JPH09296054A - Molded object of additive-containing thermoplastic resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded object of an additive-containing thermoplastic resin which is advantageous in that it is free from the volatilization of the additive contained therein over the course of time, and also the transparency thereof is almost never lowered; and a method for producing the molded object. SOLUTION: This molded object comprises a thermoplastic resin having ester groups or carboxy groups in side chains thereof and, incorporated therein, an additive having a functional group selected from the group consisting of an amino group, a hydroxyl group, a carboxy group and an ester group, wherein the additive is bonded with a side chain of the polymer molecule of the thermoplastic resin through an ester bonding formed by transesterification reaction between them. This molded object of an additive- containing thermoplastic resin is produced by a method comprising compounding the additive with the thermoplastic resin, to thereby effect the transesterification reaction of the additive with a side chain of the polymer molecule, prior to subjecting the thermoplastic resin to heating, melting and molding into a predetermined shape. When an additive having two functional groups is transesterificated with the side chain, there is obtained a molded object comprising a polymer molecule being three- dimensionally cross-linked through the additive, which is improved in physical properties such as heat resistance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin molded product containing various additives so as not to volatilize and disappear, and a method for producing the same.

[0002]

2. Description of the Related Art Molded articles such as exterior building materials molded from thermoplastic resins often contain additives such as ultraviolet absorbers and antifouling agents in order to improve weather resistance and stain resistance. . Among them, the exterior building materials made of acrylic resin are
It has relatively good transparency and weather resistance, and is used for applications requiring various lighting properties such as roofing materials, outer wall materials, skylights, and soundproofing boards.

[0003]

However, since the conventional additive-containing thermoplastic resin moldings are those in which the additives are physically mixed and dispersed, the additives volatilize and disappear over time. However, there is a problem that weather resistance and stain resistance cannot be maintained for a long time.

Further, when the additives are physically mixed and dispersed, the excellent heat resistance and mechanical strength inherent in the thermoplastic resin may be deteriorated, and the transparency of the acrylic resin is greatly impaired. I was afraid.

The present invention has been made in view of the above circumstances, and provides an additive-containing thermoplastic resin molded product in which the additive does not evaporate with time and transparency is hardly deteriorated, and a method for producing the same. The main purpose is that. And, in a desirable embodiment, it is intended to further improve the heat resistance, the stain resistance, the weather resistance and the like of the molded body and the reaction rate of the additive.

[0006]

To achieve the above object, the additive-containing thermoplastic resin molding according to claim 1 of the present invention comprises a thermoplastic resin having an ester group or a carboxyl group in the side chain of a polymer molecule. In the molded body of, amino group,
Hydroxyl group, carboxyl group, containing an additive having any functional group of the ester group, characterized in that the additive is transesterified with the side chain of the polymer molecule of the thermoplastic resin to form an ester bond, The molded body according to claim 2 is characterized in that the thermoplastic resin is an acrylic resin, and the molded body according to claim 3 is such that the additive is bifunctional and the polymer molecule of the thermoplastic resin has side chains thereof. A three-dimensionally cross-linked by a bifunctional additive ester-bonded to, the molded article according to claim 4, wherein the additive is a functional group of any one of an amino group, a hydroxyl group, a carboxyl group and an ester group. A polydimethylsiloxane having a content of 0.1 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin. Two Hydroxyl group of the above carboxyl group, a 2-hydroxybenzophenone derivative or 2-hydroxyphenyl-benzotriazole derivatives having any one functional group of the ester group, the thermoplastic resin 100
It is characterized in that the content is 0.01 to 5 parts by weight with respect to parts by weight.

Further, in the production method according to claim 6 of the present invention, before the thermoplastic resin having the ester group or the carboxyl group in the side chain of the polymer molecule is melted by heating and molded into a predetermined shape, an amino group, Hydroxyl group, carboxyl group, an additive having any functional group of an ester group is blended with a thermoplastic resin, characterized in that the side chain of the polymer molecule of the thermoplastic resin in a heat-melted state and the additive transesterification reaction The manufacturing method according to claim 7 is characterized in that the additive is bifunctional.

Since the thermoplastic resin constituting the molded article of the present invention has an ester group or a carboxyl group in the side chain of its polymer molecule, the thermoplastic resin is heated and melted in the same manner as in the production method of the present invention to give a predetermined amount. Before molding into a shape, if an additive having a functional group of amino group, hydroxyl group, carboxyl group, or ester group is blended with a thermoplastic resin in a heat-melted state, the side chain of the additive and the polymer molecule becomes an ester. An exchange reaction occurs, and the additive is immobilized by ester bond to the side chain of the polymer molecule. The molded article of the present invention molded with the thermoplastic resin in which the additive is immobilized in this way maintains the effect of the additive for a long period of time because the additive does not volatilize and disappear over time. be able to.

Further, when the additive is ester-bonded to the side chain of the polymer molecule, the additive becomes finely dispersed at the molecular level, so that the dispersed particles of the additive and the thermoplastic resin have different optical refractive indexes. Also, refraction and scattering of transmitted light are reduced. Therefore, the decrease in the transparency of the molded product due to the additive is extremely slight, and the additive physically dispersed as in the conventional molded product is secondarily aggregated to significantly increase the original transparency of the thermoplastic resin. It is possible to eliminate the demerit. This effect is
It is remarkably exhibited when an additive is ester-bonded to the acrylic resin.

Further, when the polymer molecule of the thermoplastic resin is three-dimensionally cross-linked by a bifunctional additive having an ester bond to its side chain as in the molded article of claim 3, the cross-linking of the molded article is caused by this cross-linking. The physical properties, in particular the heat resistance, are remarkably improved, and as shown in the experimental data described later, the glass transition point (Tg) is increased by about 20 ° C. as compared with a molded product made of thermoplastic alone.

Further, as in the molded article according to claim 4, as an additive, polydimethylsiloxane having a functional group of any of amino group, hydroxyl group, carboxyl group and ester group is added to 100 parts by weight of the thermoplastic resin. Since the above polydimethylsiloxane is a silicon compound having water repellency, it is necessary to maintain good stain resistance for a long period of time because the polydimethylsiloxane is contained in a proportion of 1 to 5 parts by weight and has an ester bond. Further, as in the molded article of claim 5, the compound of the 2-hydroxybenzophenone derivative or the 2-hydroxyphenylbenzotriazole derivative having the same functional group as an additive is added in an amount of 0.01 to 5 parts by weight. Those contained and ester-bonded have good weather resistance over a long period of time because these compounds have ultraviolet absorption ability. It is possible.

[0012]

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, in the case of continuously extruding a plate-shaped molded product of an acrylic resin containing an additive (acrylic resin plate containing an additive). Is an example.

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 an additive injection hopper provided in the middle of the molding machine, 1c is a screw inside the molding machine, 1d is a molding machine provided at the tip of the molding machine. A die 1e is a carbon dioxide blowing port provided in an intermediate portion of molding, 2 is a pair of upper and lower cooling rolls, 3 is a conveyor belt, and 4 is a cutting machine.

In this embodiment, the raw material acrylic resin 5 dried by preheating is charged into the molding machine 1 from the hopper 1a at the rear of the molding machine, and the acrylic resin 5 is melted at a temperature above the melting temperature (but below the decomposition temperature). ) And kneading with the screw 1c while melting. Then, the additive 6 having any functional group of amino group, hydroxyl group, carboxyl group and ester group is charged from the hopper 1b in the middle part of the molding machine and heated while blowing carbon dioxide from the carbon dioxide blowing port 1e. The acrylic resin 5 and the additive 6 in a molten state are uniformly kneaded by a screw 1c to cause a transesterification reaction, and then extruded into a plate shape from a die 1d at the tip, and the plate-shaped molded body 50 is vertically paired. It is taken up while being cooled by the cooling rolls 2 and 2, and is conveyed to the cutting machine 4 by the conveyor belt 3 and cut into a predetermined length.

The raw material acrylic resin 5 has a polymer molecule represented by the following structural formula [Chemical Formula 1], and specifically, polyacrylic acid or polymethacrylic acid having a carboxyl group in its side chain. An acid or a polyacrylic acid alkyl ester or a polymethacrylic acid alkyl ester having a methyl ester group, an ethyl ester group or a propyl ester group in the side chain is used.

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Since the side chain carboxyl group and ester group of the acrylic resin 5 are functional, the acrylic resin 5 is heated in the molding machine 1 to a temperature above the melting temperature and below the decomposition temperature as described above. When in a molten state and kneaded with the additive 6 having any functional group of amino group, hydroxyl group, carboxyl group and ester group, the side chain of the polymer molecule and the additive undergo transesterification reaction, and the additive is polymer molecule. It is immobilized by ester bond to the side chain of. In that case, a transesterification catalyst such as iron chloride, cobalt acetate, or trimethylamine is added to 0.001 to 100 parts by weight of the acrylic resin.
When it is mixed in a proportion of about 0.5 part by weight, the transesterification reaction is promoted.

In particular, when carbon dioxide is blown into the molding machine 1 to carry out the transesterification reaction in a carbon dioxide atmosphere as in the present embodiment, the transesterification reaction is remarkable due to the plasticizing effect of carbon dioxide and the solvent effect. It is promoted and its reaction rate is greatly improved. The former plasticizing effect is that carbon dioxide acts as a plasticizer of the thermoplastic resin and reduces the melt viscosity of the resin, so that the ester group or carboxyl group of the side chain of the polymer molecule contacts the functional group of the additive. It is considered that the transesterification reaction is promoted by increasing the number of opportunities to do so, and the latter solvent effect is that carbon dioxide and -COO- of the ester group or carboxyl group of the polymer molecule side chain have the same elemental constitution. Therefore, it is considered that the carbon dioxide gas gathers around the ester group or the carboxyl group and acts as a solvent to facilitate the reaction of the ester group or the carboxyl group to promote the transesterification reaction.

In the above embodiment, an acrylic resin is used as the raw material resin, but a thermoplastic resin other than acrylic resin may be used as long as it is a thermoplastic resin having an ester group or a carboxyl group in the side chain. Even when maleated polyethylene or maleated polystyrene is used, the additive is similarly ester-bonded and immobilized.

The molded product 50 obtained by extrusion-molding the acrylic resin having the additives fixed therein as described above is added over a long period of time because the additives do not volatilize and disappear over time. The efficacy of the agent can be maintained. Moreover, the additive is finely dispersed at the molecular level by an ester bond, and the particles of the additive do not secondarily aggregate as in the case of being physically dispersed. Therefore, the dispersed particles of the additive and the acrylic resin Even if the light refraction index is different, the transparency of the molded body 50 hardly decreases due to refraction and scattering of transmitted light, and the molded body 50 has good transparency which is not so different from that of the acrylic resin alone. Can hold.

The additive 6 has a functional group of an amino group, a hydroxyl group, a carboxyl group, or an ester group at the molecular end or in the molecule and is capable of transesterification with the side chain of the polymer molecule of the acrylic resin. All of them can be used, and it is possible to select and use various ones which can impart the desired effect to the desired acrylic resin molded body. Then, the content of the additive 6 may be appropriately determined so that the effect is sufficiently exhibited.

For example, when the acrylic resin molded body is required to have stain resistance, the additive 6 is represented by the following [Chemical formula 2].
A polydimethylsiloxane having an amino group at both ends of the molecule represented by the structural formula, a polydimethylsiloxane having an amino group in the molecule represented by the structural formula of [Chemical Formula 3] below,
Polydimethylsiloxane having a carboxyl group at one end of the molecule represented by the structural formula of [Chemical Formula 4], polydimethylsiloxane having a hydroxyl group at both ends of the molecule represented by the structural formula of [Chemical Formula 5] below, A silicon compound such as polydimethylsiloxane having an ester group at both ends of the molecule represented by the structural formula [6] can be preferably used as an antifouling agent, and fluorinated bisphenol A [having a hydroxyl group at both ends of the molecule] Fluorine compounds such as 2,2-bis- (4-hydroxyphenyl) -hexafluoropropane] can also be suitably used as the antifouling agent.

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[Chemical 6]

These silicon-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 acrylic resin to form an ester bond to the side chain of the polymer molecule. It is possible to impart a good water repellent property to the molded article and maintain excellent stain resistance for a long period of time.
In some cases, the following [Chemical Formula 7] having no functional group
The polydimethylsiloxane represented by the structural formula (1), fluorocarbon, or the like may be used in combination with the antifouling agent.

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When the acrylic resin molded body is required to have weather resistance, 2- (2'-hydroxy-5'-carboxyphenyl) benzotriazole having a carboxyl group at the molecular end is used as the additive 6. -Hydroxybenzophenone-4-oxyacetic acid, or 2-hydroxy-4- (2'-hydroxyethoxy) benzophenone having two or more hydroxyl groups at the molecular end, 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.

When these UV absorbers are blended in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the acrylic resin to form an ester bond to the side chain of the polymer molecule, deterioration of the molded product due to ultraviolet rays is suppressed. Therefore, excellent weather resistance can be maintained for a long period of time.

In addition, flame retardants such as tetrabromobisphenol, radiation-resistant agents such as thiodiphenol, and antioxidants such as N, N-diphenyl-p-phenylenediamine depending on the effect required for the acrylic resin molded article. Various additives such as agents, antibacterial agents such as tributyltin laurate, antistatic agents such as tetraphenyldipropylene glycol diphosphite, plasticizers such as dioctyl phthalate and dodecanol can be used.

When a bifunctional additive having functional groups at both ends of the molecule is used among the above additives, the polymer molecule of the acrylic resin is three-dimensionally crosslinked by the bifunctional additive having an ester bond to its side chain. Due to this structure, the physical properties of the acrylic resin molded body 50, particularly the heat resistance, are significantly improved. For example, polymethylmethacrylate (PMMA: polymethylmethacrylate) is used as the acrylic resin 5, and polydimethylsiloxane (PDMS) of [Chemical Formula 2] having amino groups at both ends of the molecule is used as the additive 6, When both are transesterified inside the molding machine, as shown in the following [Chemical formula 8], both ends of PDMS molecules are crosslinked by ester bonds to the side chains of the adjacent PMMA polymer molecules. Each polymer molecule has a three-dimensionally crosslinked structure by many PDMS ester-bonded to, and the glass transition point of the obtained molded product is higher than that of the non-crosslinked molded product of PMMA alone, as shown in the data of the Examples below. The temperature rises by about 20 ° C and the heat resistance is greatly improved. However, not all of the compounded bifunctional PDMS contributes to three-dimensional crosslinking, and some PDMS
In MS, only one end of the molecule is ester-bonded to the side chain of the polymer molecule to be in a non-crosslinked state, and unreacted PDMS is contained in the molded body in a free state.

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The reaction rate of transesterification varies somewhat depending on the type of acrylic resin and the type of additive, but is usually 1
The reaction is almost completed in about 15 minutes. Therefore, when the transesterification reaction is performed inside the molding machine 1 as in this embodiment for extrusion molding, the additive 6 is charged into the molding machine 1 and kneaded with the acrylic resin 5 for about 1 to 15 minutes. Additive-filling hopper 1b so as to be extruded from the mold 1d later
It is important to set the position, screw design, and other extrusion conditions so that the transesterification reaction is carried out sufficiently. As the molding machine 1, a twin-screw extruder capable of performing uniform kneading with two screws 1c is suitably used.

In this embodiment, the acrylic resin 5 and the additive 6 are individually charged into the molding machine 1 from the hoppers 1a and 1b. However, for example, both may be charged together from the hopper 1a or the hopper 1a. A mixture of both from 1b may be added in an appropriate amount, and thus the addition method can be appropriately selected. In addition, in this embodiment, the molten acrylic resin to which the additive is ester-bonded is extruded in a single layer from the mold 1d to manufacture the plate-shaped molded body 50.
By changing the mold 1d etc., sheets, films, odd-shaped products, etc.
Needless to say, molded articles of various shapes can be produced, and further, using a coextrusion molding machine or the like, a molten acrylic resin in which an additive is ester-bonded is used as an upper layer, and the additive is less than or completely absent from the upper layer. A two- or three-layered plate-shaped molded product in which an acrylic resin layer containing an additive is laminated on the surface by co-extruding a molten acrylic resin or another resin not containing it into upper and lower two or three layers. Of course, it is possible to manufacture. Even in the case of injection molding, if the additive is mixed and the transesterification reaction is performed before the molten acrylic resin is injected into the mold of the injection molding machine, the transparency of the additive does not evaporate as well. It is possible to obtain various molded products.

[0030]

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

[Example 1] 100 parts by weight of polymethylmethacrylate (PMMA) which is an acrylic resin as a thermoplastic resin, and polydimethylsiloxane (H ₂ N-PDMS-NH ₂₎ having amino groups at both ends of a molecule as an additive. )
Was mixed in an amount of 2.00 parts by weight and iron chloride as a catalyst in a ratio of 0.001 parts by weight, and the mixture was put into a twin-screw extruder and melt-kneaded at 232 ° C. for 5 minutes to carry out a transesterification reaction. Then, it was extrusion-molded into a plate shape from a mold of a molding machine to obtain a molded body. Then, after dissolved in a solvent (dichloromethane) to cut the molded body, was precipitated with diethyl ether to H ₂ N-PDMS-NH ₂ to remove unreacted, dissolved in dichloromethane precipitate again, this Was cast to prepare a test film having a thickness of 70 μm.

About this test film, H ₂ N--P
When the reaction rate of the transesterification reaction of DMS-NH ₂ was determined by the following method, the amount of H ₂ N-PDMS-NH ₂ that had undergone the transesterification reaction was 0.4 as shown in [Table 1] below.
It was 2 parts by weight, and the reaction rate was 21.0%.

(Test Method for Reaction Rate of Transesterification Reaction)
¹ HN of heavy chloroform solution with test film dissolved
The MR spectrum was measured, H by ester exchange reaction from the intensity of protons of the _{Si-CH 3 2 N-PDMS} -NH _ 2
Is calculated, and the reaction rate is calculated from the following formula [Equation 1].

[Equation 1]

Next, regarding this test film, 55
When the transmittance of 0 nm light and the glass transition temperature (Tg) were measured, the light transmittance was 88 as shown in [Table 1] below.
%, The glass transition temperature was 102 ° C.

Further, the above test film was dipped in a blue-black ink, which is an office ink, at room temperature, and the light transmittance at 550 nm after the dipping for 2 weeks was measured. As a result, as shown in Table 1 below, The transmittance was 70%.

Example 2 The same as Example 1 except that carbon dioxide was blown into the twin-screw extruder and the transesterification reaction between PMMA and H ₂ N-PDMS-NH ₂ was carried out in a carbon dioxide atmosphere. A test film having a thickness of 70 μm was produced.

This test film was subjected to transesterification reaction in the same manner as in Example 1, H ₂ N-PDMS-.
The amount of NH ₂ , the reaction rate, the light transmittance, and the glass transition temperature were measured, and the same stain resistance test as in Example 1 was performed. The results are shown in [Table 1] below.

Comparative Example 1 PMMA used in Example 1
Was dissolved in dichloromethane and cast to give a thickness 7 without H ₂ N-PDMS-NH _2.
A 0 μm film was made.

With respect to this film, the light transmittance and the glass transition temperature were measured in the same manner as in Example 1, and further, Example 1
The same stain resistance test was performed. The results are shown in [Table 1] below.

[Comparative Example 2] PMMA used in Example 1
A thickness of physically dispersed H ₂ N-PDMS-NH ₂ was obtained by dissolving a mixture of 100 parts by weight and 0.42 part by weight of H ₂ N-PDMS-NH ₂ in dichloromethane, and casting the mixture. A 70 μm film was prepared.

With respect to this film, the light transmittance and the glass transition temperature were measured in the same manner as in Example 1, and further, Example 1
The same stain resistance test was performed. The results are shown in [Table 1] below.

[Comparative Example 3] PMMA used in Example 1
A mixture of 100 parts by weight and 1.04 parts by weight of H ₂ N-PDMS-NH ₂ was dissolved in dichloromethane, and the mixture was cast to obtain a thickness at which H ₂ N-PDMS-NH ₂ was physically dispersed. A 70 μm film was prepared.

With respect to this film, the light transmittance and the glass transition temperature were measured in the same manner as in Example 1, and further, Example 1
The same stain resistance test was performed. The results are shown in [Table 1] below.

[Table 1]

From Table 1, it can be seen that the film of Comparative Example 1 containing only PMMA containing no H ₂ N-PDMS-NH ₂ has a high light transmittance of 90% and excellent transparency. It can be seen that the light transmittance after immersion for 2 weeks in the stain resistance test was significantly reduced to 50%, and the stain resistance was poor. Also,
The glass transition temperature is also 90 ° C., and it cannot be said that the heat resistance is sufficient.

On the other hand, the film of Example 1 was H ₂ N--P
Since DMS-NH ₂ is ester-bonded to the side chain of PMMA and finely dispersed at the molecular level, the light transmittance is 88%.
Which is only 2% lower than the light transmittance (90%) of the film of Comparative Example 1 containing PMMA alone.
It can be seen that it has good transparency. The film of Example 1 had a light transmittance of 70% after being immersed for 2 weeks in the stain resistance test, and did not show a significant decrease in the light transmittance due to ink stain. You know that you have. Further, in the film of this Example 1, the polymer molecules are three-dimensionally crosslinked by the ester-bonded H ₂ N-PDMS-NH ₂ , so that the glass transition temperature of the film is the glass transition temperature of the PMMA single film of Comparative Example 1 ( 90 ° C)
The higher temperature is 102 ° C., which shows that the heat resistance is improved.

On the other hand, the film of Comparative Example 2 in which H ₂ N-PDMS-NH ₂ was physically dispersed was H ₂ N-PD.
The content of MS-NH ₂ is the same as that of the film of Example 1.
Despite 42 parts by weight, the light transmittance is significantly reduced to 45%, which shows that the transparency is poor. This is because secondary particles of dispersed H ₂ N-PDMS-NH ₂ aggregate to increase refraction and scattering of transmitted light. This film also has a glass transition temperature of 91.
It was lower than that of the film of Example 1 at 0 ° C., and the heat resistance was hardly improved, and the light transmittance after soaking for 2 weeks in the stain resistance test was significantly reduced to 28%, and the stain resistance was improved. It turns out that it's not very good.

Furthermore, since the film of Example 2 was transesterified in a carbon dioxide atmosphere, its reaction rate was remarkably improved to 51.9%, and the reaction rate of the film of Example 1 was improved. About 2.5 times, and 1.04 parts by weight of H ₂ N-PDMS-NH ₂ is contained as an ester bond. Thus, the film of Example 2 had H ₂ N-PD
Despite the content of MS-NH ₂ is large, the light transmittance of 87% for almost the same light transmittance of the film of Example 1 has a good transparency. This is H
_{This is because 2} N-PDMS-NH ₂ is finely dispersed and immobilized at the molecular level by an ester bond and is not secondary aggregated. And, in the case where a large amount of H ₂ N-PDMS-NH ₂ is ester-bonded like the film of Example 2, the cross-linking density becomes high, the heat resistance is remarkably improved, and the glass transition temperature rises to 110 ° C. are doing. Moreover, since a large amount of H ₂ N-PDMS-NH ₂ strengthens the water repellency of the film, the light transmittance after immersion for 2 weeks in the stain resistance test hardly decreases to 82%, and the stain resistance is excellent. It is understood that there is.

On the other hand, Comparative Example 3 in which the same amount of H ₂ N-PDMS-NH ₂ as in the film of Example ₂ was physically dispersed.
It can be seen that the film of No. 2 has an extremely low light transmittance of 32% and has poor transparency. The film had a glass transition temperature of 90 ° C., which was lower than that of the film of Example 1, and showed no improvement in heat resistance. The light transmittance after immersion for 2 weeks in the stain resistance test was 20%, which is considerably high. reduced, H ₂
It can be seen that the stain resistance is not so good despite the large content of N-PDMS-NH ₂ .

Example 3 The same as Example 1 except that carbon dioxide was blown into the twin-screw extruder and the transesterification reaction of PMMA and H ₂ N-PDMS-NH ₂ was carried out in a carbon dioxide atmosphere. To obtain a molded body. Then, the molded body was cut, dissolved in a solvent (dichloromethane), and cast to obtain 1.04 parts by weight of H ₂ N-.
A 110 μm-thick test film was produced in which PDMS-NH ₂ was ester-bonded and 0.96 parts by weight of H ₂ N-PDMS-NH ₂ was contained unreacted.

With respect to this test film, the light transmittance before heating (550 nm), the light transmittance after heating at 90 ° C. for 30 minutes, and the light transmittance after heating at 90 ° C. for 1 hour were measured. . The results are shown in [Table 2] below.

[Comparative Example 4] In the same manner as in Comparative Example 1, H ₂
Thickness of PMMA alone without N-PDMS-NH ₂ 1
A film having a thickness of 10 μm was prepared, and in the same manner as in Example 3, the light transmittance was measured before heating at 90 ° C. for 30 minutes and at 90 ° C. for 1 hour. The results are shown in [Table 2] below.

Comparative Example 5 H ₂ N-PDMS-NH ₂ was physically prepared in the same manner as in Comparative Example 2 except that the compounding amount of H ₂ N-PDMS-NH ₂ was changed to 2.00 parts by weight. A dispersed film having a thickness of 110 μm was produced, and in the same manner as in Example 3, the light transmittance was measured before heating at 90 ° C. for 30 minutes and after heating at 90 ° C. for 1 hour. The results are shown in [Table 2] below.
Shown in

[Table 2]

From this Table 2, the film of Example 3 has H
Despite having a large amount of ₂ N-PDMS-NH ₂ of 2.00 parts by weight, it has a light transmittance of 83.7% which is almost the same as the film of Comparative Example 4 containing PMMA alone. It can be seen that the transparency is good. This is 2.00
Among the parts by weight of H ₂ N-PDMS-NH ₂ , 1.04 parts by weight of H ₂ N-PDMS-NH ₂ are ester-bonded and finely dispersed at the molecular level. It is considered that H ₂ N-PDMS-NH _{2 of} No. ₂ was also finely dispersed. On the other hand, the film of Comparative Example 5 in which 2.00 parts by weight of H ₂ N-PDMS-NH ₂ in the same amount as the film of Example 3 was physically dispersed had a light transmittance of 3.8.
It is 7%, which means that the transparency is almost lost.

The films of Example 3 and Comparative Example 4 had light transmittances of 83.7% and 8 before heating, respectively.
The value of 5.0% decreased to 77.7% and 80.0% after heating at 90 ° C. for 30 minutes, respectively, but the reduction rate of the light transmittance before and after heating was almost the same. . Therefore, the decrease in the light transmittance of the Example 3 is a decrease in the acrylic resin itself, it can be seen that not the influence of _{H 2 N-PDMS-NH 2} . Further, the film of Comparative Example 5 has a large rate of decrease in light transmittance before and after heating, and it can be seen that this is greatly affected by physically dispersed H ₂ N-PDMS-NH ₂ . From this, the H ₂ N-PDM of Example 3 was obtained.
It can be seen that the dispersed state of S-NH ₂ is not changed even by heating because it is dispersed at the molecular level.

Example 4 A test film having a thickness of 70 μm was produced in the same manner as in Example 2 except that the additive was changed to polydimethylsiloxane (HO-PDMS) having a hydroxyl group at the terminal of the molecular piece.

With respect to this film, the light transmittance and the glass transition temperature were measured in the same manner as in Example 1, and further, Example 1
The same stain resistance test was performed. The results are shown in Table 3 below.

[Table 3]

Looking at this Table 3, HO-PDMS has a small reaction amount, and only 0.80% by weight is reacted. This is because HO-PDMS is monofunctional and bifunctional H ₂ N-.
This is because there are less chances of reaction than PDMS-NH ₂ and due to the difference in reactivity between —NH ₂ and —OH. From this, it is understood that the bifunctional additive is preferable to the monofunctional additive. Further, the glass transition temperature is 90 ° C., which is almost the same temperature as PMMA, and it is understood that three-dimensional crosslinking is not carried out.

[0058]

As is clear from the above description, in the additive-containing thermoplastic resin molded product of the present invention, the additive is finely dispersed at the molecular level to form an ester bond with the side chain of the polymer molecule of the thermoplastic resin. Since it is immobilized on the surface, it has good properties that are almost the same as the original excellent properties of the thermoplastic resin. When the thermoplastic resin is an acrylic resin, its excellent transparency is substantially reduced. There is no need to worry,
Since the ester-bonded additive does not volatilize with time, the effect of the additive can be retained for a long period of time, and especially, the bifunctional additive in which the polymer molecule is ester-bonded to the side chain of the additive causes tertiary The original cross-linked molded body is
It has a remarkable effect of improving heat resistance.

Further, the production method of the present invention is carried out by using a conventional general-purpose molding machine and simply adding a step of adding an additive to the thermoplastic resin in a heated and melted state before the melt-molding to perform an ester exchange reaction. Because it is possible, it is economical without the need to install special molding machines and equipment newly,
As in the conventional case, it is possible to efficiently mass-produce molded products.

[Brief description of drawings]

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

[Explanation of symbols]

 1 Extrusion Molding Machine 1e Carbon Dioxide Blow Port 5 Acrylic Resin 6 Additive 50 Additive-Containing Acrylic Resin Molded Product

Claims (7)

[Claims] 1. A thermoplastic resin molded product having an ester group or a carboxyl group in the side chain of a polymer molecule contains an additive having a functional group of any of an amino group, a hydroxyl group, a carboxyl group and an ester group. An additive-containing thermoplastic resin molded article, wherein the additive is transesterified with a side chain of a polymer molecule of the thermoplastic resin to form an ester bond. 2. The molded article according to claim 1, wherein the thermoplastic resin is an acrylic resin. 3. The additive is bifunctional, and the polymer molecule of the thermoplastic resin is three-dimensionally cross-linked by the bifunctional additive having an ester bond to its side chain. The molded product according to claim 2. 4. The additive is polydimethylsiloxane having a functional group of amino group, hydroxyl group, carboxyl group or ester group, and is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin. The molded product according to any one of claims 1 to 3, which is contained in a ratio. 5. The additive is an amino group, two or more hydroxyl groups,
A 2-hydroxybenzophenone derivative or a 2-hydroxyphenylbenzotriazole derivative having a functional group of any of a carboxyl group and an ester group,
The molded product according to any one of claims 1 to 3, which is contained in a proportion of 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 6. A thermoplastic resin having an ester group or a carboxyl group on the side chain of a polymer molecule is heated and melted before being molded into a predetermined shape, and a functional group of any of an amino group, a hydroxyl group, a carboxyl group and an ester group. A method for producing an additive-containing thermoplastic resin molded article, which comprises adding an additive having a group to a thermoplastic resin, and subjecting the additive to a side chain of a polymer molecule of the thermoplastic resin in a heat-melted state and the additive for transesterification reaction. . 7. The production method according to claim 6, wherein the additive is bifunctional.