JP5032013B2 - Polycarbonate resin composition having plant-derived components - Google Patents

Description

  The present invention relates to a resin composition having a plant-derived component having improved reliability against stress. More specifically, the present invention relates to a resin composition containing a plant-derived component having improved elongation at break and improved moldability.

  Polycarbonate resins are excellent in transparency, heat resistance, and impact resistance, and are currently widely used in the electrical / electronic field, automobile field, optical part field, and other industrial fields. However, the polycarbonate resin has a problem that it is expensive and has a high melt viscosity and poor molding processability (fluidity). As one method for solving these problems, a polymer alloy with an ABS resin is known (for example, Patent Document 1). However, the elongation at break and other mechanical properties in the tensile test of a polymer alloy composed of polycarbonate resin and ABS resin are smaller than those of polycarbonate alone, that is, when stress is applied by adding ABS. There was a problem that it became poor in reliability. In order to improve this point, it is considered to add various third substances (for example, Patent Documents 2 to 5).

In addition, since the resin composition obtained in this way is manufactured using raw materials obtained from petroleum resources, there is a concern about global warming due to carbon dioxide generated due to the exhaustion of petroleum resources and incineration of waste. However, it is not a preferable material in recent years, and a material with a smaller environmental load and excellent recyclability is awaited.
In order to cope with such a problem, research on polycarbonate made of plant-derived materials has also been conducted (for example, Patent Document 6). However, since polycarbonate alone has a low elongation at break in a tensile test, a polymer having low reliability in stress and improved molding processability has been demanded.

Japanese Examined Patent Publication No. 38-15225 Japanese Patent Publication No. 48-12170 Japanese Patent Publication No.55-27579 Japanese Patent Publication No.57-21530 Japanese Patent Publication No.58-12300 International Publication No. 2004/111106 Pamphlet

  The object of the present invention is to solve these problems of the prior art described above, consisting of two components, a polycarbonate resin containing a plant-derived component as a polymerization unit and an addition polymerization type polymer, and further improving the elongation at break in a tensile test. It is to provide a polymer alloy.

（Ｒ_１〜Ｒ_４はそれぞれ独立に水素原子、アルキル基、シクロアルキル基およびアリール基）
で表されるジオール残基を含んで成り、全ジオール残基中式（１）で表されるジオール残基が４０〜１００モル％を占めるポリカーボネート１００重量部とＡＢＳ樹脂８０〜９９重量部とからなる樹脂組成物である。 That is, the present invention provides the following formula (1):

(R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group)
And 100 parts by weight of a polycarbonate in which the diol residues represented by the formula (1) occupy 40 to 100 mol% and 80 to 99 parts by weight of an ABS resin. It is a resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer alloy which consists of two components of the polycarbonate resin which contains a plant-derived component as a polymerization unit, and an addition polymerization type polymer, and the elongation at break improved in the tension test can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, these Examples and description illustrate the present invention, and do not limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.

（Ｒ_１〜Ｒ_４はそれぞれ独立に水素原子、アルキル基、シクロアルキル基およびアリール基）
で表されるジオール残基を含んで成り、全ジオール残基中式（１）で表されるジオール残基が４０〜１００モル％を占めるポリカーボネート１００重量部と付加重合型ポリマー２５〜４００重量部とからなる樹脂組成物である。 The resin composition according to the present invention has the following formula (1):

(R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group)
And 100 parts by weight of a polycarbonate in which the diol residues represented by the formula (1) occupy 40 to 100 mol% and 25 to 400 parts by weight of an addition-polymerizable polymer. It is the resin composition which consists of.

  If the weight ratio of the addition-polymerizable polymer to the polycarbonate is smaller than this range, the resulting resin composition has a high melt viscosity and requires a higher molding temperature, which is not preferable. If the weight ratio is larger than this range, sufficient heat resistance for use in various industrial applications cannot be obtained. The addition polymerization type polymer is preferably 25 to 150 parts by weight, more preferably 67 to 150 parts by weight, further preferably 80 to 150 parts by weight, and further preferably 80 to 99 parts by weight with respect to 100 parts by weight of the polycarbonate. .

  The diol residue represented by Formula (1) is 40-100 mol% in all the diol residues. When the ratio of the diol residue represented by the formula (1) is smaller than this range, the glass transition temperature of the resulting resin is lowered and the heat resistance is lowered, which is not preferable. On the other hand, when the ratio of the diol residue is larger than this range, the melt viscosity becomes high, a polymer having a high degree of polymerization cannot be obtained, and molding processing becomes difficult, which is not preferable. The ratio of the diol residue represented by the formula (1) is preferably 60 mol% or more and 90 mol% or less than the total diol residues.

  The polycarbonate preferably has a reduced viscosity of 0.1 dl / g or more, more preferably 0.35 dl / g or more, and further preferably 0.5 dl / g or more. Further, the weight average molecular weight is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 30,000 or more. When it is within this range, it has good melt fluidity and further has sufficient mechanical strength.

  To describe the glass transition temperature in more detail, the glass transition temperature of the polycarbonate represented by the above formula (1) is preferably 90 ° C. or higher. If the glass transition temperature is lower than this, it is not preferable because practically sufficient heat resistance and formability cannot be obtained. More preferably, the glass transition temperature is 100 ° C. or higher and 160 ° C. or lower. When the glass transition temperature is higher than 160 ° C., the melt viscosity of the polymer at the time of polymerization becomes so high that a polymer having a high degree of polymerization cannot be obtained, and molding may be difficult.

（Ｒ_５は炭素数が２から１２である脂肪族ジオールまたは脂環族ジオールから選ばれる少なくとも一つのジオール残基）
で表されるジオール残基をさらに含むことが好ましい。該ジオール残基は全ジオール残基中０〜６０モル％であり、より好ましくは１０〜４０モル％である。 As a diol residue in polycarbonate, the following formula (2)

(R ₅ is at least one diol residue selected from an aliphatic diol or an alicyclic diol having 2 to 12 carbon atoms)
It is preferable that the diol residue further represented by these is included. This diol residue is 0-60 mol% in all diol residues, More preferably, it is 10-40 mol%.

  Here, as the diol constituting the diol residue of the above formula (2), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Among these, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are preferable in that the degree of polymerization is easily increased in the synthesis of the polymer and the glass transition point is also high in the physical properties of the polymer. 1,3-propanediol is more preferred. Polycarbonate polymerized using 1,3-propanediol has a higher degree of polymerization and a higher glass transition temperature than polycarbonates polymerized using other aliphatic diols such as 1,4-butanediol and 1,6-hexanediol. Excellent mechanical properties and heat resistance.

  Specific examples of the diol constituting the diol residue represented by the above formula (1) include isosorbide, isomannide, and isoidide represented by the following formulas (3), (4), and (5). These saccharide-derived diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide can be obtained by hydrogenating D-glucose obtained from starch and then subjecting it to dehydration. Other diols can be obtained by the same reaction except for the starting material.

  In particular, a polycarbonate comprising an isosorbide residue as the diol residue is preferred. Isosorbide is a diol that can be easily made from starch and the like, and can be obtained in abundant resources. In addition, it is superior in terms of ease of manufacture, properties, and wide range of applications compared to isomannide and isoidide. Of the diol residues represented by the formula (1), the isosorbide residue is preferably 60 to 100% by weight.

  The addition polymerization type polymer used in the present invention is preferably a styrene resin, and more preferably an ABS resin (acrylonitrile-butadiene-styrene graft copolymer). ABS resin is a well-balanced thermoplastic resin with excellent physical properties such as impact resistance, rigidity, and moldability, as well as good surface appearance and ease of secondary workability. By blending ABS resin, the fluidity during molding can be improved without impairing the impact strength of polycarbonate resin.

  When the tensile test of the resin composition of the present invention is performed by a method according to ISO 527-1 and ISO 527-2, the elongation at break is preferably 10% or more. The molding temperature of the resin composition of the present invention is preferably 230 ° C. or lower.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
The reduced viscosity of the polymer was determined by measuring the viscosity at 35 ° C. of a solution obtained by dissolving 120 mg of polycarbonate in 10 ml of a mixed solvent of phenol / tetrachloroethane (volume ratio 50/50) using a Uderobe viscometer. The unit is dl (liter) / g. The weight average molecular weight was determined in terms of polystyrene by gel permeation chromatogram (GPC) using GPC System-11 manufactured by Shodex. The glass transition temperature was measured using DSC2920 manufactured by TA instruments. The tensile test and the bending test were performed using UCT-1T manufactured by Orientec. Here, the tensile test was measured according to ISO 527-1 and ISO 527-2, and the bending test was measured according to ISO 178. Yield point stress was similarly determined according to ISO 527-1 and ISO 527-2.

[Example 1]
Isosorbide (233.8 g, 1.6 mol), 1,3-propanediol (30.4 g, 0.4 mol) and diphenyl carbonate (428.4 g, 2.0 mol) were placed in a reactor and 2,2-bis (4 -Hydroxyphenyl) propane disodium salt (0.0272 mg, 1.0 × 10 ⁻⁷ mol) and tetramethylammonium hydroxide (3.65 mg, 4.0 × 10 ⁻⁵ mol) were added and melted at 180 ° C. in a nitrogen atmosphere. Under stirring, the pressure in the reaction vessel was reduced to 100 mmHg, and the reaction was carried out for about 20 minutes while distilling off the produced phenol. Next, after raising the temperature to 200 ° C., the pressure was reduced to 30 mmHg while distilling off the phenol, and the temperature was further raised to 215 ° C. Next, the pressure was gradually reduced, and the reaction was continued at 20 mmHg for 10 minutes and at 10 mmHg for 10 minutes. To complete the reaction. The obtained polycarbonate is designated as Bio-PC. Bio-PC had a reduced viscosity of 0.60 to 0.69, a molecular weight measurement by gel permeation chromatogram (GPC) of 32,000 to 45,000, and a glass transition point of 140 to 144 ° C. by DSC measurement.

  A molded product was prepared by injection-molding a mixture of 82 parts by weight of ABS resin (Nippon A & L Co., Ltd., Santac AT-05) to 100 parts by weight of Bio-PC obtained here. A bending test was performed (weight ratio: Bio-PC / ABS = 55/45). The results are shown in Table 1.

[ Reference Example 1 ]
The amounts of raw materials used in Example 1 were respectively adjusted to isosorbide (1023 g, 7.0 mol), 1,3-propanediol (239.7 g, 3.15 mol), diphenyl carbonate (2142 g, 10.0 mol), 2,2- The same procedure as in Example 1 except that bis (4-hydroxyphenyl) propane disodium salt (0.681 mg, 2.5 × 10 ⁻⁶ mol) and tetramethylammonium hydroxide (18.2 mg, 2.0 × 10 ⁻⁴ mol) were used. Bio-PC was synthesized by The obtained Bio-PC had a reduced viscosity of 0.68 to 0.70 and a glass transition point by DSC measurement of 123 to 124 ° C. A molded product was produced by injection molding a mixture of 100 parts by weight of Bio-PC obtained above and 150 parts by weight of ABS resin (Nippon A & L Co., Ltd., Santac AT-05). A bending test was performed (weight ratio: Bio-PC / ABS = 40/60). The results are shown in Table 1.

[Comparative Example 1]
A mixture of 11 parts by weight of ABS resin with 100 parts by weight of Bio-PC obtained by the same polymerization as in Example 1 was injection-molded and subjected to a tensile test and a bending test (weight ratio: Bio-PC / ABS = 90/10). The results are shown in Table 1.

[Comparative Example 2]
82 parts by weight of ABS is mixed with 100 parts by weight of a general type polycarbonate made of bisphenol A (abbreviated as PC, Teijin Chemicals Ltd., K-1300Y), injection molded, and the same measurement as in Example 1 is performed. (Weight ratio: PC / ABS = 55/45). The results are shown in Table 1.

[Comparative Example 3]
150 parts by weight of ABS was mixed with 100 parts by weight of PC and injection molded, and the same measurement as in Example 1 was performed (weight ratio: PC / ABS = 40/60). The results are shown in Table 1.

As can be seen from Table 1, in Example 1 and Reference Example 1 , the moldability is improved compared to Comparative Examples 1, 2, and 3, and the elongation at break is dramatically higher than that of PC / ABS having the same composition ratio. It has improved.

Claims (8)

Following formula (1)

(R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group)
And 100 parts by weight of a polycarbonate in which the diol residues represented by the formula (1) occupy 40 to 100 mol% and 80 to 99 parts by weight of an ABS resin. Resin composition. As a diol residue in polycarbonate, the following formula (2)

(R ₅ is at least one diol residue selected from an aliphatic diol or an alicyclic diol having 2 to 12 carbon atoms)
The resin composition according to claim 1, further comprising a diol residue represented by:   The resin composition according to claim 1 or 2, wherein the polycarbonate has a glass transition point of 90 ° C or higher. 2. The resin composition according to claim 1, wherein the polycarbonate has a diol residue represented by the formula (1) among all diol residues of 60 mol% or more and 90 mol% or less . The resin composition according to claim 2 or 3 , wherein the aliphatic diol of the formula (2) is 1,3-propanediol. As the diol residue represented by formula (1), comprising isosorbide residue, it claims 1-3 or resin composition according to any one of 5,. The resin composition according to claim 1, wherein the polycarbonate has a weight average molecular weight of 10,000 or more. The resin composition according to claim 1, wherein the polycarbonate has a glass transition point of 100 ° C. or higher and 160 ° C. or lower .