KR20200059497A - Compositions of polycarbonate resin for food container and manufacturing method the same - Google Patents

Abstract

Disclosed are: a polycarbonate resin excellent in applicability for food while maintaining conventional physical properties with only an antioxidant added to the polycarbonate resin; and a method of manufacturing the same. The present invention provides a polycarbonate resin composition for food, including 98 to 99.98 wt% of polycarbonates, 0.01 to 1 wt% of an antioxidant consisting of a phosphorus-based antioxidant, 0.01 to 1 wt% of a releasing agent, and 0.1 to 10 ppm of a colorant; and a method of manufacturing the same.

Description

Composition of polycarbonate resin for food and its manufacturing method

The present invention relates to a polycarbonate resin composition and a method for manufacturing the same, and more particularly, to a polycarbonate resin composition for food and a method for manufacturing the same.

Polycarbonate resin is used as a container or packaging material in contact with food. For example, polycarbonate resins are applied to various uses such as food containers, baby bottles, bottled water bottles, cups, and cooking utensils, but safety standards and standards for resins applied to food containers have recently been strengthened, and limited products It is gradually expanding.

To prevent oxidation of polycarbonate resins, phenol-based primary antioxidants are used. However, phenol-based primary antioxidants have a problem that their use for food is limited due to their low molecular weight and easy dissolution and decomposition. In addition, in order to solve this problem, when a phenol-based primary antioxidant having a high molecular weight is added, there is a problem in that discoloration and color are affected by a large amount of phenol functional groups.

On the other hand, it can be considered that the primary antioxidant is not added to the polycarbonate resin, but in general, the coloring agent is dissolved in the primary antioxidant and then added, so there is a problem that the coloring agent cannot be introduced into the production process.

Korean Registered Patent No. 0898899 proposes a composition that improves the thermal stability and hydrolysis resistance of polycarbonate by removing a residual catalyst of polycarbonate by adding a sulfonic acid ester compound, but there is a problem that safety is poor when it comes into contact with food.

The present invention has been devised to solve the above problems, and to provide a polycarbonate resin composition having excellent applicability for food and a method for manufacturing the same while adding only phosphorus-based antioxidants to the polycarbonate resin and maintaining existing properties.

In order to solve the above problems, the present invention is polycarbonate for food comprising 98 to 99.98% by weight of polycarbonate, 0.01 to 1% by weight of an antioxidant consisting of phosphorus-based antioxidant, 0.01 to 1% by weight of a release agent, and 0.1 to 10 ppm of a coloring agent. Provided is a resin composition.

In addition, the phosphorus antioxidant is tris-2,4-di-t-butylphenyl-phosphite, bis-2,4-dicumylphenyl-pentaerythritol-diphosphite, tetrakis-2,4-di-t -Butylphenyl-1,1-biphenyl-4,4-diylbisphosphite and bis-2,6-di-t-butyl-4-methylphenyl-pentaerythritol-diphosphite It provides a polycarbonate resin composition for food, characterized in that the above.

In addition, the release agent provides a polycarbonate resin composition for food, characterized in that at least one member selected from the group consisting of pentaerythritol tetrastearate, glycerin monostearate, stearyl stearate, and propanediol stearate.

In addition, the colorant is a solvent violet 59 (Solvent Violet 59, CAS No. 6408-72-6), a solvent violet 36 (Solvent Violet 36, CAS No. 61951-89-1), a solvent violet 31 (Solvent Violet 31, CAS No. 70956-27-3), Solvent Violet 13, CAS No. 81-48-1, Solvent Blue 122, CAS No. 67905-17-3, Solvent Blue 45 (Solvent Consisting of Blue 45, CAS No. 37229-23-5), Solvent Blue 97, CAS No. 61969-44-6 and Solvent Blue 104 (Solvent Blue 104, CAS No. 116-75-6) It provides a polycarbonate resin composition for food, characterized in that at least one selected from the group.

In order to solve the above another problem, the present invention is to prepare a polycarbonate resin composition by adding and mixing an antioxidant, a release agent and a coloring agent made of a phosphorus-based antioxidant in a polycarbonate in a mixer, but dissolving the coloring agent in a release agent It provides a method for producing a polycarbonate resin composition for food comprising a step.

In addition, the mixing provides a method for producing a polycarbonate resin composition for food, characterized in that is performed at a temperature condition of 100 ~ 250 ℃.

In order to apply the polycarbonate as a resin in contact with food, it should not contain a compound having properties that are easily eluted and decomposed, but the present invention is a polycarbonate resin composition that does not contain a phenol-based primary antioxidant, so that the elution is safe when it comes into contact with food. It is suitable for, it is possible to provide a polycarbonate resin composition excellent in optical properties, long-term heat resistance, mechanical properties.

Further, in the present invention, in the production of a polycarbonate resin composition in which only a phosphorus-based antioxidant is used as an antioxidant and a colorant is mixed, the additive is dissolved without using a phenol-based primary antioxidant by dissolving the colorant in a release agent and then adding it. It is possible to provide a method for preparing a polycarbonate resin composition for foods having excellent acidity and solubility.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the description of the present invention, when it is determined that a detailed description of related known technologies may obscure the subject matter of the present invention, the detailed description will be omitted. Throughout the specification, when a part “includes” a certain component, this means that other components may be further included instead of excluding other components, unless specifically stated to the contrary.

The present inventors faced a problem of limited use for food due to the dissolution and decomposition characteristics of the phenol-based primary antioxidant used to prevent the oxidation of the polycarbonate resin. As a result of repeated studies, polycarbonate resin It is possible to implement a polycarbonate resin composition excellent in applicability for food while maintaining the existing properties while adding only the antioxidant, and dissolving the coloring agent in the release agent in the production process of the polycarbonate resin composition to prepare an antioxidant as an antioxidant. It has been discovered that the use of bays can solve the problems of dispersibility and solubility of additives that have not been solved, leading to the present invention.

Accordingly, the present invention provides a polycarbonate resin composition for food comprising 98 to 99.98% by weight of polycarbonate, 0.01 to 1% by weight of antioxidant made of phosphorus-based antioxidant, 0.01 to 1% by weight of release agent, and 0.1 to 10 ppm of colorant. , As a method of preparing the polycarbonate resin composition of the composition, the polycarbonate resin composition is prepared by adding and mixing an antioxidant, a release agent, and a colorant composed of a phosphorus-based antioxidant into a polycarbonate, and dissolving the colorant in a release agent. It provides a method for producing a polycarbonate resin composition for food comprising the step of.

Hereinafter, each component of the polycarbonate resin composition according to the present invention will be described in more detail, and then a method of manufacturing the polycarbonate resin composition will be described in detail.

(A) Polycarbonate

In the present invention, the polycarbonate is obtained by reacting a divalent phenol and a carbonate precursor, and examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound, The production method of the polycarbonate used in the present invention is not particularly limited.

In the present invention, the polycarbonate resin may have a weight average molecular weight of 5,000 to 200,000, preferably 10,000 to 80,000, and branched chains may be used, preferably 0.05 to 2 with respect to the total amount of diphenol used for polymerization. Molar% tri- or higher polyfunctional compounds, such as those prepared by adding a compound having a trivalent or higher phenol group, may be used.

In addition, the polycarbonate resin may be used as a polymer of bisphenol-A having a melt index (300 ° C, 1.2 kg load) of 3 to 40 g / 10min, preferably 5 to 28 g / 10min. . When the melt index is less than 3 g / 10min, the processing temperature may be high, so that molding may be difficult, and when it exceeds 40 g / 10min, the strength may be weak.

In the present invention, the polycarbonate resin is included in a content of 98 to 99.98% by weight for balance of physical properties such as elution safety, optical properties, long-term heat resistance, and mechanical properties of the final polycarbonate resin composition in consideration of the phosphorus-based antioxidant and release agent contents described later, Preferably it may be included in a content of 98.6 to 99.9% by weight, more preferably 99.2 to 99.9% by weight.

(B) Phosphoric antioxidant

In the present invention, as an antioxidant for preventing the oxidation of polycarbonate, phosphorus-based antioxidants are mixed and used alone in consideration of the problem of limited use for food due to dissolution and decomposition characteristics of conventional phenol-based primary antioxidants.

The phosphorus-based antioxidant is not particularly limited, such as tris-2,4-di-t-butylphenyl-phosphite, bis-2,4-dicumylphenyl-pentaerythritol-diphosphite, tetrakis-2, 4-di-t-butylphenyl-1,1-biphenyl-4,4-diylbisphosphite, bis-2,6-di-t-butyl-4-methylphenyl-pentaerythritol-diphosphite, etc. are preferred. Can be used, more preferably tris-2,4-di-t-butylphenyl-phosphite can be used.

It is preferable that the phosphorus-based antioxidant has a weight average molecular weight of 300 to 1,000 and a melting point of 100 to 300 ° C.

In the present invention, the phosphorus-based antioxidant is included in an amount of 0.01 to 1% by weight for the balance of physical properties such as elution safety, optical properties, long-term heat resistance, and mechanical properties of the final polycarbonate resin composition, preferably 0.02 to 0.6% by weight, more preferably It may be included in a content of 0.05 to 0.3% by weight. When the phosphorus-based antioxidant content is less than 0.01% by weight, thermal decomposition and yellowing of polycarbonate may occur, and when it exceeds 1% by weight, the color tone of polycarbonate may be affected or the transmittance may be reduced.

(C) release agent

In the present invention, a mold release agent is included to improve the processing and moldability of the polycarbonate resin composition.

The release agent is not particularly limited, for example, pentaerythritol tetrastearate, glycerin monostearate, stearyl stearate, propanediol stearate, and the like can be preferably used, and more preferably pentaerythritol tetrastearate Can be used.

In the present invention, the release agent is included in an amount of 0.01 to 1% by weight to balance the physical properties of the final polycarbonate resin composition, and more preferably 0.05 to 0.8% by weight, more preferably 0.1 to 0.5% by weight in consideration of the processability of the resin. Content.

(D) Coloring agent

In the present invention, a colorant for realizing the color of the polycarbonate resin is included.

When using a phenol-based primary antioxidant in a conventional polycarbonate resin, it may be considered that a primary antioxidant is not added to solve the problem of limited use for food due to elution and decomposition. In general, a coloring agent is used as a primary antioxidant. Since it is injected after dissolving in this case, in this case, there was a problem that the coloring agent could not be added to the production process, and when considering the addition of the antioxidant, there was a problem of dispersibility and solubility of the additive, but in the present invention, phosphorus-based antioxidant was used alone as an antioxidant. Meanwhile, it is possible to solve this problem by dissolving the colorant in the release agent and then adding it.

The colorant is not particularly limited, for example, solvent violet 59 (Solvent Violet 59, CAS No. 6408-72-6), solvent violet 36 (Solvent Violet 36, CAS No. 61951-89-1), solvent violet 31 ( Solvent Violet 31, CAS No. 70956-27-3), Solvent Violet 13, CAS No. 81-48-1, Solvent Blue 122, CAS No. 67905-17-3, Solvent Blue 45, CAS No. 37229-23-5, Solvent Blue 97, CAS No. 61969-44-6, Solvent Blue 104, CAS No. 116-75 -6) and the like can be preferably used, and more preferably, solvent violet 59 or solvent blue 97 can be used.

In the present invention, the colorant is included in an amount of 0.1 to 10 ppm for the balance of physical properties of the final polycarbonate resin composition, and in consideration of the color tone characteristics of the resin, it is preferably 0.2 to 5 ppm, more preferably 0.3 to 1 ppm. Can be included.

On the other hand, the polycarbonate resin composition according to the present invention may further include additives according to each use within a range not departing from the purpose. As an additive, a light stabilizer, a lubricant, a lubricant, a UV stabilizer, a coupling enhancer, a heat stabilizer, a plasticizer, and an impact modifier may be added alone or in a mixture of two or more, and the polycarbonate resin may be additionally added. 0.1 to 10 parts by weight based on 100 parts by weight of the composition may be added.

In the case of the heat stabilizer, a polycarbonate resin composition may be included to prevent a decrease in molecular weight and color deterioration. As the heat stabilizer, phosphorous acid, phosphoric acid, aphosphonic acid, phosphonic acid, and esters thereof may be used.

Hereinafter, a method for manufacturing a polycarbonate resin composition for food according to the present invention will be described in more detail.

The preparation of the polycarbonate resin composition for food according to the present invention can be basically performed by a known method. For example, an antioxidant, a release agent, and a colorant made of a phosphorus-based antioxidant may be added to a polycarbonate obtained by melt polymerization to a mixer such as an additive drum mixer and mixed to prepare a polycarbonate resin composition in which additives are mixed.

However, in the present invention, in order to solve the dispersibility and solubility problem when adding a phosphorus-based antioxidant in place of a conventional phenol-based antioxidant added to a polycarbonate resin, especially when adding a colorant, a method that has not been suggested in the conventional method That is, it is possible to provide a polycarbonate resin composition for foods excellent in dispersibility and solubility of an additive without using a phenol-based primary antioxidant by dissolving and adding a colorant to a release agent.

At this time, it is preferable to adjust the temperature condition in the mixing after the additive is added to 100 to 250 ° C, more preferably 130 to 180 ° C, and even more preferably 140 to 160 ° C.

Hereinafter, a specific embodiment according to the present invention will be described.

First, the specifications of the components used in Examples and Comparative Examples of the present invention are as follows.

(A) Polycarbonate resin

A polycarbonate resin (Lotte Chemical) of bisphenol-A having a melt index (300 ° C., 1.2 kg load) of 22 g / 10 min and a weight average molecular weight of 20,000 to 25,000 was used.

(B) Phosphoric antioxidant

ADK 2112 (adeca) of tris (2,4-di-tert-butylphenyl) phosphite structure was used.

(C) release agent

P861 (Emery) having a pentaerythritol tetrastearate structure was used.

(D) Coloring agent

A mixture of Solvent Violet 59 and Solvent Blue 97 (Solusys) was used.

(E) Phenolic primary antioxidant (1)

AO-50 (adeca) having an octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate structure was used.

(F) Phenolic primary antioxidant (2)

AO-60 (adeca) having a pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate structure was used.

Example 1

0.19.7 parts by weight of a phosphorus-based antioxidant, 0.2 parts by weight of a release agent, and 0.4 ppm of a colorant were added to and mixed with the additive drum mixer in 99.7 parts by weight of polycarbonate resin obtained by melt polymerization. When the additives were added, the colorant was dissolved in the release agent, and the additive drum temperature was adjusted to 150 ° C. The mixed mixture is extruded using a twin screw extruder (twin screw extruder, screw diameter 26 mm, L / D = 40) under the conditions of an extrusion temperature of 270 to 300 ° C and a screw rotation speed of 200 rpm to produce a pellet-like polycarbonate resin composition. Then, a specimen of 50 × 70 × 3mm (width × length × height) was molded using a 170MT injection machine.

Example 2

When adding the additive in Example 1, the specimen was molded in the same manner as in Example 1, except that the colorant was added without dissolving it in other additives.

Example 3

When adding the additive in Example 1, the colorant was added without dissolving it in other additives, and the specimen was molded in the same manner as in Example 1, except that the additive drum temperature was adjusted to 220 ° C.

Example 4

When adding the additive in Example 1, the specimen was molded in the same manner as in Example 1, except that the colorant was dissolved and added to the phosphorus-based antioxidant.

Example 5

In Example 1, when the additive was added, the colorant was dissolved in phosphorus-based antioxidant, and the specimen was molded in the same manner as in Example 1, except that the additive drum temperature was adjusted to 220 ° C.

Comparative Example 1

99.6 parts by weight of polycarbonate resin obtained by melt polymerization was added and mixed with 0.02 parts by weight of phenol-based primary antioxidant (1), 0.1 parts by weight of phosphorus-based antioxidant, 0.2 parts by weight of release agent, and 0.4 ppm of colorant to the additive drum mixer. When the additives were added, the colorant was dissolved in the phenolic primary antioxidant (1), and the additive drum temperature was adjusted to 150 ° C. The mixed mixture is extruded using a twin screw extruder (twin screw extruder, screw diameter 26 mm, L / D = 40) under the conditions of an extrusion temperature of 270 to 300 ° C and a screw rotation speed of 200 rpm to produce a pellet-like polycarbonate resin composition. Then, a specimen of 50 × 70 × 3mm (width × length × height) was molded using a 170MT injection machine.

Comparative Example 2

In Comparative Example 1, a specimen was molded in the same manner as in Comparative Example 1, except that the phenolic primary antioxidant (2) was used instead of the phenolic primary antioxidant (1).

Test example

The dissolution stability, yellowing index (YI), long-term heat resistance (YI), and IZOD impact strength were measured for the specimens according to Examples 1 and 2 according to the following method, and the results are shown in Table 1 below. , In the case of preparing the polycarbonate resin composition according to Examples 1 to 5, dispersibility and solubility are relatively evaluated and the results are shown in Table 2 below.

[How to measure]

(1) Dissolution safety in food contact

It was judged according to FDA 21 CFR 178. 2010 regulations.

(2) Yellowness Index (YI)

The specimen was injection molded at 300 ° C, and the yellowing index was measured according to the ASTM D1925 evaluation method.

(3) Long-term heat resistance (Yellowness Index, YI)

The specimens were injection molded at 300 ° C, and after a long-term heat resistance evaluation in an oven at 135 ° C for 500 hours, the yellowing index was measured according to ASTM D1925 evaluation method.

(4) IZOD impact strength

Notched specimens (1/8 ") were measured for IZOD impact strength (23 ° C) according to ASTM D256 evaluation.

Referring to Table 1 above, the polycarbonate resin composition (Example 1) containing only a phosphorus-based antioxidant and not a phenol-based primary antioxidant as an antioxidant according to the present invention is poly containing a phenol-based primary antioxidant. Compared to the carbonate resin composition (Comparative Examples 1 and 2), it can be confirmed that the dissolution safety upon food contact, the initial yellowing index, long-term heat resistance, and △ YI and IZOD impact strength are all excellent.

In addition, referring to Table 2, when adding and dissolving the colorant in the release agent when the additive is added (Example 1), the colorant is directly added (Examples 2 and 3), or when the colorant is dissolved in a phosphorus-based antioxidant. It can be seen that, compared to (Examples 4 and 5), the dispersibility of the additive in the additive drum and the superiority are excellent.

The preferred embodiments of the present invention have been described above in detail. The description of the present invention is for illustrative purposes, and those skilled in the art to which the present invention pertains will appreciate that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Therefore, the scope of the present invention is indicated by the following claims rather than the description of the present invention, and it is interpreted that all changes or modified forms derived from the meaning, scope and equivalent concepts of the claims are included in the scope of the present invention. Should be.

Claims (6)

Polycarbonate resin composition for food comprising 98 to 99.98% by weight of polycarbonate, 0.01 to 1% by weight of antioxidant made of phosphorus-based antioxidant, 0.01 to 1% by weight of release agent, and 0.1 to 10 ppm of colorant. According to claim 1,
The phosphorus antioxidant is tris-2,4-di-t-butylphenyl-phosphite, bis-2,4-dicumylphenyl-pentaerythritol-diphosphite, tetrakis-2,4-di-t-butyl One or more selected from the group consisting of phenyl-1,1-biphenyl-4,4-diylbisphosphite and bis-2,6-di-t-butyl-4-methylphenyl-pentaerythritol-diphosphite Characterized by a polycarbonate resin composition for food. According to claim 1,
The release agent is a pentaerythritol tetrastearate, glycerin monostearate, stearyl stearate and propanediol stearate at least one member selected from the group consisting of food polycarbonate resin composition. According to claim 1,
The colorant is Solvent Violet 59 (Solvent Violet 59, CAS No. 6408-72-6), Solvent Violet 36 (Solvent Violet 36, CAS No. 61951-89-1), Solvent Violet 31 (Solvent Violet 31, CAS No. 70956-27-3), Solvent Violet 13, CAS No. 81-48-1, Solvent Blue 122, CAS No. 67905-17-3, Solvent Blue 45 , CAS No. 37229-23-5), Solvent Blue 97, CAS No. 61969-44-6 and Solvent Blue 104, CAS No. 116-75-6 Polycarbonate resin composition for food, characterized in that at least one selected. A method for preparing a polycarbonate resin composition for food, comprising adding and mixing an antioxidant, a release agent, and a coloring agent made of a phosphorus-based antioxidant into a polycarbonate into a mixer to dissolve the coloring agent into a release agent and then adding it. . The method of claim 5,
The mixing is a polycarbonate resin composition manufacturing method for food, characterized in that is carried out at a temperature condition of 100 ~ 250 ℃.