyethoxy) benzophenone, 2,4- Di-t-butylphenyl- (3 ', 5'-di-t-butyl-4'-
Hydroxy) benzophenone, 2-hydroxybenzophenone-4-methyloxyacetate, 2- (2'-acryloyloxy-5'-methyl) benzotriazole and the like are used.

These ultraviolet absorbers are preferably added in a proportion of 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the polyester resin. When the blending amount of the ultraviolet absorber is less than 0.01 parts by weight, it is difficult to impart excellent ultraviolet absorbing ability because the amount of the ultraviolet absorber contained and retained in the obtained resin molded product is small. Conversely, 10.
When the amount is more than 0 parts by weight, the molecular weight of the polymer is reduced and the polymer is colored, so that the commercial value is reduced. Therefore, if these UV absorbers are used in combination with a UV absorber having no carboxyl group, hydroxyl group, or amino group at the terminal of the molecule, or a UV absorber having no ester bond in the molecule, the colorability is improved. be able to.

In the present invention, various additives may be contained in place of the above-mentioned ultraviolet absorber to give the resin molded article a performance suitable for the intended use. Examples of the types of additives include heat resistance improvers, flame retardants, radiation resistant agents, anti-fog agents, anti-oxidants, ozone resistant agents, antibacterial agents, antistatic agents, and plasticizers. Must be a compound having a carboxyl group, a hydroxyl group or an amino group at the end of the molecule, or a compound having an ester bond in the molecule.

As the heat resistance improver, for example, polydimethylsiloxane having a molecular terminal closed with a carboxyl group, a hydroxyl group or an amino group, a polydimethylsiloxane having an ester bond in the molecule, or a fluorinated bisphenol [for example, 2 , 2-bis- (4-hydroxyphenyl)-
Hexafluoropropane] and the like are used. As the flame retardant, for example, polydimethylsiloxane whose molecule ends are closed by a hydroxyl group or an amino group, tetrabromobisphenol, or the like is used, and the above-mentioned fluorinated bisphenol is also used as the flame retardant. In addition, thiodiphenol or the like is used as the radiation resistant agent, the above-mentioned fluorinated bisphenol or the like is used as the antifogging agent, N, N-diphenyl-p-phenylenediamine or the like is used as the antioxidant or ozone resistant agent, and the antibacterial agent is used. Tributyltin laurate or the like is used as the antistatic agent, tetraphenyldipropylene glycol diphosphite or the like is used as the antistatic agent, and dioctylphthalate or dodecanol or the like is used as the plasticizer. The blending amount of these additives may be the same as the blending amount of the above-mentioned ultraviolet absorber. However, the amount of the plasticizer can be appropriately increased depending on the application.

Additives having a carboxyl group, a hydroxyl group, or an amino group at the terminal of the molecule are highly reactive, and there are some which cause a transesterification reaction without a catalyst, but an additive having an ester bond in the molecule is a catalyst. Some do not undergo the transesterification reaction without it, so when such an additive having poor reactivity is used, it is necessary to add a catalyst. As the catalyst, catalysts for transesterification reaction such as oxides, hydroxides and carboxylates of alkali metals and alkaline earth metals are used. These catalysts are polyester-based resin 100
It is suitable to add 0.001 to 0.5 parts by weight to parts by weight.

The transesterification reaction between the polyester-based resin and the additive occurs when the polyester-based resin is heated to a temperature above the melting temperature and below the decomposition temperature to be in the molten state as described above. Therefore, for example, when a polycarbonate resin is used as the polyester resin, it may be heated in the molding machine 1 to a temperature of about 230 to 330 ° C. to be melted.

The reaction rate of transesterification is generally highest in the case of the additive having a hydroxyl group, and then in the order of the additive having an amino group, the additive having a carboxyl group, and the additive having an ester bond. The reaction rate also changes depending on the type of resin. Therefore, the time required for the transesterification reaction is slightly different depending on the type of the reactive group of the additive and the type of the polyester resin, but in any case, the reaction is completed in about 1 to 15 minutes. Therefore, when a resin plate is extrusion-molded as in the above-mentioned embodiment, the additive 6 (ultraviolet absorber) is added to the molten polyester resin 5 inside the molding machine 1 and kneaded for about 1 to 15 minutes before It is necessary to set the position of the additive-introducing hopper 1b, the screw design, and other extrusion conditions so that the resin is extruded from the mold 1d at the tip end to sufficiently carry out the transesterification reaction. In this case, a twin-screw extruder or kneader is preferably used.

In the above embodiment, the polyester resin 5 and the ultraviolet absorber 6 are separately charged into the molding machine 1 from the hoppers 1a and 1b, but both may be charged together from the hopper 1a. Alternatively, a mixture of the two may be supplied from the hopper 1b in appropriate amounts, and thus the method of adding the additives can be appropriately selected.

In the above embodiment, the resin plate is manufactured by extruding a molten polyester resin, which has been transesterified with an ultraviolet absorber (additive), in a single layer from the mold 1d to manufacture a resin plate. It is needless to say that extrusion molded products of various shapes such as sheets, films, and odd-shaped products can be manufactured by changing 1d and the like, and a melt polyester system in which additives are ester-bonded using a coextrusion molding machine or the like. A resin is used as an upper layer, and a molten polyester resin or other resin containing less or no additive than the upper layer is coextruded into upper and lower two layers or three layers, and a polyester resin layer containing an additive is formed on the surface. It is of course possible to manufacture a laminated resin plate having a two-layer or three-layer structure.

Also in the case of injection molding, if a melted polyester resin is added with an additive before the injection into a mold of an injection molding machine and a transesterification reaction is carried out, a resin with almost no volatilization of the additive is likewise obtained. A molded product can be obtained.

Next, more specific examples of the present invention will be described.

[Example 1] Polycarbonate as a polyester resin, 2-hydroxy- as an ultraviolet absorber
Dry blending was carried out in advance at a compounding ratio of 1.0 part by weight of 4- (2-methacryloyloxyethoxy) benzophenone to 100 parts by weight of polycarbonate and 0.02 part by weight of disodium maleate as a catalyst. The blended product is put into an extruder and heated at 270 ° C. for melt-kneading, and a transesterification reaction is carried out for about 10 minutes to perform extrusion molding from a mold of the molding machine to obtain a thickness of 0.1 m.
m film was obtained. And with this film the test piece
Created (1).

With respect to this test piece (1), the quantitative ratio (reaction rate) of the ester-bonded ultraviolet absorber and the unreacted mixed ultraviolet absorber was examined by the test method described below. It was found that the ultraviolet absorber was transesterified at a reaction rate of about 50%.

Further, this test piece (1) was subjected to an accelerated weathering test to examine the relationship between the irradiation time, the degree of yellowing (ΔYI), and the residual rate of the ultraviolet absorber. The results are shown in Table 1 below. The accelerated weather resistance test was performed using a xenon weatherometer (manufactured by Atlas) for 100 hours and 500 hours.
Acceleration test by irradiation for r and 1000 hours was performed, and ΔYI was obtained by measuring with a Σ90 color measuring system (manufactured by Nippon Denshoku Co., Ltd.). The remaining rate is
Using a visible ultraviolet spectrophotometer UV-3100 (manufactured by Shimadzu Corporation), the ultraviolet absorbance of the test piece at each irradiation time was measured, and the absorbance change of the maximum absorption wavelength of the ultraviolet absorbent was measured at the irradiation time of 0 hr. It is a value calculated with the residual rate being 100.

(Test method of reaction rate) Confirmation of reaction rate is conducted by GP.
It is performed using a C (gel permeation chromatography) apparatus. The maximum ultraviolet absorption wavelength (λmax) of the ultraviolet absorber 2-hydroxy-4- (2-methacryloyloxyethoxy) benzophenone used in Example 1 is 325n.
m. Therefore, the polycarbonate blended with the UV absorber and the catalyst are matched with the detection wavelength of the UV detector of the GPC at 325 nm which is not detected in the measured sample concentration. For the purpose of comparison with Example 1, the solvent is mixed at the same blending ratio, and a blend product which has not undergone transesterification reaction is referred to as Comparative Example 1. The molecular weight distribution curve of GPC of Comparative Example 1 is as shown in FIG. 2, and the peak (a) of the ultraviolet absorber appears on the low molecular side (right side of the horizontal axis). On the other hand, the molecular weight distribution curve of GPC of the test piece (1) prepared in Example 1 is as shown in FIG. Although it appears at the same elution time as peak (a), the detection intensity becomes lower, and the attenuated peak (b) is on the polymer side (left side of the horizontal axis).
It shifts to the peak (c) and appears. That is, the peaks shift due to the high molecular weight of the ultraviolet absorber due to the reaction between the ultraviolet absorber and the ends of the polycarbonate. (C)
Shows a peak of a reaction part and (b) shows a peak of an unreacted part. The reaction rate is obtained from the area ratio of the peak (b) and the peak (c) of the molecular weight distribution curve. Then, the test piece (1) prepared in Example 1 was purified to remove the unreacted ultraviolet absorber, and F
It is confirmed by T-IR, 1H, 13C-NMR that the ultraviolet absorber has an ester bond at the terminal. From this, it can be confirmed that the peak (c) is not the homopolymerization of only the ultraviolet absorber.

[Example 2] Polycarbonate as a polyester resin and 2- (2'-hydroxy-5'-carboxyphenyl) benzotriazole (λmax = 325 nm) as an ultraviolet absorber were used in an amount of 0.8 per 100 parts by weight of the polycarbonate. A test piece was prepared in the same manner as in Example 1 except that the dry blending was carried out in advance in an amount of 0.08 part by weight of triphenyl phosphite as a catalyst.
(2) was created.

With respect to this test piece (2), the reaction rate of the ultraviolet absorber was determined by the above-mentioned test method, and it was found that the ultraviolet absorber was transesterified at a reaction rate of about 37%. Further, this test piece (2) was subjected to the accelerated weathering test in the same manner as in Example 1, and the irradiation time and the degree of yellowing (ΔY
I), the relationship with the residual rate of the ultraviolet absorber was investigated. The results are shown in Table 1 below.

[Example 3] Polycarbonate as a polyester resin, 2- (2 ', 4' as an ultraviolet absorber)
-Dihydroxyphenyl) benzotriazole (λmax
= 344 nm) in an amount of 1.2 parts by weight relative to 100 parts by weight of polycarbonate, and phenylphosphonic acid as a catalyst in a blending ratio of 0.05 parts by weight. (3) was created.

With respect to this test piece (3), the reaction rate of the ultraviolet absorber was determined by the above-mentioned test method (however, the wavelength of the UV detector of GPC is 344 nm). Was found to undergo a transesterification reaction. Further, this test piece (3) was subjected to the accelerated weathering test in the same manner as in Example 1, and the irradiation time and the degree of yellowing (ΔYI),
The relationship with the residual rate of the ultraviolet absorber was investigated. The results are shown in Table 1 below.

[Example 4] Polycarbonate as a polyester resin, 2-hydroxy- as an ultraviolet absorber
4- (2'-hydroxyethoxy) benzophenone (λ
A test piece (4) was prepared in the same manner as in Example 1 except that dry blending was carried out in advance at a compounding ratio of 1.1 parts by weight with respect to 100 parts by weight of polycarbonate.

With respect to this test piece (4), the reaction rate of the ultraviolet absorber was determined by the above-mentioned test method (however, the wavelength of the UV detector of GPC is 330 nm). Was found to undergo a transesterification reaction. Further, this test piece (4) was subjected to the accelerated weathering test in the same manner as in Example 1, and the irradiation time and the degree of yellowing (ΔYI),
The relationship with the residual rate of the ultraviolet absorber was investigated. The results are shown in Table 1 below.

[Example 5] Polycarbonate as a polyester resin, and 2- (2'-hydroxy-5'-carboxyphenyl) benzotriazole (λmax = 325 nm) as an ultraviolet absorber were used in an amount of 1.0 with respect to 100 parts by weight of the polycarbonate. A test piece (5) was prepared in the same manner as in Test Example 1 except that dry blending was performed in advance at a blending ratio of parts by weight. With respect to this test piece (5), the reaction rate of the ultraviolet absorber was determined by the above-mentioned test method, and it was found that the ultraviolet absorber was transesterified at a reaction rate of about 18%. Further, this test piece (5) was subjected to the accelerated weathering test in the same manner as in Example 1, and the irradiation time and the degree of yellowing (ΔY
I), the relationship with the residual rate of the ultraviolet absorber was investigated. The results are shown in Table 1 below.

Comparative Example 1 A test piece for comparison (thickness) in which 1.0 part by weight of the ultraviolet absorber 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole was mixed with 100 parts by weight of the polycarbonate. (According to Example 1), the accelerated weather resistance test was conducted in the same manner as in Example 1 to examine the relationship between the irradiation time, the degree of yellowing (ΔYI), and the residual rate of the ultraviolet absorber. The results are shown in Table 1 below.

[0041]

[Table 1]

As can be seen from Table 1, in the test piece for comparison in which the ultraviolet absorber is simply mixed, the ultraviolet absorber easily volatilizes with time, and thus the residual rate of the ultraviolet absorber after irradiation for 1000 hours is up to 69%. While the deterioration of the test piece progresses and the yellowing degree increases to 3.9, the test piece of the example of the present invention in which most of the ultraviolet absorber is ester-bonded to the polymer of polycarbonate (1 ) To (5), since the ester-bonded ultraviolet absorber is fixed and the unreacted ultraviolet absorber is volatilized over time, even if the residual ratio of the ultraviolet absorber after irradiation for 1000 hours is at least 84. %, The yellowing degree is 1.9 at the maximum, which is less than half of the comparative test piece,
It can be seen that excellent weather resistance is maintained.

Example 6 Polycarbonate as a polyester resin and 2,2-bis (4 as a heat resistance improver
-Hydroxyphenyl) -hexafluoropropane (B
HPHFP) was dry blended in advance at a compounding ratio of 5 parts by weight with respect to 100 parts by weight of polycarbonate. This blended product was put into an extruder and melt-kneaded at 270 ° C., and a transesterification reaction was carried out by staying for about 10 minutes. Then, a resin plate having a thickness of about 1 mm is manufactured by extrusion molding into a plate shape from a mold of a molding machine, and the resin plate is cut to obtain a test piece (6).
It was created.

For this test piece (6), the reaction rate of the transesterification reaction of BHPHFP was determined by the infrared spectrum method. First, the test piece (6) was dissolved in methylene chloride and reprecipitated with methanol to remove unreacted BHPHFP in the test piece to obtain a purified test piece (6A). And this test piece
The reacted BHPHFP was quantified from the intensity of the peak resulting from BHPHFP in the infrared spectrum of (6A). As a result, the reaction rate of BHPHFP was 70%.

Further, a Soxhlet extraction test (methanol) was conducted on this test piece (6A) to determine the extraction time and BHPH.
The relationship with the residual rate of FP was investigated. The results are shown in Table 2 below.
Shown in.

For comparison, a 1 mm thick polycarbonate resin plate containing 3.5 parts by weight of BHPHFP without reacting with 100 parts by weight of polycarbonate was produced by a casting method and cut to make a comparison. For the test pieces for the same, extraction time and BHPHFP
The relationship with the residual rate was investigated. The results are shown in Table 2 below.

[0047]

[Table 2]

From Table 2, in the comparative test piece, almost all of BHPHFP was extracted in 48 hours, whereas in the purified test piece (6A) of the present invention, BHPHFP was immobilized by ester bond. It turns out that it is not extracted with methanol.

The glass transition temperature of the test piece (6A) and the test piece for comparison were measured with a differential scanning calorimeter before and after extraction with methanol for 48 hours. The test piece (6A) of the present invention was extracted. There was no change in heat resistance at 150 ° C before and after. On the other hand, the comparison test piece is 150 before extraction.
It was found that the test piece (6A) of the present invention had an improved heat resistance after extraction of 10 ° C. at 140 ° C. after extraction.

Further, when the thermal decomposition temperature (temperature at the time of 1% weight loss) of the above test piece (6A) and the test piece for comparison was measured with a thermogravimeter, the test piece (6A) of the present invention was Both before and after extraction were 460 ° C., whereas the comparative test piece had 460 ° C. before extraction and 430 ° C. after extraction, and therefore the thermal decomposition temperature of the test piece (6A) of the present invention after extraction was improved by 30 ° C. It turned out that

Example 7 Polycarbonate 10 was used as the polyester resin, and polydimethylsiloxane having an amino group at the end was used as the heat resistance improver.
Dry blending was performed in advance at a compounding ratio of 5 parts by weight to 0 parts by weight. This blended product was put into an extruder and melt-kneaded at 270 ° C., and a transesterification reaction was carried out by staying for about 10 minutes. Then, a resin plate having a thickness of about 1 mm was manufactured by extrusion molding into a plate shape from a mold of a molding machine, and this was cut to prepare a test piece (7).

For this test piece (7), the reaction rate of the transesterification reaction of polydimethylsiloxane was determined by the NMR spectrum method. First, the test piece (7) was dissolved in methylene chloride and reprecipitated with ether to remove unreacted polydimethylsiloxane in the test piece to obtain a purified test piece (7A).
Then, the reacted polydimethylsiloxane was quantified from the intensity of the peak due to the polydimethylsiloxane in the NMR spectrum of this test piece (7A). As a result, the reaction rate of polydimethylsiloxane was 50%.

Further, this test piece (7A) was subjected to a Soxhlet extraction test (ether) to examine the relationship between the extraction time and the residual ratio of polydimethylsiloxane. The results are shown in Table 3 below.

For comparison, a polycarbonate resin plate having a thickness of 1 mm, which was made to contain 2.5 parts by weight of polydimethylsiloxane without reacting with 100 parts by weight of the polycarbonate, was produced by a casting method, and cut to prepare it. Similarly, the relationship between the extraction time and the residual rate of polydimethylsiloxane was examined for the comparative test pieces. The results are shown in Table 3 below.

[0055]

[Table 3]

From Table 3, it can be seen that in the comparative test piece, almost all of the polydimethylsiloxane was extracted in 48 hours, whereas in the purified test piece (7A) of the present invention, polydimethylsiloxane had an ester bond. It can be seen that it is immobilized and not extracted with ether.

Further, the glass transition temperature of the test piece (7A) and the test piece for comparison were measured with a differential scanning calorimeter before and after extraction with ether for 48 hours.
(7A) was 150 ° C. both before and after extraction, whereas the comparative test piece had a decrease of 150 ° C. before extraction and 140 ° C. after extraction, and therefore the test piece (7A) of the present invention was It was found that the heat resistance was improved by 10 ° C.

Example 8 Polycarbonate as a polyester resin and thiodiphenol as a radiation resistant agent were preliminarily dry blended at a compounding ratio of 5 parts by weight with respect to 100 parts by weight of the polycarbonate. This blend is put into an extruder and melt-kneaded at 270 ° C.
A transesterification reaction was carried out with a residence time of 0 minutes. Then, a resin plate having a thickness of about 1 mm was manufactured by extrusion molding into a plate shape from a mold of a molding machine, and this was cut to prepare a test piece (8).

With respect to this test piece (8), the reaction rate of the transesterification reaction of thiodiphenol was determined by the infrared spectrum method. First, the test piece (8) was dissolved in methylene chloride and reprecipitated with methanol to remove unreacted thiodiphenol in the test piece for purification. Then, the reacted thiodiphenol was quantified from the intensity of the peak due to thiodiphenol in the infrared spectrum of this purified product. as a result,
The reaction rate of thiodiphenol was 30%.

[0060]

As is clear from the above description and the test results, the additive-containing resin molded article of the present invention has a long-term property because the additive is ester-bonded and fixed to the polymer molecules of the polyester resin. Almost never volatilize into
It has a remarkable effect that the performance of the additive can be maintained for a long period of time. Further, the production method of the present invention can be carried out by simply using a conventional general-purpose molding machine and adding a step of adding an additive before the molding and performing a transesterification reaction with the polymer molecules of the polyester resin in a heat-melted state. From
It is economical because there is no need to newly install a special molding machine or device, and it is possible to mass-produce molded products as efficiently as in the past.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing one embodiment of a manufacturing method of the present invention.

FIG. 2 is a molecular weight distribution curve of the blend of Comparative Example 1 by GPC.

FIG. 3 is a molecular weight distribution curve of the test piece (1) by GPC.

[Explanation of symbols]

 1 Extruder 5 Polyester resin 6 Additive 50 Resin molded product

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[Procedure amendment]

[Submission date] May 28, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Additives having a carboxyl group, a hydroxyl group, or an amino group at the terminal of the molecule are highly reactive, and there are some that cause a transesterification reaction without a catalyst, but an additive having an ester bond in the molecule is a catalyst. Some do not undergo the transesterification reaction without it, so when such an additive having poor reactivity is used, it is necessary to add a catalyst. As the catalyst, alkali metal carbonate (for example, potassium carbonate),
Lucari metal bicarbonate (eg sodium bicarbonate)
), Alkali metal oxides (eg sodium oxide)
), Alkali metal hydroxides (eg sodium hydroxide)
), Alkali metal carboxylates (eg sodium acetate)
Um), alkali metal alkoxides (eg, sodium
Mumethoxide), carbonates of alkaline earth metals (eg charcoal)
Calcium acid), oxides of alkaline earth metals (eg acid
Calcium hydroxide), hydroxides of alkaline earth metals (eg
Calcium hydroxide), carboxylate of alkaline earth metal
(Eg calcium acetate), alkaline earth metal alcohol
Xides (eg magnesium methoxide), of transition metals
Oxides (eg antimony trioxide), transition metal halogens
(Eg iron chloride), transition metal alkoxides (eg
For example, tetraethoxy titanium), inorganic acid (eg sulfuric acid),
A catalyst for transesterification such as sulfonic acid (eg P-toluenesulfonic acid) is used. These catalysts are added in an amount of 0.000 relative to 100 parts by weight of the polyester resin.
It is suitable to add at a ratio of 1 to 0.5 parts by weight.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display area C08K 5/09 5/17 KJX 7242-4J C08L 67/02 KJV 8933-4J // C09K 3/00 104 8517- 4H B29K 67:00 (72) Inventor Yoichiro Makimura 2-33-1 Azuchicho, Chuo-ku, Osaka Takiron Co., Ltd. (72) Hirofumi Takase 2-3-3 Azuchi-cho, Chuo-ku, Osaka Takiron Within the corporation

Claims (8)

[Claims] 1. A molded product made of a polyester resin contains an additive having a carboxyl group, a hydroxyl group or an amino group at the molecular end, or an additive having an ester bond in the molecule, and the additive is a polyester. An additive-containing resin molded article, which is characterized by having an ester bond through a transesterification reaction with a polymer molecule of a base resin. 2. The additive-containing resin according to claim 1, wherein the additive is an ultraviolet absorber having a carboxyl group, a hydroxyl group or an amino group at the terminal of the molecule, or an ultraviolet absorber having an ester bond in the molecule. Molding. 3. A benzophenone-based or benzotriazole-based UV absorber in which the additive has a carboxyl group, a hydroxyl group, or an amino group at the terminal of the molecule, or a benzophenone-based or benzotriazole-based UV light having an ester bond in the molecule. The additive-containing resin molded article according to claim 1, which is an absorbent and the polyester resin is polycarbonate. 4. The additive according to claim 1, wherein the additive is a heat resistance improver having a carboxyl group, a hydroxyl group, or an amino group at the terminal of the molecule, or a heat resistance improver having an ester bond in the molecule. Contains resin molded products. 5. An additive having a carboxyl group, a hydroxyl group or an amino group at the molecular end, or an additive having an ester bond in the molecule before the polyester resin is heated and melted to be molded into a predetermined shape. Is added to cause a transesterification reaction with the polymer molecules of the polyester resin in a heated and melted state. 6. The additive-containing resin according to claim 5, wherein the additive is an ultraviolet absorber having a carboxyl group, a hydroxyl group or an amino group at the terminal of the molecule, or an ultraviolet absorber having an ester bond in the molecule. Molded article manufacturing method. 7. A benzophenone-based or benzotriazole-based UV absorber, wherein the additive has a carboxyl group, a hydroxyl group, or an amino group at the molecular end, or a benzophenone-based or benzotriazole-based UV absorber having an ester bond in the molecule. The method for producing an additive-containing resin molded article according to claim 5, which is an absorbent and the polyester resin is polycarbonate. 8. The additive according to claim 5, wherein the additive is a heat resistance improver having a carboxyl group, a hydroxyl group or an amino group at the terminal of the molecule, or a heat resistance improver having an ester bond in the molecule. A method of manufacturing a resin-containing molded product.