JPH07145246A - Molded article of resin containing ultraviolet absorber and its production - Google Patents

Abstract

PURPOSE:To obtain a molded article of resin containing an ultraviolet absorber, which is solidified and does not vaporize, having excellent weather resistance for a long period of time, by transesterifying a specific ultraviolet absorber with a polymer molecule of a polyester-based resin in the presence of a transesterification catalyst to form ester bond. CONSTITUTION:In a molded article of a polyester-based resin containing (A) a benzotriazole-based or benzophenone-based ultraviolet absorber, preferably one having a molecular structure of formula I or II [R is (CH2)n, O(CH2)n, (OCH2CH2)n, etc.] such as 2-(2'-hydroxy-4'-hydroxyethoxyphenyl)benzotriazole or 2-hydroxy-4-hydroxyethoxybenzophenone and (B) an amine-based compound or a halide of a transition metal as a catalyst for transesterification, the component A and the polymer molecule of the polyester-based resin are subjected to ester bonding to give the objective molded article of the resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a molded article made of a polyester resin in which a benzotriazole-based or benzophenone-based ultraviolet absorber is contained so as not to volatilize and disappear, and weather resistance is greatly improved, and a production thereof. Regarding the method.

[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 mixed into the resin to prevent deterioration of the resin due to ultraviolet rays and improve weather resistance. I am trying to

[0003]

However, even if a conventionally used UV absorber is physically mixed into the polyester resin, the UV absorber does not chemically bond with the polymer molecules of the resin, There is a problem in that the ultraviolet absorber is easily volatilized and disappears during melting and molding of the resin, and is gradually volatilized and disappears even after molding. For this reason, the 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 were cases.

The present invention has been made in view of the above problems, and it is an object of the present invention to absorb ultraviolet rays having a small amount of volatilization and disappearance of the ultraviolet absorbent and to maintain the ultraviolet absorbing ability for a long period of time, which has extremely good weather resistance. An object is to provide an agent-containing polyester resin molded article and a method for producing the same.

[0006]

In order to achieve the above object, the ultraviolet absorbent-containing resin molded article of the present invention comprises a benzotriazole-based or benzophenone-based ultraviolet absorbent,
An amine compound or a halide of a transition metal is contained as a transesterification catalyst in a molded article made of a polyester resin, and the above-mentioned ultraviolet absorber is transesterified with a polymer molecule of the polyester resin to form an ester bond. In addition, the production method of the present invention, the above-mentioned ultraviolet absorber and the catalyst for transesterification are added before heating and melting the polyester resin to form a predetermined shape, and the above-mentioned ultraviolet absorption. It is characterized in that the agent is subjected to a transesterification reaction with a polymer molecule of a polyester resin in a heat-melted state.

And, preferably as an ultraviolet absorber,
Among the 2- (2'-hydroxyphenyl) benzotriazole derivatives, 3 ', 4'of the hydroxyphenyl group,
Use a derivative obtained by substituting hydrogen for 5 ′, 6 ′ or hydrogen for 3, 4, 5, 6 of benzene ring of benzotriazole group with a functional group having a hydroxyl group, or
Among the hydroxybenzophenone derivatives, 3, 4, 5, 6 hydrogens on the benzene ring or 2 ', 3', 4 ',
A derivative obtained by substituting any of 5'and 6'hydrogen with a functional group having a hydroxyl group is used.

[0008]

[Function] The benzotriazole-based or benzophenone-based UV absorber does not substantially cause a transesterification reaction when mixed alone with a polyester resin in a heat-melted state before molding, but a transesterification catalyst is added. Then, the benzotriazole-based ultraviolet absorber causes an ester exchange reaction at the ester bond portion of the polymer molecule of the polyester resin, and is ester-bonded and immobilized. This transesterification reaction is carried out by using 2- (2'-
Of the hydroxyphenyl) benzotriazole derivatives, 3 ', 4', 5 ', 6'hydrogen of the hydroxyphenyl group or the benzene ring of the benzotriazole group 3,
When a derivative obtained by substituting any one of hydrogens 4, 5, and 6 with a functional group having a hydroxyl group is used, or among the 2-hydroxybenzophenone derivatives, 3, 4 of the benzene ring,
The reaction rate becomes higher when a derivative obtained by substituting hydrogen of 5 or 6 or hydrogen of 2 ', 3', 4 ', 5', 6'with a functional group having a hydroxyl group is used. Then, the unreacted ultraviolet absorber is mixed in the polymer molecules in a dispersed state.

When the benzotriazole-based or benzophenone-based ultraviolet absorber is contained in the resin molded product in the state of being ester-bonded to the polymer molecule of the polyester resin as described above, the ultraviolet absorber is volatilized from the resin molded product, Although it does not disappear, if the transesterification catalyst is other than an amine compound or a transition metal halide, the reaction may be significantly reduced, or the reaction may cause yellowing. For example, when an alkali metal salt such as sodium methoxide is used as a transesterification catalyst, the reaction rate is high, but the ultraviolet absorber is affected by the alkali metal. The polyester resin molded product turns yellow. However, when an amine compound or a halide of a transition metal is used as a transesterification catalyst as in the present invention, it exhibits excellent ultraviolet absorbing ability for a long period of time without causing the above inconvenience at all, and yellowing occurs. It is possible to significantly improve the weather resistance by suppressing the above.

[0010]

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

FIG. 1 is a schematic explanatory view showing one embodiment of the manufacturing method of the present invention, and illustrates a case where a polyester resin is melt-extruded to manufacture a plate-shaped molded product (resin plate). is there.

In FIG. 1, 1 is a melt extrusion molding machine, 1a
Is a resin injection hopper provided at the rear of the molding machine, 1b is a hopper provided in the middle of the molding machine, 1c is a screw built into the molding machine, 1d is a molding die provided at the tip of the molding machine, and 2 is A pair of upper and lower cooling rolls, 3 is a conveyor belt, 4
Is 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 at the decomposition temperature). The following) is heated and melted, and kneaded with the screw 1c. Then, a mixture 6 of a benzotriazole-based or benzophenone-based ultraviolet absorber and a transesterification catalyst is added to the hopper 1 in the middle of the molding machine.
It is charged from b, is kneaded uniformly with the polyester resin 5 in a heated and molten state by the screw 1c, and is extrusion-molded into a plate shape from the mold 1d.

When the benzotriazole-based or benzophenone-based UV absorber and the transesterification catalyst are kneaded in this manner, the UV absorber causes a transesterification reaction at the ester bond portion in the polymer molecule of the polyester resin 5 to cause a molecular end. The UV absorber produces a polymer molecule with an ester bond. This transesterification reaction is performed in a state where the polyester resin 5 is melted.

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

In the ultraviolet absorbent-containing polyester resin plate (molded product) produced by the above method, the benzotriazole or benzophenone ultraviolet absorbent is immobilized by ester bonding to the end of the polymer molecule of the polyester resin. Therefore, it does not volatilize and disappear from the resin plate over time.

The polyester resin 5 as a raw material is preferably one having a relatively high melting temperature and easily causing a transesterification reaction. For example, a thermoplastic polyester such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate or polycaprolactone. A system resin is used.

As the ultraviolet absorber, one having a carboxyl group, a hydroxyl group or an amino group at the terminal of the molecule is used. Particularly, a benzotriazole having a molecular structure shown in the following [Chemical formula 1] is used. A system ultraviolet absorber or a benzophenone system ultraviolet absorber having a molecular structure as shown in the following [Chemical Formula 2] is preferably used.

[Chemical 1]

[Chemical 2]

That is, the ultraviolet absorber of [Chemical formula 1] is
Among the (2'-hydroxyphenyl) benzotriazole derivatives, 3 ', 4', 5'of the hydroxyphenyl group,
The 6'hydrogen or the benzene ring of the benzotriazole group is substituted with any of the hydrogens of 3, 4, 5 and 6 by a functional group -ROH having a hydroxyl group, and the ultraviolet absorber of [Chemical Formula 2] is Among 2-hydroxybenzophenone derivatives, 3, 4, 5, 6 hydrogens or 2'of the benzene ring,
Any of the hydrogens 3 ', 4', 5'and 6'is replaced by a functional group -ROH having a hydroxyl group. The benzotriazole-based UV absorber and the benzophenone-based UV absorber having such a molecular structure cause a transesterification reaction with the polymer of the polyester resin at a higher reaction rate than the UV absorbers having other molecular structures.

Particularly, R of the functional group is an alkylene chain, an alkylene oxide chain or a polyalkylene oxide chain as exemplified in [Chemical Formula 1] or [Chemical Formula 2], and the functional group -RO
A benzotriazole-based UV absorber in which H is attached to the 4-position carbon of the hydroxyphenyl group and a benzophenone-based UV absorber in which the functional group -ROH is attached to the 4-position carbon of the benzene ring are very suitably used. Specific examples of such a benzotriazole-based ultraviolet absorber include 2-
(2'-hydroxy-4'-hydroxyethoxyphenyl) benzotriazole, 2- (2'-hydroxy-
4'-hydroxymethoxyphenyl) benzotriazole and the like, and specific examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-hydroxyethoxybenzophenone and the like.

In the present invention, in addition to the above, it is also possible to use a benzotriazole-based or benzophenone-based ultraviolet absorber whose functional group is simply a hydroxyl group.

The above-mentioned benzotriazole-based or benzophenone-based ultraviolet absorbers are added to the polyester resin either alone or in an appropriate mixture, and the addition amount thereof is 0.01 with respect to 100 parts by weight of the polyester resin. ~ 1
It is desirable to set the ratio to 0.0 parts by weight. When the addition 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. On the other hand, when the amount is more than 10.0 parts by weight, the molecular weight of the polymer is remarkably reduced, and the commercial value is reduced.

On the other hand, as a transesterification catalyst, it is necessary to use an amine compound or a halide of a transition metal, and any other catalyst is not suitable for the present invention. When an amine compound or a halide of a transition metal is used as in the present invention, the transesterification rate becomes as high as 80% or more as shown in the experimental data described later, and therefore, a benzotriazole-based or benzophenone-based ultraviolet ray that forms an ester bond is used. Since the amount of absorbent increases, and these catalysts do not adversely affect the ultraviolet absorbent, it is possible to maintain excellent ultraviolet absorption ability for a long period of time, suppress yellowing and greatly improve weather resistance. Becomes On the other hand, if another catalyst such as an alkali metal salt such as sodium methoxide is used, the transesterification rate is high, but it is difficult for the UV absorber to exert sufficient UV absorbing ability due to the influence of the alkali metal. Therefore, there is a disadvantage that the polyester resin molded product is yellowed, which is not preferable.

As the transition metal halide, for example, tin chloride, zinc chloride, ferric chloride, lead chloride, etc. are used.
Among them, ferric chloride having the highest transesterification rate is particularly preferably used. As the amine compound, for example, triethylamine, trimethylamine or the like 3
A secondary amine such as a primary amine or dimethylamine is preferably used. These transesterification catalysts are added in an amount of 0.0005 to 0.
It is suitable to add 5 parts by weight.

The transesterification reaction between the polyester-based resin and the benzotriazole-based or benzophenone-based ultraviolet absorber occurs when the polyester-based resin is heated to a temperature not lower than the melting temperature and not higher than the decomposition temperature to be in the molten state as described above. . Therefore, when using, for example, a polycarbonate resin as the polyester resin, about 2
It may be heated to a temperature of 30 to 330 ° C. to be melted. The time required for the transesterification reaction varies somewhat depending on the type of the ultraviolet absorber, the type of the polyester resin, etc., but the reaction is completed in about 1 to 15 minutes. Therefore, when the resin plate is extruded as in the above-mentioned embodiment, the mixture 6 of the ultraviolet absorber and the transesterification catalyst is put into the molten polyester resin 5 inside the molding machine 1 and kneaded for about 1 to 15 minutes. After that, it is necessary to set the position of the intermediate hopper 1b, the screw design, and other extrusion conditions so that the resin is extruded from the mold 1d at the tip to sufficiently carry out the transesterification reaction. In that case, a twin-screw extruder or kneader is preferably used.

In the above-mentioned embodiment, the polyester resin 5 is introduced into the molding machine 1 from the hopper 1a and the mixture 6 of the ultraviolet absorber and the transesterification catalyst is introduced into the molding machine 1 from the hopper 1b. The polyester resin 5 and the mixture 6 may be added together, or the ultraviolet absorber and the catalyst may be added separately.

Further, in the above-mentioned embodiment, the molten polyester resin which has been transesterified with the ultraviolet absorber is used in the mold 1.
Although the resin plate is manufactured by extrusion molding from d as a single layer, it is needless to say that it is possible to manufacture extrusion molded products of various shapes such as a sheet, a film, and a modified product by changing the mold 1d. Using a coextrusion machine or the like, a molten polyester-based resin in which an ultraviolet absorber is ester-bonded is used as an upper layer, and a molten polyester-based resin or other resin containing less or no ultraviolet absorber than the upper layer is used as upper and lower layers. It is of course possible to produce a resin plate having a two-layer or three-layer structure in which a polyester resin layer containing an ultraviolet absorber is laminated on the surface by coextrusion molding into a layer or a three-layer structure.

Even in the case of injection molding, before injecting the molten polyester resin into the mold of the injection molding machine,
If a transesterification reaction is carried out by adding a benzotriazole-based or benzophenone-based ultraviolet absorber and a transesterification catalyst, it is possible to obtain a resin molded product in which the ultraviolet absorber is less volatile.

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

[Example 1] Polycarbonate as a polyester resin, 1.0 part by weight of 2- (2'-hydroxy-4'-hydroxyethoxyphenyl) benzotriazole as an ultraviolet absorber per 100 parts by weight of polycarbonate, ester As an exchange catalyst, triethylamine was preliminarily dry blended at a compounding ratio of 0.001 part by weight. The blended product was put into an extruder 27
A film having a thickness of 0.1 mm was obtained by heating at 0 ° C. for melt-kneading, carrying out transesterification reaction for about 3 minutes, and extruding from a mold of a molding machine. And the test piece (1) was created with this film.

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 80%.

Further, this test piece (1) was subjected to an accelerated weathering test to examine the relationship between the irradiation time, the residual ratio of the ultraviolet absorber and the degree of yellowing (ΔYI). The results are shown in Table 1 below. The accelerated weather resistance test was performed using a xenon weatherometer (manufactured by Atlas Co., Ltd.) for 100 hours and 500 hours.
Acceleration test by irradiation for 1,000 hours with Δh
Is measured by a Σ90 color measuring system (manufactured by Nippon Denshoku Co., Ltd.). Moreover, the residual ratio of the ultraviolet absorber is measured by a visible ultraviolet spectrophotometer UV-3100.
(Shimadzu Corporation) was used to measure the ultraviolet absorbance of the test piece at each irradiation time, and the absorbance change of the maximum absorption wavelength of the ultraviolet absorbent was calculated with the residual rate at irradiation time of 0 hr as 100. Is.

(Test method of reaction rate) Confirmation of reaction rate can be conducted by GP.
It is performed using a C (gel permeation chromatography) apparatus. Ultraviolet absorber 2- (2 ′) used in Example 1
The maximum ultraviolet absorption wavelength (λmax) of -hydroxy-4'-hydroxyethoxyphenyl) benzotriazole is
325 nm. Therefore, the polycarbonate and the catalyst blended with the ultraviolet absorber are matched with the detection wavelength of the ultraviolet detector of the GPC at 325 nm which is not detected in the measured sample concentration. For comparison with Example 1, as shown in Comparative Example 1 to be described later, the ultraviolet absorber of Example 1 was melt-kneaded with polycarbonate at the same compounding ratio without extrusion of a catalyst, and extrusion-molded. No transesterification reaction was performed. The film is used as a test piece (1 ') for comparison. This test piece (1 ')
The molecular weight distribution curve of GPC is 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. 3, and the peak (b) is the UV absorber of the UV absorber seen when the transesterification reaction is not carried out. Although it appears at the same elution time as the peak (a), the detection intensity decreases, and the attenuated peak (b) shifts to the peak (c) on the polymer side (left side of the horizontal axis). 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 the peak of a reaction part, (b) shows the peak of an unreacted part. The reaction rate is determined from the ratio of the sum of the areas of peak (b) and peak (c) to the area of peak (c) of the molecular weight distribution curve. Then, in order to remove the unreacted ultraviolet absorber, the test piece (1) prepared in Example 1 was purified, and the ultraviolet absorber was ester-bonded to the end by FT-IR, ¹ H-NMR, ¹³ C-NMR. Check that you are doing. 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, 1.0 part by weight of 2- (2'-hydroxy-4'-hydroxyethoxyphenyl) benzotriazole as an ultraviolet absorber per 100 parts by weight of a polycarbonate, a catalyst A test piece (2) was prepared in the same manner as in Example 1 except that the ferric chloride was dry blended in advance at a compounding ratio of 0.001 part by weight.

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 90%. Furthermore, about this test piece (2), Example 1
An accelerated weathering test was conducted in the same manner as in, and the relationship between the irradiation time and the residual rate of the ultraviolet absorber and the degree of yellowing (ΔYI) was examined. The results are shown in Table 1 below.

[Example 3] Polycarbonate as a polyester resin, 2-hydroxy- as an ultraviolet absorber
The same procedure as in Example 1 was performed except that dry blending was performed in advance at a compounding ratio of 1.0 part by weight of 4-hydroxyethoxybenzophenone to 100 parts by weight of polycarbonate and 0.001 part by weight of ferric chloride as a catalyst. To prepare a test piece (3).

With respect to this test piece (3), 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 90%. Furthermore, about this test piece (3), Example 1
An accelerated weathering test was conducted in the same manner as in, and the relationship between the irradiation time and the residual rate of the ultraviolet absorber and the degree of yellowing (ΔYI) was examined. The results are shown in Table 1 below.

Comparative Example 1 UV absorber 2- (2'-hydroxy-4'-hydroxyethoxyphenyl) benzotriazole was mixed in an amount of 1.0 part by weight per 100 parts by weight of the polycarbonate, and no transesterification catalyst was added. A comparative test piece (1 ′) was prepared from a film having a thickness of 0.1 mm extruded in Step 1. And this test piece (1 ')
Was subjected to an accelerated weathering test in the same manner as in Example 1 to investigate the relationship between the irradiation time, the residual ratio of the ultraviolet absorber and the degree of yellowing (ΔYI). The results are shown in Table 1 below.

[Comparative Example 2] A test piece for comparison was a 0.1 mm-thick film extruded by mixing 1.0 part by weight of an ultraviolet absorber 2-hydroxy-4hydroxyethoxybenzophenone with 100 parts by weight of polycarbonate. (2 ') was created.

Then, this test piece (2 ') was subjected to an accelerated weathering test in the same manner as in Example 1 to examine the relationship between the irradiation time, the residual ratio of the ultraviolet absorber and the yellowing degree (ΔYI). The results are shown in Table 1 below.

Comparative Example 3 100 parts by weight of a polycarbonate was mixed with 1.0 part by weight of the ultraviolet absorber 2-hydroxy-4hydroxyethoxybenzophenone and 0.001 part by weight of sodium methoxide as an ultraviolet absorber, followed by extrusion molding. A comparative test piece (3 ') was prepared from the film having a thickness of 0.1 mm.

With respect to this test piece (3 '), the reaction rate of the ultraviolet absorber was determined by the above-mentioned test method, and it was about 80%.
It was found that the ultraviolet absorber was transesterified at the reaction rate of. Further, this test piece (3 ') was subjected to the accelerated weathering test in the same manner as in Example 1 to examine the relationship between the irradiation time, the residual ratio of the ultraviolet absorber and the degree of yellowing (ΔYI). The results are shown in Table 1 below.

[0043]

[Table 1]

As shown in Table 1, a test piece for comparison (1 ') in which only a benzotriazole type ultraviolet absorber was mixed without using a transesterification catalyst and a comparative test piece in which only a benzophenone type ultraviolet absorber was mixed were used. Test piece (2 ')
Is an ultraviolet absorber that hardly forms an ester bond with the polymer molecule of the polycarbonate, and is easily volatilized over time.
It can be seen that the residual rate of the ultraviolet absorber after irradiation for 000 hours decreases to 69% or less, the deterioration of the test piece progresses, and the degree of yellowing increases to 3.9 or more. On the other hand, the test pieces (1) and (2) of the present invention in which a benzotriazole-based UV absorber and a transesterification catalyst (triethylamine, ferric chloride) are mixed, and a benzophenone-based UV absorber and a transesterification catalyst. In the test piece (3) of the present invention in which (ferric chloride) is mixed, most of the ultraviolet absorber is fixed by ester bond with the polymer molecule of polycarbonate, and the unreacted ultraviolet absorber volatilizes with time. Because it is only 100
The residual rate of the ultraviolet absorber after irradiation for 0 hours is as high as 93% or more, and the yellowing degree is as low as 2.1 or less, which shows that excellent weather resistance is maintained.

Further, a benzophenone type ultraviolet absorber,
The comparative test piece (3 '), in which sodium methoxide, which is not so preferable as a transesterification catalyst, was mixed and the ultraviolet absorber was ester-bonded, had a high reaction rate of 80%, and the ultraviolet absorption after irradiation for 1000 hours was high. The remaining rate of the agent is also 92
%, But it is difficult for the UV absorber to exert sufficient UV absorbing ability due to the influence of sodium methoxide.
It can be seen that the yellowing degree after irradiation for 1000 hours becomes relatively high at 2.9, and the deterioration of the test piece (3 ') progresses to some extent.

[0046]

As is clear from the above description and the test results, the ultraviolet absorbent-containing resin molded product of the present invention is produced by the benzoic acid reaction by the catalytic action of an amine compound or a transition metal halide added as a transesterification catalyst. Since the triazole-based or benzophenone-based UV absorber is immobilized by ester bond with the polymer molecules of the polyester resin at a high reaction rate, the UV absorber is less likely to volatilize with time, and the above catalyst absorbs UV light. Since it does not adversely affect the agent and lowers the ultraviolet absorption ability, it exerts a remarkable effect of maintaining excellent ultraviolet absorption ability for a long period of time and greatly improving weather resistance.

Further, in the production method of the present invention, various general-purpose molding machines have heretofore been used, and a benzotriazole-based or benzophenone-based ultraviolet absorber and a specific transesterification catalyst are added before molding to produce a polyester-based resin in a heat-melted state. Since it can be carried out only by adding a step of transesterification reaction with the polymer molecule of the resin, it is economical without the need to newly install a special molding machine or equipment, and mass-produces molded products with excellent weather resistance efficiently. It has the effect of being able to.

[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 a test piece (1 ′) for comparison by GPC.

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

[Explanation of symbols]

1 Extruder 5 Polyester Resin 6 Mixture of Benzotriazole or Benzophenone UV Absorber and Transesterification Catalyst 50 Resin Molded Product

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 67/02 KJT // C08L 67:00

Claims (4)

[Claims] 1. A benzotriazole-based or benzophenone-based ultraviolet absorber, and an amine compound or a transition metal halide as a transesterification catalyst are contained in a molded article made of a polyester resin, and the ultraviolet absorber is a polyester. An ultraviolet absorber-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 ultraviolet absorber is a 2- (2'-hydroxyphenyl) benzotriazole derivative having 3 ', 4', 5 ', 6'hydrogen of a hydroxyphenyl group or 3 of a benzene ring of a benzotriazole group. A derivative obtained by substituting any one of hydrogens of 4, 5, and 6 with a functional group having a hydroxyl group, or among the 2-hydroxybenzophenone derivatives, hydrogens of 3, 4, 5, 6 of the benzene ring or 2 '. The ultraviolet absorbent-containing resin molded article according to claim 1, which is a derivative obtained by substituting any of 3 ', 4', 5 ', and 6'hydrogen with a functional group having a hydroxyl group. 3. A benzotriazole-based or benzophenone-based UV absorber and an amine-based compound or a transition metal halide as a transesterification catalyst are added before a polyester-based resin is heated and melted to form a predetermined shape. ,
A method for producing an ultraviolet absorbent-containing resin molded article, which comprises subjecting the above ultraviolet absorbent to a transesterification reaction with polymer molecules of a polyester resin in a heat-melted state. 4. The ultraviolet absorber is a 2- (2'-hydroxyphenyl) benzotriazole derivative having 3 ', 4', 5 ', 6'hydrogen of a hydroxyphenyl group or 3 of a benzene ring of a benzotriazole group. A derivative obtained by substituting any one of hydrogens of 4, 5, and 6 with a functional group having a hydroxyl group, or among the 2-hydroxybenzophenone derivatives, hydrogens of 3, 4, 5, 6 of the benzene ring or 2 '. The method for producing an ultraviolet absorbent-containing resin molded article according to claim 3, which is a derivative obtained by substituting any of 3 ', 4', 5 ', and 6'hydrogen with a functional group having a hydroxyl group.