JP2002121399A - Resin composition and film - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To produce or discolor dot or streak-like appearance defects
Almost no discoloration, excellent transparency and excellent transparency
A composition that has both heat resistance and other properties, and is particularly suitable for optical applications.
Resin composition suitable for obtaining shaped articles and from the resin composition
To provide a film. SOLUTION: Total light transmittance is 88% or more, photoelastic coefficient
1.0 × 10 ^-11Pa^-1Below and glass transition
Thermoplastic amorphous resin 10 having a temperature of 120 to 200 ° C.
0 parts by weight of polymer carbon radical scavenger 0.0
0.5 to 0.5 parts by weight is added.
Resin composition, polymer carbon radical scavenger
Acrelay in compound or molecule with lactone structure
A compound having a hydroxyl group and a phenolic hydroxyl group
The resin composition described above, and any one of the above trees
A fill characterized by being formed from a fat composition
And optical films.
Note film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition and a film (including a sheet) obtained by molding the same.

[0002]

2. Description of the Related Art A resin molded product used for an optical application, particularly for a liquid crystal display element part, has high transparency, a photoelastic coefficient having a small absolute value, high heat resistance, and a small number of spot-like or streak-like appearance defects. It is required that coloring and discoloration are small.
The point-like or streak-like appearance defect referred to in the present invention is a circle, an ellipse, a straight line, or a circle observed on the surface or inside of a molded product.
Defects such as curves and irregular shapes are meant. The above-mentioned defects include buttocks, fish eyes, aggregates thereof, etc. derived from a cross-linked product, which are generated as a result of thermal decomposition of a resin, bubbles inside a molded product derived from a decomposition gas, and broken bubbles on the surface of a molded product. Is included. The term “coloring or discoloration” as used in the present invention means that a molded article that is originally transparent changes color or discoloration from yellow to brown. The coloring and discoloration include coloring and discoloration resulting from decomposition and degradation of the resin, and coloring and discoloration resulting from decomposition and degradation of additives such as phenolic antioxidants.

An amorphous resin is more advantageous than a crystalline resin for obtaining high transparency and a photoelastic coefficient having a small absolute value, and a resin having a high glass transition temperature is required for obtaining high heat resistance. Since it is more advantageous, a resin molded product obtained by molding an amorphous resin having a high glass transition temperature is particularly suitable for the above application.

However, amorphous resins generally have higher melt viscosities than crystalline resins, and therefore need to be molded at a high temperature when performing thermoplastic molding. In particular, 120-200
Using an amorphous resin having a high glass transition temperature of about ℃, in order to thermoplastically mold parts for optical applications with less distortion, it is necessary to mold at a high temperature of 260 ℃ or more,
Since the high molding temperature of 260 ° C. or higher is close to the decomposition temperature of the resin, there is a problem that the molded product has a point-like or streak-like appearance defect, or is colored or discolored due to the partial decomposition of the resin.

[0005] Generally, in order to prevent the appearance of the thermoplastic resin from being defective during molding, and to prevent the thermoplastic resin from being colored or discolored,
It is widely used to add a phenolic antioxidant to a thermoplastic resin. However, the addition of a phenolic antioxidant alone cannot sufficiently prevent the appearance defects, coloring, discoloration, and the like from occurring, and depending on the type of resin and the type of the phenolic antioxidant, the molded product can be rather modified. Coloring and discoloration may be significant.

In addition, the combined use of a phenolic antioxidant and a phosphorus-based antioxidant has been used to prevent the appearance defects, coloration and discoloration of molded articles from occurring due to the synergistic effect. However, although the use of a phosphorus-based antioxidant has the effect of preventing coloration and discoloration of a molded article derived from a phenolic antioxidant to some extent, depending on the manufacturing conditions, the appearance defect of the molded article can be sufficiently prevented. Sometimes it could not be prevented.

As described above, in the prior art in which a phenol-based antioxidant or a phosphorus-based antioxidant is simply added to a thermoplastic amorphous resin having a high glass transition temperature, spot-like or streak-like appearance defects are small, and coloring is not performed. It is difficult to obtain a molded article with little discoloration by an economically advantageous thermoplastic molding method.

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, it is an object of the present invention to produce almost no spot-like or streak-like appearance defects or coloration or discoloration, and to provide excellent transparency and excellent transparency. Another object of the present invention is to provide a resin composition having both heat resistance and the like, and particularly suitable for obtaining a molded product suitable for optical applications, and a film comprising the resin composition.

[0009]

The resin composition according to the present invention has a total light transmittance of 88% or more, an absolute value of a photoelastic coefficient of 1.0 × 10 ^-11 Pa ^-1 or less, and It is characterized by adding 0.005 to 0.5 parts by weight of a polymer carbon radical scavenger to 100 parts by weight of a thermoplastic amorphous resin having a glass transition temperature of 120 to 200 ° C.

According to a second aspect of the present invention, there is provided the resin composition according to the first aspect, wherein the polymer carbon radical scavenger comprises a compound having a lactone structure in the molecule or an acrylate group in the molecule. It is a compound having a phenolic hydroxyl group.

[0011] A film according to the third aspect of the present invention is characterized by being formed from the resin composition according to the first or second aspect.

Further, a film according to a fourth aspect is characterized in that the film according to the third aspect is an optical film.

The thermoplastic amorphous resin used in the present invention has a total light transmittance of 88% or more, an absolute value of photoelastic coefficient of 1.0 × 10 ⁻¹¹ Pa ⁻¹ or less, and a glass transition. It is necessary that the temperature be 120 to 200 ° C., preferably, the total light transmittance is 90% or more, the absolute value of the photoelastic coefficient is 5.0 × 10 ⁻¹² Pa ⁻¹ or less, and glass The transition temperature is 130-180 ° C.

The total light transmittance, photoelastic coefficient and glass transition temperature referred to in the present invention mean the total light transmittance, photoelastic coefficient and glass transition temperature, respectively, measured by the following methods.

[Measurement method of total light transmittance] ASTM D
According to 1003, a thermoplastic amorphous resin having a thickness of 3.2
mm, and the total light transmittance of the molded sheet is measured using a haze meter. [Method of measuring photoelastic coefficient] The photoelastic coefficient of the thermoplastic amorphous resin is measured using a birefringence measuring device. [Method for measuring glass transition temperature] Differential scanning calorimeter (DS
The glass transition temperature of the thermoplastic amorphous resin is measured using C).

If the above-mentioned total light transmittance of the thermoplastic amorphous resin is less than 88%, the luminance may be insufficient when a molded article comprising the obtained resin composition is mounted on, for example, a liquid crystal display device. .

When the absolute value of the photoelastic coefficient of the thermoplastic amorphous resin exceeds 1.0 × 10 ⁻¹¹ Pa ⁻¹ , a molded article made of the obtained resin composition is mounted on, for example, a liquid crystal display device. When a durability test of the liquid crystal display device is performed, the contrast may be reduced.

If the above-mentioned glass transition temperature of the thermoplastic amorphous resin is lower than 120 ° C., the heat resistance of a molded article comprising the obtained resin composition becomes insufficient, and for example, when the resin is used as a component mounted on an automobile. May shrink at high temperatures,
On the other hand, when the temperature exceeds 200 ° C., the melt viscosity of the obtained resin composition becomes too high, and the molding process may be extremely difficult.

The thermoplastic amorphous resin used in the present invention may be any thermoplastic amorphous resin as long as it has the above-mentioned various properties. And the like, such as thermoplastic amorphous resin disclosed in the publication, as a specific example thereof,
For example, the product name “ARTON G” manufactured by JSR Corporation
Series, product name "Zeonor # 160" manufactured by Zeon Corporation of Japan
0R "," Zeonor # 1400 "," Zeonex # 4 "
90K ", product name" Apel # 6015 "manufactured by Mitsui Chemicals, Inc.
And the like. These thermoplastic amorphous resins may be used alone or in combination of two or more.

In the resin composition of the present invention, the polymer carbon radical scavenger is added in an amount of 0.005 to 100 parts by weight of the thermoplastic amorphous resin having the above-mentioned various properties.
It is necessary to add 0.5 parts by weight, preferably 0.01 to 0.3 parts by weight.

The polymer carbon radical scavenger may be any as long as it can scavenge polymer carbon radicals generated as a result of molecular chain cutting or hydrogen abstraction reaction during molding. And a compound having an acrylate group and a phenolic hydroxyl group in the molecule. As an example of the former, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one can be mentioned, and the trade name “Irganox HP” manufactured by Ciba Specialty Chemicals Inc. -136 ". Examples of the latter include “Sumilyzer GM” and “Sumilyzer G”, trade names of Sumitomo Chemical Co., Ltd. represented by the following formulas (1) and (2), respectively.
S ". These polymer carbon radical scavengers may be used alone or in combination of two or more.

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If the amount of the polymer carbon radical scavenger added is less than 0.005 parts by weight based on 100 parts by weight of the thermoplastic amorphous resin, the effect of scavenging the polymer carbon radicals may not be sufficiently obtained. If the amount exceeds 0.5 parts by weight, a new appearance defect may be generated in the obtained molded product due to grease, dirt on a cooling roll, or the like.

In the resin composition of the present invention, other than the above-mentioned polymer carbon radical scavenger, other phenolic antioxidants and phosphorus-based antioxidants may be used, if necessary, as long as the achievement of the object of the present invention is not hindered. It may be added. These phenol-based antioxidants and phosphorus-based antioxidants may be used alone or in combination.

Other phenolic antioxidants include, for example, hindered phenolic antioxidants and semi-hindered phenolic antioxidants, and specific examples thereof include, for example, tetrakis [methylene-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate] methane (for example, trade name “Irganox 1010” manufactured by Ciba Specialty Chemicals), n
-Octadecyl-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate (e.g.,
Ciba Specialty Chemicals' product name “Irganox 1076” etc.), 3,9-bis {2- [3- (3
-T-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy] -1,1-dimethylethyl}-
2,4,8,10-tetraoxaspiro [5,5] undecane (for example, trade name “ADEKA STAB AO-80” manufactured by Asahi Denka Kogyo KK), 1,3,5-tris (3,5-di -T-butyl-4-hydroxybenzyl) -1,3,5
-Triazine-2,4,6 (1H, 3H, 5H) -trione (for example, trade name "Irganox 3114" manufactured by Ciba Specialty Chemicals) and the like.
These other phenolic antioxidants may be used alone or in combination of two or more.

Examples of the phosphorus-based antioxidant include phosphite-based antioxidants and phosphonite-based antioxidants. Specific examples thereof include tris (2,4-di-t-butylphenyl). ) Phosphite (for example, trade name “IRGAFOSS 168” manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “ADK STAB 2112” manufactured by Asahi Denka Kogyo Co., Ltd., trade name “Sumilyzer P-16” manufactured by Kyodo Yakuhin Co., Ltd., manufactured by Yoshitomi Fine Chemical Co., Ltd.) And the like, such as “Tomiphos 202”), bis (2,4-dicumylphenyl) pentaerythritol-diphosphite (for example,
Product name "ADK STAB PEP-45" manufactured by Asahi Denka Kogyo Co., Ltd.
Etc.), bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite (for example, trade name “ADEKA STAB PEP-3” manufactured by Asahi Denka Kogyo KK)
6 "), tetrakis (2,4-t-butylphenyl)
[1,1-Biphenyl] -4,4′-diylbisphosphonite (for example, trade name “Sandstub P-EPQ” manufactured by Sando Co., Ltd., trade name “Irgafos P-EPQ” manufactured by Ciba Specialty Chemicals Co., Ltd.) ), Bis [2,4-
Bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid (for example, “IRGAFOS 38” (trade name, manufactured by Ciba Chemical Co., Ltd.)
Etc.), di-t-butyl-m-cresyl-phosphonite (for example, "GSY" manufactured by Yoshitomi Fine Chemical Co., Ltd.)
-P101 "), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (for example,
And Ciba-Salty Chemicals (Irgafos 126), Asahi Denka Kogyo Co., Ltd. (Adecastab PEP-24). These phosphorus-based antioxidants may be used alone or in combination of two or more. The phosphorus antioxidants are listed in descending order of hydrolysis resistance.

Among the above phosphorus-based antioxidants, tris (2,4-di-t-butylphenyl) is preferred because it has high hydrolysis resistance and can obtain an excellent effect economically by adding a smaller amount thereof. Phosphite is particularly preferably used.

In general, hydrolysis of a phosphorus-based antioxidant is remarkable in an acidic region. Therefore, when the same type of phosphorus-based antioxidant is provided by a plurality of manufacturers, the content of acidic impurities is as small as possible. It is preferable to select and use. Examples of the acidic impurities that may be contained in the phosphorus-based antioxidant include, for example, impurities containing a halogen atom.

The resin composition of the present invention comprises the thermoplastic amorphous resin and the polymer carbon radical scavenger, which are essential components, and the other phenolic antioxidants and phosphorus-based In addition to the antioxidant, if necessary within the range not hindering the achievement of the object of the present invention, an internal lubricant, an anti-greasy agent, an anti-blocking agent, a slip agent, a release agent,
One or more of various additives such as an antistatic agent, a flame retardant, a coloring agent, an antioxidant other than a phenolic antioxidant and a phosphorus antioxidant, a light stabilizer, and an ultraviolet absorber are added. May be. In addition, it is preferable that the additive which does not show acidity is selected and used.

Next, the film of the present invention is formed from the above-described resin composition of the present invention. Although the film of the present invention is suitably used for any application, it is particularly suitably used as an optical film because it has excellent various performances.

The method for forming the film of the present invention is not particularly limited. For example, a thermoplastic amorphous resin 10 may be used.
0 parts by weight of polymer carbon radical scavenger 0.0
0.5 to 0.5 parts by weight and one or two or more predetermined amounts of other phenolic antioxidants or phosphorus-based antioxidants or other various additives which are added as necessary, and then the resin is first added. A composition is made. Then, using the obtained resin composition, the resin composition is thermoplastically molded into a film by an ordinary film forming method, whereby a desired film can be obtained.

As a method of adding the polymer carbon radical scavenger to the thermoplastic amorphous resin, for example, a predetermined amount of the solid thermoplastic amorphous resin and a predetermined amount of the powdered polymer carbon radical scavenger are previously determined. After mixing, heating, a method of melting and kneading the both may be adopted, or a predetermined amount of the thermoplastic amorphous resin that is heated and melted, in a powder state or a heat melting state or in a small amount of an organic solvent. A predetermined amount of the polymer carbon radical scavenger in a dissolved or diluted state may be added and kneaded, or a master batch composed of a thermoplastic amorphous resin and a polymer carbon radical scavenger may be prepared in advance. After preparing, after mixing a predetermined amount of the thermoplastic amorphous resin and a predetermined amount of this master batch, heating, may be adopted a method of melting and kneading both, Because of excellent uniformity of mixing with feces, it is preferable to adopt a master batch method.

Prior to the formation of the film, the thermoplastic amorphous resin or the resin composition may or may not be dried in advance. Drying may be performed by a conventional resin drying method using an ordinary dryer such as described above.

As a method of thermoplastic molding into a film, a usual thermoplastic molding method such as an extrusion molding method using an extruder equipped with a T die may be used. In addition, the resin composition may be thermoplastically molded after being once brought into a solid state, or may be continuously thermoplastically molded in a state of being heated and melted.

The resin composition of the present invention is suitably used not only for molding the above-mentioned film but also for molding molded articles of any shape and molded articles for any applications. Since it is possible, it is particularly suitably used for forming a thin film or an extrusion method using an extruder equipped with a T-die.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.

Example 1 A thermoplastic amorphous resin having a total light transmittance of 93%, a photoelastic coefficient of 2.6 × 10 ⁻¹² Pa ⁻¹ and a glass transition temperature of 171 ° C. was manufactured by JSR Corporation. Trade name "ARTON G6810".
The above "ARTON G6810" was analyzed by liquid chromatography, and it was found that the phenolic antioxidant was 0.2% by weight.
Only detected.

A compound having a lactone structure in the molecule (trade name “Irganox HP”) was used as a polymer carbon radical scavenger in 100 parts of the above “ARTON G6810”.
-136 "), and kneaded with a mixer until the powder of" Irganox HP-136 "uniformly adheres to the surface of the pellet-like" ARTON G6810 "using a mixer to prepare a resin composition. Produced. Next, this resin composition was dried at 100 ° C. for 6 hours using a hot air dryer.

Next, the above resin composition was heated and melted at 330 ° C. by using an extruder (equipment name “Laboplast Mill”, manufactured by Toyo Seiki Co., Ltd.) equipped with a mold, and led to a T-die mold. Extrusion was performed to obtain a film having a thickness of 50 μm.

Example 2 0.045 of polymer carbon radical scavenger "Irganox HP-136" was added to 100 parts of thermoplastic amorphous resin "ARTON G6810".
In the same manner as in Example 1 except that 0.085 part of trade name "Irganox 1010" as a phenolic antioxidant and 0.17 part of trade name "Irgafos 38" as a phosphorus antioxidant were added. Thus, a resin composition was prepared, and a film having a thickness of 50 μm was obtained using the resin composition.

Example 3 A compound having an acrylate group and a phenolic hydroxyl group in the molecule as a polymer carbon radical scavenger (trade name "Sumilyzer G") was used as a polymer carbon radical scavenger for 100 parts of a thermoplastic amorphous resin "ARTON G6810".
M ") A resin composition was prepared in the same manner as in Example 1 except that 0.1 part was added, and a resin composition having a thickness of 5
A 0 μm film was obtained.

Example 4 A compound having an acrylate group and a phenolic hydroxyl group in the molecule as a polymer carbon radical scavenger (trade name “Sumilyzer G”) was used as a polymer carbon radical scavenger for 100 parts of a thermoplastic amorphous resin “ARTON G6810”.
S ") A resin composition was prepared in the same manner as in Example 1 except that 0.1 part was added, and a resin composition having a thickness of 5
A 0 μm film was obtained.

Comparative Example 1 A thermoplastic amorphous resin "ARTON G6810" was used alone without adding a polymer carbon radical scavenger and an antioxidant. After drying “ARTON G6810” at 100 ° C. for 6 hours using a hot-air drier, the thickness was reduced to 50 μm in the same manner as in Example 1.
m was obtained.

The appearances of the films obtained in Examples 1 to 4 and Comparative Example 1 were visually observed, and the number of point defects having a diameter of 50 μm or more per 1 m ² of the film was counted. The presence or absence of defects was confirmed. Also, JIS
K-7105 "Test method for optical properties of plastics"
The yellowness (YI) of the film in the C light source was measured using a spectrocolorimeter according to the following standard. The results are shown in Table 1.

[0044]

[Table 1]

[0045]

As described above, the resin composition of the present invention is obtained by adding a specific amount of the polymer carbon radical scavenger to a specific amount of the thermoplastic amorphous resin. Polymer carbon radicals generated as a result of molecular chain scission, hydrogen abstraction reaction and the like are effectively captured. Therefore, even when molding is performed at a high temperature, there is almost no occurrence of spot-like or streak-like appearance defects or coloring or discoloration due to thermal decomposition of the resin.

The thermoplastic amorphous resin has specific total light transmittance, photoelastic coefficient, and glass transition temperature, and thus exhibits excellent transparency, excellent heat resistance, and the like.

That is, the resin composition of the present invention has almost no occurrence of spot-like or streak-like appearance defects or almost no occurrence of coloring or discoloration, and has both excellent transparency and excellent heat resistance.
In particular, it is suitable for obtaining molded articles suitable for optical applications.

Further, since the film of the present invention is formed from the resin composition of the present invention, it has both of the above-mentioned excellent properties and is suitably used as a film for various uses. However, it is particularly suitably used as an optical film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04

Claims (4)

[Claims] 1. A thermoplastic amorphous resin 10 having a total light transmittance of 88% or more, an absolute value of a photoelastic coefficient of 1.0 × 10 ⁻¹¹ Pa ⁻¹ or less, and a glass transition temperature of 120 to 200 ° C.
0 parts by weight of polymer carbon radical scavenger 0.0
A resin composition characterized by adding from 0.5 to 0.5 part by weight. 2. The resin composition according to claim 1, wherein the polymer carbon radical scavenger is a compound having a lactone structure in the molecule or a compound having an acrylate group and a phenolic hydroxyl group in the molecule. 3. A film formed from the resin composition according to claim 1 or 2. 4. The film according to claim 3, which is an optical film.