JPH1060125A - Preparation of additive-containing thermoplastic resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for preparing an additive-contg. thermoplastic resin molding which, in the preparation of a thermoplastic resin molding with an additive incorporated therein so as not to cause the volatilization of the additive by the transesterification of a polymer molecule of a thermoplastic resin with the additive, can significantly improve the rate of transesterification in a short time. SOLUTION: Before a thermoplastic resin wherein the polymer molecule has an ester bond or a carboxyl group is heat-melted and molded into a predetermined form, an additive having any one of an amino group, a hydroxyl group, a carboxyl group, and an ester bond is incorporated into the thermoplastic resin, followed by the transesterification of the polymer molecule of the thermoplastic resin in a heat-melted state with the additive in a carbon dioxide atmosphere. The plasticization effect, solvent effect, and catalytic effect attained by the carbon dioxide can markedly improve the rate of transesterification in a short time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermoplastic resin molded article containing various additives so as not to volatilize or exude.

[0002]

2. Description of the Related Art Molded articles such as exterior building materials molded with a thermoplastic resin are used by adding additives such as an ultraviolet absorber and an antifouling agent in order to improve weather resistance and stain resistance. ing.

[0003] However, the conventional additive-containing thermoplastic resin molded article is obtained by physically mixing and dispersing additives, so that the additives volatilize and disappear over time, and the weather resistance and the resistance to weathering are increased. It was difficult to maintain the contamination and the like for a long time.

Accordingly, the present inventors have focused on the transesterification reaction and prior to hot-melt molding the polyester resin, added an additive having any of an amino group, a hydroxyl group, a carboxyl group and an ester bond to the polyester resin. Mix
A method for producing an additive-containing resin molded article, which comprises subjecting a polymer molecule of a polyester resin in a heat-melted state to a transesterification reaction with an additive (Japanese Patent Application No. 5-128456).
No.) and further expand the application range of this method, and before heat-melting and molding a thermoplastic resin having an ester bond or a carboxyl group in the side chain of a polymer molecule, blending the same additives to carry out a transesterification reaction. A method for producing an additive-containing resin molded article (Japanese Patent Application No. 8-131201)
No.).

[0005] The resin molded article produced by these methods is:
Since the additive is immobilized by ester bond with the polymer molecule, the additive does not volatilize or exude over time, and the effect of the additive can be maintained for a long time.

[0006]

However, the above-mentioned production method is not so efficient in transesterification,
Even if an appropriate transesterification catalyst is added, the reaction rate cannot be increased unless the reaction time is extended, and there is room for improvement in this respect.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing an additive-containing thermoplastic resin molded article capable of greatly improving the transesterification reaction rate in a short time. .

[0008]

In order to achieve the above object, a method for producing an additive-containing thermoplastic resin molded article according to the present invention comprises heating and melting a thermoplastic resin having a polymer molecule having an ester bond or a carboxyl group. Before molding into a predetermined shape, an additive having an amino group, a hydroxyl group, a carboxyl group, or an ester bond is blended with the thermoplastic resin, and a polymer molecule of the thermoplastic resin in a heated and molten state in a carbon dioxide atmosphere. It is characterized by subjecting it to a transesterification reaction with an additive. The transesterification reaction is preferably performed in a pressurized carbon dioxide atmosphere, more preferably in a supercritical carbon dioxide atmosphere. Here, carbon dioxide in a supercritical state is
Carbon dioxide in a state of 31.1 ° C. or more and 73 atm or more.

When a polymer molecule of a thermoplastic resin and an additive are transesterified in a carbon dioxide atmosphere as in the production method of the present invention, even if an appropriate transesterification catalyst is not added, the experimental data described below will be obtained. As shown, the transesterification reaction rate is remarkably improved to 60% or more, and it is possible to obtain a thermoplastic resin molded article in which 60% or more of the additives are ester-bonded to the polymer molecules and fixed.

[0010] It is presumed that the remarkable improvement in the reaction rate when a transesterification reaction is performed in a carbon dioxide atmosphere as described above is due to a plasticizing effect, a solvent effect, and a catalytic effect of carbon dioxide.

The plasticizing effect of carbon dioxide means that carbon dioxide acts as a plasticizer for the thermoplastic resin and reduces the melt viscosity of the resin. It is thought that the transesterification reaction is promoted by increasing the chance of contact with the functional group.

The solvent effect of carbon dioxide refers to the ester bond portion of a polymer molecule or -CO of a carboxyl group.
Since O- and carbon dioxide have the same elemental composition, carbon dioxide gathers around the ester bond or carboxyl group and acts as a solvent, and the ester bond or carboxyl group reacts easily to form an ester. It is considered that the exchange reaction is promoted.

The catalytic effect of carbon dioxide is considered to be that carbon dioxide is converted to carbonic acid and acts as an acid catalyst to promote the transesterification reaction.

In the production method of the present invention, although the transesterification is remarkably improved as described above even when the transesterification reaction is carried out in a carbon dioxide atmosphere at normal pressure, the reaction is carried out in a pressurized carbon dioxide atmosphere. Then, carbon dioxide easily permeates between the polymer molecules of the thermoplastic resin, and the plasticizing effect, the solvent effect, and the catalytic effect by carbon dioxide are further promoted, so that the transesterification reaction rate is further improved. . In particular, when a transesterification reaction is performed in a carbon dioxide atmosphere in a supercritical state, carbon dioxide penetrates into the resin very quickly, so that a plasticizing effect, a solvent effect, and a catalytic effect are remarkably exhibited, and the transesterification reaction rate is reduced. It becomes even more remarkably improved.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic explanatory view showing one embodiment of the production method of the present invention, and illustrates a case where a plate-shaped molded article of a thermoplastic resin containing an additive is continuously extruded.

In FIG. 1, 1 is a melt extruder, 1a
Is a resin input hopper provided at the rear of the molding machine, 1b is an additive input hopper provided at an intermediate portion of the molding machine, 1c is a screw provided inside the molding machine, and 1d is a molding hopper provided at the tip of the molding machine. A mold, 1e is a carbon dioxide blowing port provided in an intermediate portion of the molding machine, 2 is a pair of upper and lower cooling rolls, 3 is a conveyor belt, and 4 is a cutter. As the molding machine 1, a twin-screw extruder capable of performing uniform kneading with two screws 1c is suitably used.

In this embodiment, a raw material thermoplastic resin 5 dried by preheating is introduced into the molding machine 1 from a hopper 1a at a rear portion of the molding machine, and the thermoplastic resin 5 is heated to a temperature higher than a melting temperature and lower than a thermal decomposition temperature. The mixture is kneaded with the screw 1c while being heated and melted. Then, the additive 6 is introduced from the hopper 1b in the middle part of the molding machine, and the thermoplastic resin 5 in the heated and molten state and the additive 6 are uniformly kneaded with the screw 1c while blowing carbon dioxide through the carbon dioxide blowing port 1e. Then, after a transesterification reaction in a carbon dioxide atmosphere, the mixture is extruded into a plate shape from the die 1d at the tip, and the plate-shaped formed body 50 is taken out and conveyed while being cooled by a pair of upper and lower cooling rolls 2 and 2. Is conveyed to the cutting machine 4 by the use belt 3 and cut into a predetermined length.

Any thermoplastic resin 5 can be used as long as it has an ester bond or a carboxyl group in the main chain or side chain of the polymer molecule and can undergo a transesterification reaction with the additive 6. Illustrative examples thereof include, as the thermoplastic resin having an ester bond or a carboxyl group in the main chain of the polymer molecule, polyester resins such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone, and polylactide. No. Examples of the thermoplastic resin having an ester bond or a carboxyl group in the side chain of the polymer molecule include polyacrylic acid, polymethacrylic acid, their alkyl esters (methyl ester, ethyl ester, propyl ester, etc.), maleated polyethylene, maleic Polystyrene, polyvinyl acetate and the like.

On the other hand, the additive 6 can be used as long as it has an amino group, a hydroxyl group, a carboxyl group, or an ester bond at the molecular terminal or in the molecule and can transesterify with the thermoplastic resin. What is possible is to select and use various materials that can impart the required effect to the intended thermoplastic resin molded article. The amount of the additive 6 may be appropriately determined so that the effect is sufficiently exhibited.

As a typical example of the additive 6, when contamination resistance is required for a thermoplastic resin molded article, an amino group is added to both ends of the molecule represented by the following structural formula. A polydimethylsiloxane having an amino group in the molecule represented by the following formula [Chemical Formula 2], a polydimethylsiloxane having a carboxyl group at one terminal of a molecule represented by the following Chemical Formula 3] Dimethylsiloxane, a polydimethylsiloxane having hydroxyl groups at both molecular terminals represented by the following structural formula [Chemical formula 4],
An antifouling agent of a silicon compound such as polydimethylsiloxane having ester groups at both ends of the molecule represented by the structural formula
An antifouling agent of a fluorine-based compound such as fluorinated bisphenol A [2,2-bis- (4-hydroxyphenyl) -hexafluoropropane] having hydroxyl groups at both molecular ends is exemplified.

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When these silicone-based or fluorine-based antifouling agents are blended at a ratio of 0.1 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin and are ester-bonded to polymer molecules, the resin molded article can be favorably formed. By imparting excellent water repellency, excellent stain resistance can be maintained for a long period of time. In some cases, polydimethylsiloxane having no functional group and represented by the following structural formula [Chemical Formula 6], fluorocarbon, or the like may be used in combination with the above antifouling agent.

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When the thermoplastic resin molded article is required to have weather resistance, the additive 6 may be 2- (2'-hydroxy-5'-carboxyphenyl) benzotriazole having a carboxyl group at the molecular terminal, 2-hydroxybenzophenone-4-oxyacetic acid, or 2-hydroxy-4- (2'-hydroxyethoxy) benzophenone having two or more hydroxyl groups at molecular terminals, 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 2- (2'-hydroxy-3'-amino-5'-t-butyl) benzotriazole having an amino group at the molecular terminal, or an ester in the molecule 2-hydroxy-4- (2'-methacryloyloxyethoxy) benzophenone having a group, 2,4-di-t-butylphenyl-
(3 ', 5'-di-t-butyl-4'-hydroxy) benzophenone, methyl 2-hydroxybenzophenone-4-oxyacetate, 2- (2'-acryloyloxy-
An ultraviolet absorber of a 2-hydroxybenzotriazole derivative or a 2-hydroxyphenylbenzophenone derivative such as 5'-methyl) benzotriazole is preferably used.

These ultraviolet absorbers are thermoplastic resins 1
When it is blended in an amount of 0.01 to 5 parts by weight with respect to 00 parts by weight and ester-bonded to the polymer molecule, deterioration of the molded article due to ultraviolet rays can be suppressed, and excellent weather resistance can be maintained for a long time.

In addition, depending on the effect required for the thermoplastic resin molded article, a flame retardant such as tetrabromobisphenol, a radiation-resistant agent such as thiodiphenol, and an antioxidant such as N, N-diphenyl-p-phenylenediamine. Various additives can be used, such as an antimicrobial agent, an antibacterial agent such as tributyltin laurate, an antistatic agent such as tetraphenyldipropylene glycol diphosphite, and a plasticizer such as dioctyl phthalate and dodecanol.

Among the above-mentioned additives 6, a bifunctional additive having a functional group at both ends of the molecule is selectively used, and a thermoplastic resin 5 having an ester bond or a carboxyl group in a side chain of a polymer molecule is used. When the transesterification reaction is selectively performed, the polymer molecules of the thermoplastic resin have a structure three-dimensionally cross-linked by a bifunctional additive ester-bonded to the side chain. Physical properties, especially heat resistance, are significantly improved.

The transesterification reaction between the thermoplastic resin 5 and the additive 6 occurs in an air atmosphere or a nitrogen atmosphere. However, when the transesterification reaction is performed in a carbon dioxide atmosphere by blowing carbon dioxide as in this embodiment, the transesterification reaction is already performed. As described above, the transesterification reaction is remarkably promoted by the plasticizing effect, the solvent effect and the catalytic effect of carbon dioxide, and the reaction rate is 60 at normal pressure (1 atm) without adding an appropriate transesterification catalyst.
% Or more.

In this case, when the pressure of carbon dioxide is increased and transesterification is performed in this pressurized carbon dioxide atmosphere, carbon dioxide easily penetrates between the polymer molecules of the thermoplastic resin, and plasticization by carbon dioxide is performed. Since the effect, the solvent effect, and the catalytic effect are further promoted, the reaction rate is further improved. In particular, when a transesterification reaction is carried out in a carbon dioxide atmosphere in a supercritical state, carbon dioxide penetrates into the thermoplastic resin very quickly, so that the transesterification reaction rate is further remarkably improved. Further, it is preferable to add an appropriate transesterification catalyst since the transesterification reaction is promoted and the reaction rate is further improved. As the transesterification catalyst, Lewis acids (eg, iron chloride, cobalt acetate), tertiary amines (eg, trimethylamine) and the like are preferably used. These catalysts are used in thermoplastic resins 10
It is appropriate to mix it in a ratio of 0.001 to 0.5 part by weight with respect to 0 part by weight, and if it is added in a larger amount, there arises a disadvantage that the resin molded body 50 is colored.

The transesterification reaction rate varies somewhat depending on the type of the thermoplastic resin and the type of the additive, but is usually 1 to 3.
The reaction is almost completed in about 15 minutes. Therefore, when extruding by performing a transesterification reaction inside the molding machine 1 as in this embodiment, the additive 6 is charged into the molding machine 1 and kneaded with the thermoplastic resin 5 for about 1 to 15 minutes. Later mold 1d
It is important to set the position of the additive hopper 1b, the screw design, and other extrusion conditions so that the transesterification reaction is sufficiently performed so that the transesterification reaction is sufficiently performed.

The thermoplastic resin molded article 50 obtained by the above-described production method of the present invention has a high transesterification reaction rate, so that most of the additives contained are immobilized by ester bonding to polymer molecules. Since the additive thus immobilized does not volatilize or exude over time, the efficacy of the additive can be maintained for a long period of time. Moreover, when a transparent thermoplastic resin molded article is produced by this method, the additives are finely dispersed at the molecular level by ester bonds, and the particles of the additives do not secondary aggregate as in the case of physically dispersing. Even if the additive particles and the thermoplastic resin have different optical refractive indices, the transparency of the molded article hardly decreases due to the refraction and scattering of transmitted light, and it is very different from the molded article made of a transparent resin alone. No good transparency can be maintained.

In the embodiment illustrated in FIG. 1, the thermoplastic resin 5 and the additive 6 are separately charged into the molding machine 1 from the hoppers 1a and 1b. Alternatively, a mixture of both may be charged from the hopper 1b in appropriate amounts, and the charging method can be appropriately selected. Further, in this embodiment, the plate-like molded body 50 is manufactured by extruding the molten thermoplastic resin in which the additives are ester-bonded in a single layer from the mold 1d. Of course, it is possible to produce molded articles of various shapes such as films, irregularly shaped articles, and further, using a co-extrusion molding machine or the like, forming an upper layer of a molten thermoplastic resin in which additives are ester-bonded, and adding from the upper layer. A two- or three-layer plate-like molded product obtained by co-extrusion of a molten thermoplastic resin containing little or no additives into upper and lower two or three layers and laminating a thermoplastic resin layer containing additives on the surface It is of course possible to produce Also, in the case of injection molding, if the additives are mixed and transesterified before the molten thermoplastic resin is injected into the mold of the injection molding machine, the additives are similarly fixed to the polymer molecules. A molded product that does not volatilize can be obtained.

[0032]

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

Example 1 As a thermoplastic resin, polymethyl methacrylate having an ester bond in a side chain (PM
MA) as an additive, and a silicone-based antifouling agent, polydimethylsiloxane (PDMS) having amino groups at both ends, at a ratio of 2.0 parts by weight. It was put into a molding machine. Then, the mixture is melt-kneaded at 230 ° C. for 20 minutes to perform transesterification while blowing carbon dioxide at 3 atm into the twin-screw extruder, and is extruded into a plate shape from the mold of the molder and molded. I got a body.

The molded body was cut and dissolved in a solvent (dichloromethane), and the solution was cast to prepare a test film having a thickness of 50 μm.

For this test film, the transesterification rate of the PDMS was determined by the following method. As shown in Table 1 below, the amount of the transesterified PDMS was 1.25 parts by weight. And the reaction rate is 6
2.6%.

(Testing Method of Transesterification Reaction Rate)
After dissolving the test film in dichloromethane and precipitating with diethyl ether to remove unreacted PDMS,
The sample was filtered and dried to obtain a sample. Then, the ¹ H NMR spectrum of a heavy chloroform solution of the sample was measured, and the
PD transesterified based on the proton intensity of CH ₃
The amount of MS was calculated, and the reaction rate was calculated from the following equation [Equation 1].

(Equation 1)

Example 2 As a thermoplastic resin, polymethyl methacrylate having an ester bond in a side chain (PM
MA) as an additive, and a silicone-based antifouling agent, polydimethylsiloxane (PDMS) having amino groups at both ends, at a ratio of 2.0 parts by weight. It was put into a molding machine. Then, a test film of Example 2 was obtained in the same manner as in Example 1, except that carbon dioxide at 80 atm was blown into the twin-screw extruder.

When the transesterification rate of this test film was determined in the same manner as in Example 1, it was as high as 85.0%, as shown in Table 1 below.

Comparative Examples 1 to 3 The test film of Comparative Example 1 (thickness: 50 μm) was prepared in the same manner as in Example 1 except that nitrogen gas was blown into the twin screw extruder instead of carbon dioxide.
Was prepared. Further, a test film (thickness: 50 μm) of Comparative Example 2 was produced in the same manner as in Example 1, except that air at 3 atm was blown into the twin-screw extruder instead of carbon dioxide. Further, a test film (thickness: 50 μm) of Comparative Example 3 was produced in the same manner as in Example 1 except that no gas was blown into the twin-screw extruder.

The transesterification rates of the test films of Comparative Examples 1 to 3 were determined in the same manner as in Example 1. The results are as shown in Table 1 below.

[Table 1]

Referring to Table 1, the test films of Comparative Examples 1 and 2 were subjected to transesterification by blowing nitrogen gas or air instead of carbon dioxide, and the transesterification reaction was conducted without blowing any gas. Each of the test films of Comparative Example 3 had a transesterification reaction rate of PDMS of 20%.
Below is a low rate. This is because no transesterification catalyst was used.

On the other hand, in the test film of Example 1 in which carbon dioxide was blown and the transesterification reaction was performed, the transesterification rate of PDMS was 62.6% even though the transesterification catalyst was not used. It can be seen that the transesterification reaction was remarkably promoted by the plasticizing effect, the solvent effect and the catalytic effect of carbon dioxide.

The test film of Example 2 in which carbon dioxide was blown at 80 atm and the transesterification reaction was performed, the transesterification rate was further improved to 85.0%, and the supercritical state (80 atm. It can be seen that the transesterification rate becomes very high with carbon dioxide at 230 ° C).

Examples 3 and 4 100 parts by weight of polymethyl methacrylate (PMMA) as a thermoplastic resin, 2.0 parts by weight of polydimethylsiloxane (PDMS) having amino groups at both molecular ends as additives, and transesterification A test film (thickness: 50 μm) of Example 3 was produced in the same manner as in Example 1, except that 0.00331 parts by weight of iron chloride (FeCl ₃ ) was mixed as a catalyst.

Then, a test film (thickness: 50 μm) of Example 4 was prepared in the same manner as above except that the amount of iron chloride was changed to 0.05 part by weight.

With respect to the test films of Examples 3 and 4, the transesterification rate of PDMS was determined in the same manner as in Example 1. As shown in Table 2 below, the test films of Example 3 were obtained. Was 92.6%, and the test film of Example 4 was an extremely high rate of 98.6%.

Comparative Examples 4 and 5 100 parts by weight of polymethyl methacrylate (PMMA) as a thermoplastic resin, 2.0 parts by weight of polydimethylsiloxane (PDMS) having amino groups at both molecular ends as an additive, and transesterification The test film of Comparative Example 4 was prepared in the same manner as in Example 1 except that 0.00331 parts by weight of iron chloride (FeCl ₃ ) was mixed as a catalyst, and nitrogen gas at 3 atm was blown in instead of carbon dioxide. (Thickness: 50 μm).

Then, a test film (thickness: 50 μm) of Comparative Example 5 was prepared in the same manner as above except that the amount of iron chloride was changed to 0.05 part by weight.

For the test films of Comparative Examples 4 and 5, the transesterification rate of PDMS was determined in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Examples 6 and 7 100 parts by weight of polymethyl methacrylate (PMMA) as a thermoplastic resin, 2.0 parts by weight of polydimethylsiloxane (PDMS) having amino groups at both molecular ends as additives, and transesterification The same procedure as in Example 1 was repeated except that 0.00331 parts by weight of iron chloride (FeCl ₃ ) was mixed as a catalyst and air at 3 atm was blown in instead of carbon dioxide. (Thickness: 50 μm).

Then, a test film (thickness: 50 μm) of Comparative Example 7 was prepared in the same manner as described above except that the amount of iron chloride was changed to 0.05 part by weight.

For the test films of Comparative Examples 6 and 7, the transesterification rate of PDMS was determined in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Examples 8 and 9 100 parts by weight of polymethyl methacrylate (PMMA) as a thermoplastic resin, 2.0 parts by weight of polydimethylsiloxane (PDMS) having amino groups at both molecular ends as an additive, and transesterification Comparative Example 8 was carried out in the same manner as in Example 1 except that 0.00331 parts by weight of iron chloride (FeCl ₃ ) was mixed as a catalyst, and no gas was blown into the twin-screw extruder.
The test film (thickness: 50 μm) was prepared.

Then, a test film (thickness: 50 μm) of Comparative Example 9 was prepared in the same manner as described above except that the amount of iron chloride was changed to 0.05 part by weight.

For the test films of Comparative Examples 8 and 9, the transesterification rate of PDMS was determined in the same manner as in Example 1 and the results are shown in Table 2 below.

[Table 2]

Comparing Table 2 with Table 1 above, the addition of a catalyst (iron chloride) drastically accelerated the transesterification reaction of PDMS in any of the test films, and Example 4 containing a large amount of the catalyst was added. The test films of Comparative Examples 5, 7, and 9 are less than those of Example 3, Comparative Example 4,
The reaction rate is higher than that of the test films of Nos. 6 and 8.

However, even when the catalyst addition amount was as large as 0.05 parts by weight, the test films of Comparative Examples 5 and 7 in which a transesterification reaction was performed by blowing nitrogen gas or air, or the ester film was blown without blowing any gas. The test films of Comparative Example 9 subjected to the exchange reaction all had a reaction rate of about 70%, whereas the test films of Example 4 in which the transesterification reaction was carried out by blowing carbon dioxide had a reaction rate of 98. As a result, it is possible to know how effective carbon dioxide is in promoting the transesterification reaction.

Example 5 100 parts by weight of polymethyl methacrylate (PMMA) as a thermoplastic resin, 2.0 parts by weight of polydimethylsiloxane (PDMS) having amino groups at both molecular ends as additives, and a transesterification catalyst A thickness of 70 μm was obtained in the same manner as in Example 1 except that iron chloride (FeCl ₃ ) was mixed at a ratio of 0.00331 parts by weight.
m of test films were prepared. This test film was different from the test film of Example 3 only in thickness, and the transesterification rate of PDMS was
92.6%, which is the same as that of the test film.

For this test film, 550 nm
Was measured and found to be 87% as shown in Table 3 below. Further, this test film was immersed in a blue-black ink for office use at room temperature,
When the light transmittance at 550 nm after immersion for a week was measured,
As shown in Table 3 below, the light transmittance was 82%.

Comparative Examples 10 to 12 100 parts by weight of polymethyl methacrylate (PMMA) as a thermoplastic resin, 2.0 parts by weight of polydimethylsiloxane (PDMS) having amino groups at both molecular ends as an additive, and transesterification 0.00331 of iron chloride (FeCl ₃ ) as a catalyst
A test film (thickness: 70 μm) of Comparative Example 10 was produced in the same manner as in Example 1 except that the components were mixed at a ratio of parts by weight and no gas was blown into the twin-screw extruder. This test film was different from the test film of Comparative Example 8 only in thickness, and the transesterification reaction rate of PDMS was the same as the test film of Comparative Example 8: 55.0.
%.

Also, 100 parts by weight of PMMA, PDMS
Was mixed at a ratio of 2.0 parts by weight, and this mixture was dissolved in dichloromethane and cast to prepare a test film (thickness: 70 μm) of Comparative Example 11 in which PDMS was physically dispersed. did.

Further, by dissolving PMMA in dichloromethane and casting the same, PDMS is obtained.
Of the test film of Comparative Example 12 containing no
m) was prepared.

For the test films of Comparative Examples 10 to 12, 550 nm before immersion in blue black ink and after immersion for 2 weeks in the same manner as in Example 5.
Was measured for light transmittance. The results are shown in Table 3 below.

[Table 3]

As can be seen from Table 3, the PMMA of Comparative Example 12
The single test film has a high light transmittance of 90% before immersion in blue-black ink and is excellent in transparency.
Since DMS is not contained at all, the light transmittance after immersion in the blue black ink is significantly reduced to 50%, which indicates that the stain resistance is poor.

The test film of Comparative Example 11 in which PDMS was physically dispersed had poor PDMS dispersibility.
The light transmittance before immersion in the blue black ink is as low as 30% because of the secondary aggregation, and the light transmittance after immersion in the blue black ink is further reduced by 10% because the PDMS is not fixed. 20%, which indicates that the transparency and the stain resistance are inferior.

On the other hand, by transesterification reaction, PDMS
In the test film of Example 5 and the test film of Comparative Example 10 in which was ester-bonded to a polymer molecule, the PDMS having the ester bond was dispersed at the molecular level.
Compared to the test film of Comparative Example 11 in which MS was physically dispersed, the light transmittance was significantly improved. However, the test film of Comparative Example 10 in which transesterification was performed without blowing any gas, the reaction rate was as low as 55%, and the PD was low.
Nearly half of the MS is dispersed in the film unreacted, so that the light transmittance before immersion in the blue-black ink is 7%.
5%, which is not so high, the light transmittance after immersion in the blue black ink is reduced to 68%, and both the transparency and the stain resistance are unsatisfactory.

On the other hand, in the test film of Example 5 in which the transesterification reaction was performed while blowing carbon dioxide by the production method of the present invention, the reaction rate was extremely high at 92.6%, and 90% or more of the PDMS was a molecule. Since the particles were finely dispersed and fixed at a level, the light transmittance before immersion in the blue-black ink was as high as 87%, and Comparative Example 12 of PMMA alone was used.
And the light transmittance after immersion in blue-black ink was 8%.
It maintains a high value of 2%, which indicates that both the transparency and the stain resistance are good.

Example 6 A test film was produced in the same manner as in Example 5, except that the thickness of the film was changed from 70 μm to 20 μm.

The contact angle of the surface of this test film was measured and found to be 84 ° as shown in Table 4 below.
Met. Next, the test film was immersed in dimethyl ether, allowed to stand at room temperature for 15 hours, and the contact angle of the surface was measured again. As shown in [Table 4] below, 8
4 °, no change.

[Comparative Examples 13 to 15] The film thickness was 7
Comparative Examples 10 to 12 except that 0 μm was changed to 20 μm.
Similarly, the transesterification rate of PDMS was 55%.
The test film of Comparative Example 13, the test film of Comparative Example 14, in which PDMS was physically dispersed, and the test film of Comparative Example 15, which contained only PMMA without PDMS, were produced.

The contact angles of the surfaces of the test films of Comparative Examples 13 to 15 before and after immersion in dimethyl ether were measured in the same manner as in Example 6. The results are shown in [Table 4] below.

[Table 4]

Referring to Table 4, the PMMA of Comparative Example 15
Since the test film alone does not contain any PDMS, the contact angle before and after immersion in dimethyl ether is 70.
° and 71 °, indicating that the water repellency is not very good.

On the other hand, the test films of Example 6 and Comparative Examples 13 and 14 containing PDMS had the same PDMS content before immersion in dimethyl ether. 85 °, indicating good water repellency. However, when immersed in dimethyl ether, the test film of Comparative Example 14 in which PDMS was physically dispersed showed that the contact angle after immersion was lower than that of Comparative Example 15 in which PMMA alone was used because the PDMS in the surface layer was eluted in dimethyl ether. 71 °, which is the same as that of the film for use, and the water repellency is greatly reduced. In the test film of Comparative Example 13 having a low transesterification reaction rate of 55%, about half of the unreacted PDMS contained in the surface layer is eluted in dimethyl ether. It decreases to 76%, and the water repellency becomes insufficient.

On the other hand, carbon dioxide was blown into 9
The test film of Example 6 subjected to transesterification at a high rate of 2.6% had a very small amount of unreacted PDMS eluted even when immersed in dimethyl ether.
Since the DMS content does not decrease, the contact angle after immersion is 84 °, which is the same as the contact angle before immersion, which indicates that good water repellency is maintained.

Examples 7 to 9 100 parts by weight of a polycarbonate (PC) having an ester bond in the main chain as a thermoplastic resin, and 2-hydroxy-5- (a benzotriazole ultraviolet absorber as an additive) 2'-hydroxyethyl) benzotriazole (HHEBT)
The mixture was mixed at a ratio of 0 parts by weight, and the mixture was charged into a twin-screw extruder. Then, while blowing carbon dioxide at 3 atm into the twin screw extruder, the above mixture is melt-kneaded at 255 ° C. for 10 minutes to cause a transesterification reaction, and then extruded into a plate shape from the mold of the extruder to be formed. I got a body.

This molded product was cut and dissolved in a solvent (dichloromethane), and this solution was cast to prepare a test film (thickness: 50 μm) of Example 7.

100 parts by weight of the above PC as a thermoplastic resin, 1.0 part by weight of the above HHEBT as an additive,
A test film (thickness: 50 μm) of Example 8 was produced in the same manner as above, except that 0.01 parts by weight of cobalt acetate was mixed as a transesterification catalyst. Further, the amount of cobalt acetate added was changed to 0.0498 parts by weight, and the transesterification reaction time was changed to 5 minutes.
The test film (thickness: 50 μm) was prepared.

For the test films of Examples 7 to 9, the transesterification rate of HHEBT was determined by the following method. The results were as shown in [Table 5] below.

(Testing method of reaction rate of transesterification reaction)
The test film was dissolved in dichloromethane and precipitated with methanol to remove unreacted HHEBT, and then filtered and dried to obtain a sample. Then, the ¹ H NMR spectrum of the deuterated chloroform solution of the sample was measured, and from the intensity of the signal of the proton of the hydroxyl group bonded to the carbon at the 2-position, the amount of the transesterified HHEBT was calculated. ] To determine the reaction rate.

(Equation 2)

Comparative Examples 16 to 18 Tests for Comparative Examples 16 to 18 were carried out in the same manner as in Examples 7 to 9 except that the transesterification reaction was carried out without blowing any gas into the twin-screw extruder. A film (thickness: 50 μm) was produced.

For the test films of Comparative Examples 16 to 18, the transesterification rate of HHEBT was determined in the same manner as in Examples 7 to 9, and the results are shown in Table 5 below.

[Table 5]

As can be seen from Table 5, the test film of Comparative Example 16 in which the transesterification was carried out without blowing any gas had no HHEBT reaction rate of only 7.6.
%, Whereas the test film without catalyst added in Example 7 in which carbon dioxide was blown to cause a transesterification reaction had a HHEBT conversion of 71.6%, a plasticizing effect of carbon dioxide, a solvent It can be seen that the transesterification reaction is remarkably promoted by the effect and the catalytic effect.

Then, cobalt acetate was used as a catalyst in 0.0
When 1 part by weight was added, the test film of Comparative Example 17 subjected to the transesterification reaction without blowing any gas was HH
While the reaction rate of EBT only increased to 50%, the test film of Example 8 in which the transesterification reaction was performed by blowing in carbon dioxide, the reaction rate of HHEBT was 9%.
The improvement is astoundingly 8.6%. Further, when the amount of cobalt acetate added was increased to 0.498 parts by weight, the test film of Example 9 in which carbon dioxide was blown and the transesterification reaction was performed, the reaction rate of HHEBT was reduced even when the reaction time was reduced to 5 minutes. Is 83.2%, which is about 21% higher than that of the test film of Comparative Example 18 in which transesterification was performed without blowing any gas. These results also indicate that carbon dioxide is extremely effective for the transesterification reaction.

Example 10 100 parts by weight of the above-mentioned PC as a thermoplastic resin, 1.0 part by weight of the above-mentioned HHEBT as an additive, and 0.01 part by weight of the above-mentioned cobalt acetate as a transesterification catalyst. After mixing, a test film having a thickness of 100 μm was prepared in the same manner as in Example 7. This test film is different from the test film of Example 8 only in the thickness, and the transesterification rate of HHEBT is 98.6%, which is the same as that of the test film of Example 8.

The test film was subjected to an accelerated weathering test for one month using a xenon weatherometer, and the degree of yellowing (ΔYI) was measured using a # 90 color measuring system (manufactured by Nippon Denshoku Co., Ltd.). , As shown in Table 6 below.

Comparative Examples 19 to 21 100 parts by weight of the above-mentioned PC as a thermoplastic resin and the above-mentioned HHE as an additive
As in Example 7, except that 1.0 part by weight of BT and 0.01 part by weight of the above-mentioned cobalt acetate as a transesterification catalyst were mixed and transesterified without blowing any gas, The test film of Comparative Example 19 (thickness 1
00 μm). This test film is different from the test film of Comparative Example 17 only in the thickness, and the transesterification reaction rate of HHEBT is 50.0%, which is the same as the test film of Comparative Example 17.

A comparative example in which HHEBT was physically dispersed by mixing 100 parts by weight of PC and 1.0 part by weight of HHEBT, dissolving the mixture in dichloromethane, and casting the mixture was used. Twenty test films (thickness: 100 μm) were prepared.

Further, by dissolving PC in dichloromethane and casting the same, the test film (thickness: 1) of PC alone containing no HHEBT was used.
00 μm).

The accelerated weathering test for one month was performed on the test films of Comparative Examples 19 to 21 in the same manner as in Example 10, and the yellowing degree (ΔYI) was measured. The results are shown in Table 6 below. .

[Table 6]

Looking at Table 6, it can be seen that Comparative Example 21 using only PC was used.
Has a large yellowing degree (ΔYI) of 6.0 and is inferior in weather resistance, and the test film of Comparative Example 20 in which HHEBT is physically dispersed is also used for one month. Because HHEBT volatilizes considerably, the degree of yellowing (ΔYI)
Is relatively large at 4.0, indicating that the weather resistance is insufficient.

On the other hand, although the test films of Example 10 and Comparative Example 19 in which HHEBT was immobilized by a transesterification reaction exhibited a decrease in the degree of yellowing (ΔYI), the test film of Comparative Example 19 was the same as that of HHEBT. Since half are unreacted, the decrease in the degree of yellowing (ΔYI) is small, and it is hard to say that it has good weather resistance. On the other hand, the test film of Example 10 in which carbon dioxide was blown and the transesterification reaction was performed at a high conversion of 98.6% was obtained by using HHE.
Since the volatilization of BT is almost zero, the degree of yellowing (ΔYI) is remarkably reduced to 1.4, indicating that the BT has excellent weather resistance.

[0092]

As is apparent from the above description, the method for producing an additive-containing thermoplastic resin molded article of the present invention is carried out in an atmosphere of carbon dioxide, which is extremely effective for a transesterification reaction, before heat-melt molding. The transesterification reaction between the polymer molecules of the thermoplastic resin in the heat-melted state and the additives makes it possible to remarkably improve the reaction rate of the transesterification reaction, whereby most of the contained additives are of the thermoplastic resin. It has a remarkable effect that it is possible to easily produce a molded article in which the effect duration of the additive is extremely long, which is immobilized in an ester bond with the polymer molecule and immobilized so as not to be volatilized.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing one embodiment of a method for producing an additive-containing thermoplastic resin molded article of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Extrusion molding machine 1e Carbon dioxide injection port 5 Thermoplastic resin 6 Additive 50 Additive-containing thermoplastic resin molded body

Claims (3)

[Claims] An amino group, a hydroxyl group, a carboxyl group, a thermoplastic resin having a polymer molecule having an ester bond or a carboxyl group before being heated and melted to form a predetermined shape.
An additive containing any one of ester bonds is blended into a thermoplastic resin, and the polymer molecules of the thermoplastic resin in a heat-melted state are subjected to a transesterification reaction with the additive in a carbon dioxide atmosphere. A method for producing a plastic resin molded article. 2. The method according to claim 1, wherein the transesterification is carried out in a pressurized carbon dioxide atmosphere. 3. The method according to claim 2, wherein the transesterification is carried out in a carbon dioxide atmosphere in a supercritical state.