KR101374367B1 - Radiation resistant resin and medical housings using the same - Google Patents

Abstract

Radiation-resistant resin of the present invention is (A) (a1) polycarbonate resin; And (a2) a base resin comprising a copolyester resin; And (B) a higher aliphatic phosphate compound. Since the radiation resistant resin has excellent radiation resistance, transparency and color stability, it can be suitably used for medical exterior materials.

Description

Radiation-resistant resins and medical exterior materials using the same

The present invention relates to a radiation-resistant resin and a medical exterior material using the same. More specifically, the present invention relates to a radiation-resistant polycarbonate resin having excellent radiation resistance, transparency and color stability by introducing a higher aliphatic phosphate, and a medical exterior material using the same.

Recently, polymer materials have been increasingly used as medical materials such as replacement of medical devices and raw materials. When a polymer material is used as a medical material, since it is used in direct or indirect contact with a living body, the physical properties of the molded product as well as sterility are very important.

In general, the sterilization method is a high-pressure method for killing microorganisms by heating in saturated steam of a suitable temperature and pressure or dry heat air, and there is an irradiation method for killing microorganisms by irradiating gamma rays, electron beams, X-rays. In addition, there is a method of killing microorganisms using a sterilizing gas such as ethylene oxide, formaldehyde, hydrogen peroxide and chlorine dioxide gas. In case of sterilization using sterilization gas, the temperature, humidity, gas concentration and sterilization time during sterilization are different according to the type of gas, and the remaining gas may adversely affect the human body. Need attention In recent years, the irradiation method to sterilize by exposure to gamma rays is evaluated as preferable, but because of the high energy irradiation for sterilization, polymer materials may adversely affect during the sterilization process. In particular, polycarbonate has favorable conditions for being used as a medical exterior material due to its high transparency and excellent physical properties. However, when gamma rays are irradiated to molded products molded using polycarbonate, yellowing phenomenon occurs seriously, and transparency is significantly reduced. This is being limited.

JP1996-048859 describes a method for adding polyester-polycarbonate polymers, polyesters, copolyesters, polysulfone-carbonates, polyamides, etc., and US Pat. No. 4,786,692 polycarbonate / copolyester blends. Reference is made to the composition. However, the resin composition blended with the polycarbonate copolyester is improved resistance to gamma rays, but yellowing occurs during high temperature processing, the initial color deteriorates, which greatly affects the color after gamma irradiation.

In US 4,657949, US 4,757,104 and US 4,804,692, sorbic acid compounds, silicone compounds, sulfone compounds, and polyalkylene glycols have been added to prevent the above problems, but problems of color stability and yellowing are not fundamentally solved. .

Therefore, the development of a radiation-resistant polycarbonate resin having excellent transparency and color stability is required.

An object of the present invention is to provide a radiation resistant resin having excellent transparency and color stability.

Another object of the present invention is to provide a radiation resistant resin that is excellent in transparency and radiation resistance and suitable for use in medical exterior materials.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a radiation resistant resin. The radiation resistant resin is (A) (a1) polycarbonate resin; And (a2) a base resin comprising a copolyester resin; And (B) a higher aliphatic phosphate compound.

In embodiments, the (B) higher aliphatic phosphate compound includes at least one of the compounds represented by Formula 2 or 3 below:

(2)

(3)

In Formulas 2 and 3, n and m are integers of 11 to 20, and n and m are the same as or different from each other.

The radiation-resistant resin is characterized in that the yellowing index (ΔYI) by ASTM D1925 after 50kGy irradiation is 10 or less.

In embodiments, the radiation resistant resin is (A) (a1) 50 to 90% by weight of a polycarbonate resin; And (a) 0.01 to 2 parts by weight of (B) phosphate compound based on 100 parts by weight of the base resin including 10 to 50% by weight of the copolyester resin.

The (a2) copolyester resin may include units derived from 1,4-cyclohexanedimethanol.

In an embodiment, the (a2) copolyester resin contains an aromatic or aliphatic dieside residue and two or more diol residues, and 1,4-cyclohexanedimethanol of the diol residues may be 50 mol% or more.

The radiation resistant resin may further include a polyalkylene oxide.

In embodiments, the polyalkylene oxide may have a number average molecular weight of 500 to 20,000 g / mol.

The radiation-resistant resin is an antibacterial agent, a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a stabilizer, a lubricant, an antistatic agent, a colorant, a weather agent, a colorant, a UV absorber, a sunscreen, a flame retardant Additives such as fillers and nucleating agents may be further included. The additives may be used alone or in combination of two or more thereof.

Another aspect of the present invention relates to a molded article molded from the radiation resistant resin. Radiation-resistant resins of the present invention, as well as transparency, color stability and impact strength, and particularly excellent radiation resistance can be preferably applied to medical exterior materials.

The present invention has the effect of the invention to provide a radiation resistant resin that is excellent in radiation resistance with excellent transparency and color stability and suitable for use in medical exterior materials.

Hereinafter, specific examples of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Radiation-resistant resin according to an embodiment of the present invention is (A) (a1) polycarbonate resin; And (a2) a base resin comprising a copolyester resin; And (B) higher aliphatic phosphate compounds.

Hereinafter, each component of the present invention will be described in detail.

(A) Basic resin

(a1) polycarbonate resin

The polycarbonate resin may be prepared by reacting a diphenol represented by the following formula (1) with phosgene, a halogen acid ester, a carbonic acid ester, or a combination thereof.

[Chemical Formula 1]

Wherein A is a single bond, a substituted or unsubstituted C1 to C30 linear or branched alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylene group A substituted or unsubstituted C1 to C30 linear or branched haloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkenylene group, a substituted or unsubstituted C5 to C10 cycloalkylidene groups, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C1 to C20 linear or branched alkoxysylene groups, halogen acid ester groups, carbonate ester groups, CO, S or SO ₂ , R ₁ and R ₂ are the same or different and each is a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, n ₁ and n ₂ each represent an integer of 0 to 4 It is an integer.)

The diphenols represented by the above formula (1) may be composed of two or more of them to form a repeating unit of a polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether, and the like. Preferred examples thereof include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1- Hexane can be used. More preferably, 2,2-bis (4-hydroxyphenyl) propane can be used.

The polycarbonate resin may use a weight average molecular weight of 10,000 g / mol to 200,000 g / mol, in the specific embodiment may be used 15,000 g / mol to 80,000 g / mol, but is not limited thereto.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin.

Examples of the linear polycarbonate resin include a bisphenol-A polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid and the like with a diphenol and a carbonate. The polyfunctional aromatic compound may be contained in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. As the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate and the like can be used.

The melt flow index (MFI) of the polycarbonate resin may be 3 to 120 g / 10 min under measurement conditions of 310 ° C. and 1.2 kgf.

The polycarbonate resin constituting the base resin, it may be included in 50 to 90% by weight of the total base resin. Preferably it may be included in 60 to 80% by weight. When the polycarbonate resin is included in the content range, it is possible to obtain a balance of physical properties of impact strength, transparency, radiation resistance and processability.

(a2) copolyester resin

The copolyester resin comprises units derived from 1,4-cyclohexanedimethanol.

In an embodiment, the (a2) copolyester resin contains an aromatic or aliphatic dieside residue and two or more diol residues, wherein 1,4-cyclohexanedimethanol is preferably at least 50 mol% of the diol residues. Preferably 60% or more. In specific embodiments, 1,4-cyclohexanedimethanol is 50 to 99 mol%, preferably 60 to 80 mol%. It is possible to give excellent balance of physical properties of fluidity and transparency in the above range.

The (a2) copolyester resin may be prepared by a conventional method by condensation polymerization of an aromatic or aliphatic dieside and two or more diols.

The dieside may be adipic acid, azelic acid, dicarboxylic dodecanoic acid, succinic acid, norbornene dicarboxylic acid, 1,4-cyclohexanedicarbosilic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4- or 1, 5-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, and the like, but are not necessarily limited thereto. These may be used alone or in combination of two or more. Among these, terephthalic acid and isophthalic acid are preferable.

As the diol, linear, branched, cyclic alkane diols having 2 to 12 carbon atoms may be used together with 1,4-cyclohexanedimethanol. For example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and the like may be used, and these may be used alone or in combination of two or more thereof. Preferably, it is a combination of 1,4-cyclohexanedimethanol and ethylene glycol.

In embodiments, the (a2) copolyester resin may be amorphous.

Melt Flow Index (MFI) of the (a2) copolyester resin may be 3 to 50 g / 10 min under measurement conditions of 250 ° C. and 1.2 kgf.

The (a2) copolyester resin constitutes a base resin, and may be included in 10 to 50% by weight of the total base resin. Preferably it may be included in 20 to 40% by weight. When the copolyester resin (a2) is included in the content range, it is possible to obtain a balance of physical properties of impact strength, transparency, radiation resistance and processability.

(B) higher aliphatic phosphate compounds

The higher aliphatic phosphate compound (B) may be a phosphate containing an alkyl group having 13 or more carbon atoms. The alkyl group is preferably a linear alkyl group.

In embodiments, the (B) phosphate compound includes at least one of the compounds represented by Formula 2 or 3:

(2)

(3)

In Formulas 2 and 3, n and m are integers of 11 to 20, and n and m are the same as or different from each other.

In Formulas 2 and 3, n and m are integers of 11 to 20, and n and m are the same as or different from each other.

N and m are preferably 15 to 20.

Preferably, the (B) higher aliphatic phosphate compound may be used in combination of two or more kinds. For example, the dialkyl acid phosphate of general formula (2) and the monoalkyl acid phosphate of general formula (3) can be mixed and used.

The (B) higher aliphatic phosphate compound may be used in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the base resin. It can have excellent radiation resistance and balance of physical properties in the above range.

(C) polyalkylene oxide

Radiation-resistant resin of the present invention may optionally further comprise a polyalkylene oxide. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polybutylene oxide and the like. These may be used alone or in combination of two or more.

In embodiments, the polyalkylene oxide may have a number average molecular weight of 500 to 20,000 g / mol. Excellent radiation resistance can be given in the above range.

When the polyalkylene oxide is included, the synergistic effect with the higher aliphatic phosphate compound (B) may be exerted to have a better radiation resistance effect. The polyalkylene oxide may be used in an amount of 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the base resin. Excellent balance of radiation resistance and moldability in the above range can be obtained.

The radiation-resistant resin is an antibacterial agent, a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a stabilizer, a lubricant, an antistatic agent, a colorant, a weather agent, a colorant, a UV absorber, a sunscreen, a flame retardant Additives such as fillers and nucleating agents may be further included. The additives may be used alone or in combination of two or more thereof.

As the antioxidant, a phenol type, phosphite type, thioether type or amine type antioxidant may be used.

The release agent may be a fluorine-containing polymer, silicone oil, metal salt of stearic acid, metal salt of montanic acid, montanic acid ester wax or polyethylene wax.

As the weathering agent, a benzophenone type or an amine weathering agent may be used, and the coloring agent may be a dye or a pigment.

Titanium dioxide (TiO ₂ ) or carbon black may be used as the sunscreen.

The filler may be glass fiber, carbon fiber, silica, mica, alumina, clay, calcium carbonate, calcium sulfate or glass beads. Talc or clay may be used as the nucleating agent.

The additive may be suitably included within a range that does not impair the physical properties of the radiation-resistant resin, in specific embodiments may be included in 40 parts by weight or less with respect to 100 parts by weight of the base resin, more specifically in the 0.1 to 30 parts by weight May be included.

Another aspect of the present invention relates to a molded article molded from the radiation resistant resin. Radiation-resistant resin of the present invention is not only excellent in transparency, color stability and impact strength, but also radiation resistance, blood oxygenator, blood collective reservoir, blood separation device, b1ood collection device, surgical instrument, kidney analysis equipment centrifuge bowl, medical It can be usefully applied to medical exterior materials such as lab equipment, hemodialyzer and the like.

The radiation resistant resin of the present invention may have a yellowing index (ΔYI) of 10 or less, preferably 0.1 to 7, more preferably 0.1 to 5, according to ASTM D1925 after 50 kGy irradiation.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specifications of each component used in the following examples and comparative examples are as follows.

(A) Basic resin

(a1) polycarbonate resin

Bisphenol A and diphenyl carbonate were prepared by transesterification in a molten state as a PC derived from bisphenol A, and a polycarbonate resin having a flow index (300 ° C., 1,2 kg) of about 8.0 g / 10 min was used.

(a2) copolyester resin

As PCTG based on terephthalic acid, ethylene glycol and 1,4-cyclonucleic acid dimethanol, the flow index (250 ° C., 1.2 kg) was used as JN200 of SK Chemical Co., Ltd., which was about 8.9 g / 10 min.

(B) higher aliphatic phosphates

AX-71 manufactured by Adeka was used.

(B ′) Aromatic Phosphate: PHOSFLEX TPP (triphenylphosphate) made from DAIHACHI P was used.

(B ") Lower aliphatic phosphate: tributyl phosphate prepared from sigma-aldrich was used.

(C) Polyalkylene oxide: PPG of BASF Mn = 2,000 was used.

(D) Additive: PEP-36 of the phosphite antioxidant Adeka was used.

Example  1 to 7 and Comparative Example  1 to 6

Each component was added in an amount as described in Table 1 below, and then extruded in a 45 φ twin screw extruder at a temperature of 230˜280 ° C. to prepare pellets. After drying the pellets hot air at 80 ~ 120 ℃ for 3 hours or more, using a 6 oz injection molding machine, to produce a specimen of thickness 3mm at a temperature of 240 ~ 290 ℃ and to prepare a physical specimen. The prepared physical property specimens were measured for physical properties by the following method and the results are shown in Table 1 below. The gamma rays produced by Co ₆₀ were irradiated with absorbed doses of 25 kGy and 50 kGy at doses of 10 kGy per hour to measure the yellowing index (ΔYI) and total light transmittance (TT) before and after gamma irradiation.

Property measurement method:

1) Total light transmittance (TT): measured in accordance with ASTM D1003 using a specimen of thickness 3mm (unit:%).

2) Yellowing index (ΔYI): 2 days after irradiation, YI-YI before irradiation was evaluated by permeation according to ASTM D1925.

Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 5 6 (a1) PC 80 70 70 70 70 70 60 100 100 70 70 70 70 (a2) PCTG 20 30 30 30 30 30 40 - - 30 30 30 30 (B) 0.2 0.1 0.2 0.5 0.2 0.2 0.2 - - - - - 3 (B ') - - - - - - - - - - 0.2 - - (B ") - - - - - - - - - - - 0.2 - (C) - - - - 0.1 0.5 - - 0.5 - - - - (D) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Joe's Dictionary
All light
Transmittance 88.7 89.1 89.3 89.2 89.2 89.3 89.4 88.9 89.0 89.2 89.0 89.1 88.9 After 50kGy irradiation
All light
Transmittance 86.4 87.9 87.9 88.0 88.1 88.5 88.4 85.9 86.4 86.5 87.8 87.5 88.4 After 50kGy irradiation
Yellowness Index
(ΔYI) 9.10 7.11 6.82 6.08 3.10 2.95 3.18 27.21 28.72 12.91 6.98 6.68 4.12

As shown in Table 1, Examples 1 to 7 can be confirmed that the decrease in transparency after UV irradiation is less than 3% and the yellowing index is low. In particular, it can be seen that Examples 5 and 6 to which a polyalkene oxide is applied are significantly lower in the yellowing index. On the other hand, Comparative Examples 1 to 3 without applying the higher aliphatic phosphate compound showed significantly higher yellowing index, and Comparative Examples 4 and 5 using the aromatic aliphatic phosphate instead of the higher aliphatic phosphate or the lower aliphatic phosphate had no radiation-resistant effect. It can be seen that there is no. In addition, Comparative Example 6, in which an excess aliphatic phosphate compound was applied, generated a large amount of gas during injection molding.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (9)

(A) 50 to 90% by weight of (a1) polycarbonate resin; And (a2) 100 parts by weight of a base resin including 10 to 50% by weight of a copolyester resin; And
(B) 0.01 to 2 parts by weight of a higher aliphatic phosphate compound;
, ≪ / RTI >
(B) the higher aliphatic phosphate compound is a radiation-resistant resin, characterized in that at least one of the compounds represented by the following formula (2) or (3):

(2)

(3)

In Formulas 2 and 3, n and m are integers of 11 to 20, and n and m are the same as or different from each other.

The radiation resistant resin of claim 1, wherein the radiation resistant resin has a yellowing index (ΔYI) of 10 or less according to ASTM D1925 after 50 kGy irradiation.
The radiation resistant resin according to claim 1, wherein the (a2) copolyester resin comprises a unit derived from 1,4-cyclohexanedimethanol.
The copolyester resin of claim 1, wherein the (a2) copolyester resin contains an aromatic or aliphatic dieside residue and two or more diol residues, wherein 1,4-cyclohexanedimethanol is 50 mol% or more in the diol residues. Radiation-resistant resin, characterized in that.
The radiation resistant resin of claim 1, wherein the radiation resistant resin further comprises a polyalkylene oxide.
6. The radiation resistant resin according to claim 5, wherein the polyalkylene oxide has a number average molecular weight of 500 to 20,000 g / mol.
The radiation-resistant resin according to claim 5, wherein the polyalkylene oxide is contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the base resin.
The method of claim 1, wherein the radiation-resistant resin is antibacterial, thermal stabilizer, antioxidant, release agent, light stabilizer, inorganic additives, surfactants, coupling agents, plasticizers, stabilizers, lubricants, antistatic agents, colorants, weathering agents, colorants, ultraviolet rays A radiation resistant resin comprising at least one additive selected from the group consisting of absorbents, sunscreens, flame retardants, fillers and nucleating agents.
A medical exterior material molded from the radiation resistant resin according to any one of claims 1 to 8.