JP3403277B2 - Polybutylene terephthalate resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polybutylene terephthalate resin composition which is a high-density thermoplastic resin having antibacterial properties. In particular, the present invention relates to a resin composition suitable for various containers, wall materials, floor materials, housing materials such as table tops, and interior decorations.

[0002]

2. Description of the Related Art Conventionally, a thermoplastic resin has been used for various containers, wall materials, floor materials, house materials such as table tops, and upholstery products because of its ease of manufacture. Japanese Patent Application Laid-Open No. 3-1
Japanese Patent No. 85069 proposes to add barium sulfate. Furthermore, in such applications, it is required to suppress bacteria generated during use and obtain a comfortable living environment. Therefore, attempts have been made to add an organic / inorganic antibacterial agent to a polymer to obtain a polymer molding having antibacterial properties.

[0003] However, many organic antibacterial agents cause many decomposition problems at high temperature during molding process and cannot exhibit desired performance, and they are more toxic than inorganic ones, and therefore have many problems in production. . Inorganic antibacterial agents are generally highly stable and have excellent antibacterial effects, but have a high water absorption rate, which reduces the molecular weight of the polymer during kneading and has the drawback of adversely affecting various physical properties. is there. Further, it has a problem in dispersibility as compared with the organic type, which causes a defect in appearance of the molded product. Therefore, the actual situation is that a thermoplastic material having antibacterial properties sufficiently satisfying the above-mentioned applications has not yet been obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high density polybutylene terephthalate resin composition having good antibacterial properties, no decrease in molecular weight, and excellent mechanical strength, especially impact resistance. To do.

[0005]

The present invention has been made to solve the above-mentioned problems, and the gist thereof is 10 to 50% by weight of polybutylene terephthalate resin, 10 to 50% by weight of polycarbonate resin, and chlorine. Content is 500
A powder of water-soluble glass containing 10 to 80% by weight of barium sulfate, which is less than or equal to ppm, and one or more metal ions selected from the group consisting of Ag ⁺ , Cu ²⁺ and Zn ^2+. It exists in a polybutylene terephthalate resin composition formed by blending.

The present invention will be described in detail below. The polybutylene terephthalate (hereinafter sometimes abbreviated as "PBT") resin in the present invention is a polymer composed of butylene terephthalate units obtained by polycondensing 1,4-butylene glycol and terephthalic acid or a derivative thereof. There may be a copolymer obtained by substituting a part of the terephthalic acid component or the 1,4 butylene glycol component with another copolymerization component. As the copolymerization component, as the acid component, dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid and cyclohexanedicarboxylic acid are used. Can be mentioned. Examples of the glycol component include ethylene glycol, trimethylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolyglycol of polyethylene glycol and polypropylene glycol. However, the proportion of the copolymerization component is preferably less than 30% by weight based on the whole polymer.

The PBT of the present invention preferably has an intrinsic viscosity of 0.5 to 2 dl / g, more preferably 1 to 2 dl measured at 30 ° C. in a mixed solvent of phenol / tetrachloroethane 1/1 (weight ratio). / G, most preferably 1.1-
One with 1.6 dl / g is used. The polycarbonate (hereinafter sometimes abbreviated as “PC”) resin in the present invention is produced by reacting a divalent phenol with a carbonate precursor by a solution method or a melting method. Typical examples of the divalent phenol include 2,2-bis- (4-hydroxyphenyl) propane [bisphenol A], bis- (4-hydroxyphenyl) methane, 1,1-bis- (4- Hydroxyphenyl) ethane, 2,2-bis- (4-hydroxy-3,5
-Dibromophenyl) propane, 2,2-bis- (4-
Hydroxy-3,5-dimethylphenyl) propane, bis- (4-hydroxyphenyl) sulfide, bis-
(4-hydroxyphenyl) sulfone and the like can be mentioned.

Of these, preferred are bisphenol A, bis- (4-hydroxyphenyl) methane, 1,
A bis- (4-hydroxyphenyl) alkane compound such as 1-bis- (4-hydroxyphenyl) ethane is used, and bisphenol A is particularly preferably used.
In addition, in manufacturing the polycarbonate resin, the above-mentioned 2
You may use a monohydric phenol individually or in mixture of 2 or more types. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like. Specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like are used. You may use these individually or in mixture of 2 or more types.

The viscosity average molecular weight of the polycarbonate resin is generally 10,000 to 100,000, preferably 15,000 to 60,000.
More preferably 15,000 to 40,000, particularly preferably 1.5
10,000 to 30,000. In producing a polycarbonate resin having these viscosity average molecular weights, an appropriate molecular weight modifier, a branching agent for improving processability, a catalyst for accelerating the reaction and the like may be added.

The amount of PBT compounded is 10 based on the total amount of the resin composition.
˜50 wt%, preferably 20-40 wt%. If this amount is too small, it is not preferable in terms of deterioration of chemical resistance. On the other hand, if the amount is too large, it is not preferable because the impact resistance is lowered. The compounding amount of PC is 10 to 50% by weight, preferably 20 to 40% by weight based on the entire resin composition. If this amount is too small, it is not preferable because the impact resistance is lowered. On the other hand, if the amount is too large, it is not preferable because the chemical resistance is lowered. Also, P
A preferable compounding ratio of BT and PC is PBT / PC =
It is 20 / 40-40 / 20. Too much PBT relative to PC is not preferable in that impact resistance is lowered. on the other hand,
If it is too small, it is not preferable in terms of deterioration of chemical resistance.

As barium sulfate in the present invention, barium sulfate having a chlorine content of 500 ppm or less is used. The chlorine content in barium sulfate is 50
If it exceeds 0 ppm, not only the color tone change of the resin after melt-kneading is significantly reduced, but also the impact resistance is adversely affected. The chlorine content is preferably 100 ppm or less,
Most preferably, it is 50 ppm or less.

The barium sulfate may be naturally produced or synthetically obtained, and as naturally produced barium sulfate, for example, natural barite crushed may be used. . Further, barium sulfate synthesized by a known synthesis method can be used as the product obtained by the synthesis. In order to make these barium sulfates have a chlorine content below a certain level specified in the present invention, the barium sulfate should be washed with hydrochloric acid, sulfuric acid, nitric acid, etc., preferably hydrochloric acid for 3 hours or more before kneading. Is preferred. Particularly, barium sulfate obtained from natural barite contains a large amount of impurities, and thus it is particularly preferable to perform such washing.

The particle size of barium sulfate used in the present invention is not particularly limited, but it is 0.5 to 50 microns, preferably 8 to 15 microns, and most preferably 10 to 12 microns. The compounding amount of barium sulfate is 10 based on the whole composition.
~ 80% by weight. If this amount is too large, it is not preferable because the impact resistance is lowered. On the other hand, if it is too small, it feels heavy.
Not good in terms of texture and appearance. The preferable range of the addition amount of barium sulfate is 30% by weight as the lower limit and 50% by weight as the upper limit.

In the present invention, the water-soluble glass particles containing one or more metal ions selected from the group consisting of Ag ⁺ , Cu ²⁺ and Zn ²⁺ are SiO ₂ , B ₂
The glass composition comprises one or more network-modifying oxides of O ₃ and P ₂ O ₅ and one or two network intermediate oxides of Al ₂ O ₃ and TiO _2. The composition contains 100% by weight of Ag ⁺ , Cu ²⁺ and Zn ²⁺ as an oxide, for example, in an amount of about 0.1 to 20.0% by weight. From the viewpoint of antibacterial effect, Ag ⁺ ions are preferable as the metal ions contained in the powdery particles of the water-soluble glass. 1 selected from the group consisting of Ag ⁺ , Cu ²⁺ and Zn ²⁺
The amount of the water-soluble glass powder or granules containing one kind or two or more kinds of metal ions is 0.1 to 10% by weight based on the whole polybutylene terephthalate resin composition, and antibacterial and mechanical properties are From the above point, it is preferably 0.5 to 5% by weight.

The water-soluble glass powder or granular material in the present invention is, for example, in the case of a water-soluble glass powder or granular material containing monovalent silver ions, due to the gelation phenomenon in water, the network-modified oxide and the network intermediate. The dissolution rate of solids consisting of body oxides in water is controlled by changing the composition ratio of the network intermediate oxides and the composition ratio of the network modifying oxides. It is produced by allowing it to be retained in a gel and gradually eluting in water. The polybutylene terephthalate resin composition of the present invention obtained by blending the water-soluble glass powder or granular material containing such a specific metal ion has excellent antibacterial properties, mechanical properties and high density.

A molded article obtained by molding the polybutylene terephthalate resin composition of the present invention holds water-soluble glass on its surface, and a glass component is formed on the surface of the molded article by a liquid which comes into contact therewith, such as moisture or moisture. Elute, Ag ⁺ , C
It is considered that u ²⁺ and / or Zn ²⁺ ions gradually elute on the surface of the molded body in accordance with the dissolution of the glass and exert an antibacterial effect.

If desired, the resin composition of the present invention may further contain other thermoplastic resin, such as polyamide, or a rubber component, as long as the effects of the present invention are not impaired. Further, in order to impart desired properties depending on its purpose, known substances generally added to thermoplastic resins, for example, flame retardants, flame retardant aids, inorganic reinforcing materials, lubricants, antioxidants, various stabilizers, Impact modifiers, plasticizers, release agents, colorants, crystallization accelerators, UV absorbers and the like can be added.

In particular, it is preferable to add an external lubricant for the purpose of improving releasability. In that case, 0.01 to 5% by weight, preferably 0.1 to 1% by weight, of the whole resin composition is added. Such external lubricants include esters of fatty acids and aliphatic alcohols, fatty acid amides, fatty acid metal salts, and the like, and specific examples thereof include calcium stearate and pentaerythritol tetrastearate. Any device or method can be used for producing the resin composition of the present invention. For example, it can be obtained by dry blending the above-mentioned necessary components with a mixer or the like and directly molding, or by melt-kneading with an extruder, a Banbury mixer, a heating roll or the like. Moreover, various additives as described above can be added as necessary.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

EXAMPLES The following components were used as the components in the following examples. In a mixed solvent of PBT: phenol / tetrachloroethane 1/1 (weight ratio), the intrinsic viscosity measured at 30 ° C. was 1.
Polybutylene terephthalate which is 4 dl / g. PC: Polycarbonate having a viscosity average molecular weight of 30,000. BaSO4: Average particle size 8 μm Antibacterial agent 1: Amoculin P-10 (powder / granule of water-soluble glass containing Ag ⁺ ions) Antibacterial agent 2: Zeolite AJ-10N

The antibacterial properties and impact resistance were evaluated by the following methods. 1 Antibacterial performance evaluation test method After dropping 0.5 ml of the test bacterial solution (prepared to 100,000 / ml) on the specimen, store at 25 ° C and store the viable cells on the specimen 48 hours after storage. It was measured by the pour plate culture method using a medium for measuring the number. ◯: Number of viable cells = 1,000 or less Δ: Number of viable cells = 1,000-10,000 ×: Number of viable cells = 10,000 or more 2 Impact resistance test method When a 1 kg steel ball was dropped on a molded product The maximum non-destructive height of was measured.

[Example-1] Predetermined amounts of the components shown in Table-1 were mixed in a mixer, and a single-screw volatile matter removal type extruder was used to set the temperature at 280 ° C and the rotation speed at 85 rpm. And extruded to produce pellets. Using the obtained pellets, at a molding temperature of 270 ° C., 30 mm × 30 mm × 2 m
An m-thick plate was injection molded. The molded articles obtained were evaluated for antibacterial properties and impact resistance. The results are shown in Table-1.

[0022]

[Table 1]

[0023]

INDUSTRIAL APPLICABILITY The polybutylene terephthalate resin composition of the present invention is a high-density resin composition having excellent antibacterial properties, less decrease in molecular weight, and excellent mechanical strength, especially impact resistance. Various containers that are required to suppress
It is suitable for wall materials, floor materials, household materials such as table tops, and upholstery.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 67/00-67/02 C08L 69/00

Claims (6)

(57) [Claims] 1. A polybutylene terephthalate resin 10 to 10.
50% by weight, polycarbonate resin 10 to 50% by weight,
Barium sulfate 10 having a chlorine content of 500 ppm or less
To 80% by weight, and polybutylene terephthalate prepared by blending powdery particles of water-soluble glass containing one or more metal ions selected from the group consisting of Ag ⁺ , Cu ²⁺ and Zn ^2+. Resin composition. 2. Barium sulfate having an average particle size of 0.5 to 5
The polybutylene terephthalate resin composition according to claim 1, which is 0 micron. 3. The polybutylene terephthalate resin composition according to claim 1, wherein the barium sulfate is obtained by washing natural barite to reduce the chlorine content to 500 ppm or less. 4. A powder of water-soluble glass containing one or more metal ions selected from the group consisting of Ag ⁺ , Cu ²⁺ and Zn ²⁺ , based on the entire polybutylene terephthalate resin composition. The polybutylene terephthalate resin composition according to any one of claims 1 to 3, wherein the granular material is blended in an amount of 0.1 to 10% by weight. 5. Gold contained in powder of water-soluble glass
Genus ion is Ag ⁺2. The method according to claim 1, wherein
Polybutylene terephthalate according to any one of Ishi 4
Resin composition. 6. The polybutylene terephthalate resin according to claim 1, wherein the lubricant is blended in an amount of 0.01 to 5 wt% with respect to the entire polybutylene terephthalate resin composition. Composition.