WO2015163479A1

WO2015163479A1 - Resin composition

Info

Publication number: WO2015163479A1
Application number: PCT/JP2015/062628
Authority: WO
Inventors: 瞬指宿
Original assignee: 帝人株式会社
Priority date: 2014-04-23
Filing date: 2015-04-21
Publication date: 2015-10-29
Also published as: TW201540774A; JP2017132822A

Abstract

The purpose of the present invention is to provide a thermoplastic resin composition having exceptional heat stability as well as excellent mechanical strength and exceptional chemical resistance. The present invention is a resin composition containing 1-10 parts by weight of (C) a core-shell polymer (component C) that comprises a core (component C-1) comprising a cross-linked acrylic-acid-ester-based elastic material configured from an acrylic acid ester having C1-4 alkyl groups and an acrylic acid ester having C5-8 alkyl groups, and a shell (component C-2) having a methacrylic acid ester as the main component, and 8-15 parts by weight of (D) a filler (component D), per 100 parts by weight of a resin component comprising 80-50 parts by weight of (A) a polycarbonate resin (component A) and 20-50 parts by weight of (B) a polyester resin (component B).

Description

Resin composition

The present invention relates to a resin composition and a molded product containing a polycarbonate resin, a polyester resin, a core-shell polymer having a specific structure, and a filler. More specifically, the present invention relates to a thermoplastic resin composition comprising a polyester resin produced using a catalyst comprising a specific element, having excellent thermal stability, and excellent mechanical strength and chemical resistance.

Resin compositions containing polycarbonate resin, polyester resin, fillers and impact modifiers improve chemical resistance while maintaining the excellent appearance, mechanical and dimensional stability of polycarbonate resin, and add rigidity. Therefore, it is widely used in electrical / electronic, mechanical, OA, vehicle, and medical applications. In addition, a molded product formed from a resin composition containing a polycarbonate resin, a polyester resin, and a filler (hereinafter sometimes referred to as PC / PEST / filler alloy) is used as a painted member or unpainted. In particular, it is useful for vehicle applications and OA applications, and various studies have been made.
In recent years, in the vehicle field and OA field, the weight reduction and cost reduction of parts are progressing rapidly. For example, as a vehicle application, technological developments using resin materials for large parts represented by body panels such as fenders and back doors are active, and PC / PEST / filler alloy has the excellent characteristics described above. To a suitable resin material. However, since the heat and moisture resistance is inferior to those of steel plates and the like that have been used up to now, the applicable parts and sizes are limited, and their use is limited.
In addition, thinning of parts for weight reduction, simultaneous reduction in the number of parts for cost reduction, and the trend toward modularization of parts are accelerating, making it easier to form thinner, more complex and large shaped products. Therefore, improvement of processing characteristics is demanded. As a method for improving the processing characteristics by using existing equipment, a method of increasing the molding temperature and increasing the fluidity is generally used, so that better thermal stability is required. Therefore, in order to achieve weight reduction and cost reduction of parts, PC / PEST / filler alloy is strongly required to have both better heat resistance and heat stability.
Furthermore, in fields where mechanical strength is particularly required, such as vehicle members, machines, buildings, etc., it is strongly required to satisfy both rigidity and impact resistance.
Patent Document 1 discusses a technique of blending an inorganic compound containing aluminum silicate as a main component in order to improve the heat and moisture resistance of a resin composition containing a polycarbonate resin and a polyester resin. In addition to the increase in the cost of the resin composition and the increase in the number of steps for producing the resin composition, the blending of such additives has a problem that the effect of weight reduction, which is the original purpose such as an increase in specific gravity, is diminished. Moreover, although there is a possibility that the thermal stability is lowered, no knowledge about the thermal stability is shown, and it cannot be said that a sufficient technical study has been made.
In patent document 2, the technique of mix | blending a phosphite-type antioxidant with PC / PEST / filler alloy is examined. Although this technique suppresses the decomposition of the resin during the molding process, no examination has been made on the resistance to moist heat, and further technical improvements are required.
Patent Document 3 discusses a technique in which an acidic phosphorus-based additive and an inorganic filler whose water content is controlled to 0.25% by weight or less are mixed with PC / PEST alloy. Mixing a filler with a water content of 0.25% by weight or less improves the melt stability. However, the management of the water content of the inorganic filler to be added means an increase in the number of steps for producing the resin composition. It is difficult to say that it is a general-purpose technology that leads to cost increase. Moreover, examination about the heat-and-moisture resistance of the obtained resin composition is not carried out, and the further improvement is required technically.
Patent Document 4 discusses a technique for controlling the dispersion state so that an inorganic compound having a pH of 8.0 or higher and an SiO ₂ unit of 30% by weight or higher does not exist in the polycarbonate resin as much as possible. Although such technology has been confirmed to improve the thermal stability during the molding process, no examination has been made on the heat and moisture resistance. Moreover, in order to obtain such a resin composition, there is a high possibility that the manufacturing method will be restricted. As a result, the number of manufacturing steps is increased and the cost is increased, which is not a highly versatile technique.
The method of adding additional additives to improve the heat and moisture resistance and thermal stability of PC / PEST / filler alloy and the method of controlling the dispersion state of the filler make it difficult to achieve both heat and moisture stability. Therefore, further technology is required.
Under such circumstances, an alloy material using PET produced with a specific polymerization catalyst has been proposed as a means for PC / PEST / filler alloy to satisfy the above requirements (see Patent Documents 5-7). In Patent Document 5, it is proposed to use a germanium catalyst to improve the color tone, melt stability, appearance, and moldability of PET produced with a general antimony compound or titanium compound as a polymerization catalyst. Yes. However, such a technique does not sufficiently satisfy the higher thermal stability currently required for vehicles and OA applications, and no knowledge about wet heat resistance is taught.
Patent Document 6 proposes to improve color tone, thermal stability, and melt stability by including a polyester resin produced by using 1 to 30 ppm of a titanium-containing catalyst compound. Although the thermal stability and melt stability are improved by reducing the amount of the catalyst, the thermal stability tends to decrease as the amount of the polyester resin increases, and further improvement is required. In addition, no knowledge about wet heat resistance is taught.
In Patent Document 7, by producing a polyester resin using a titanium-containing catalyst compound having a specific structure, the polyester resin has a good color tone (b value), little foreign matter, and excellent thermal stability during melting. It is described that a polyester resin is obtained. However, the effect on the resin composition containing a resin other than the polyester resin is not mentioned, and no knowledge about wet heat resistance is taught.
Patent Document 8 discusses the use of a filler and an impact modifier in combination as a means for PC / PEST / filler alloy to satisfy the requirements of mechanical strength. Although the strength and rigidity are improved by such a technique, the effect of the impact modifier on improving the rigidity has not been studied, and further improvement is technically necessary.
For this reason, a polycarbonate resin composition and a molded article having good wet heat resistance and thermal stability and excellent mechanical strength such as rigidity and impact resistance have not yet been provided.
JP-A-10-237295 JP-A-5-222283 JP 2002-121366 A JP 2000-313799 A Japanese Patent Laid-Open No. 51-102043 JP-T-2005-521772 WO03 / 008479 Publication JP-A-9-286904

An object of the present invention is to provide a resin composition containing a polycarbonate resin, a polyester resin, and an impact modifier, and having excellent mechanical strength such as tensile modulus and Charpy impact strength. Another object of the present invention is to provide a resin composition having excellent heat and humidity resistance and thermal stability. Another object of the present invention is to provide a molded article made of the resin composition, particularly a vehicle interior member and a vehicle exterior member.
As a result of intensive studies to achieve the above object, the present inventors have obtained a tensile elastic modulus by blending a polyester resin and a core-shell polymer having a specific structure into a polycarbonate resin, as shown in FIGS. It was also found that a resin composition having excellent Charpy impact strength can be obtained. In addition, the obtained resin composition was found to be excellent in heat and moisture resistance and heat stability, and the present invention was completed.
According to the present invention, the above-mentioned problem is based on 100 parts by weight of a resin composition comprising (A) 80 to 50 parts by weight of a polycarbonate resin (component A) and (B) 20 to 50 parts by weight of a polyester resin (component B). ,
(C) A core (C-1 component) comprising a cross-linked acrylate ester elastic body composed of an acrylate ester having 1 to 4 carbon atoms in the alkyl group and an acrylate ester having 5 to 8 carbon atoms in the alkyl group And 1 to 10 parts by weight of a core-shell polymer (component C) consisting of a shell (component C-2) containing methacrylic acid ester as the main component and 0 to 15 parts by weight of a filler (component D) (D) Is achieved.

Comparison between Example 2 and Comparative Examples 6-8 Comparison between Example 12 and Comparative Examples 9 to 11

Hereinafter, further details of the present invention will be described.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A of the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. 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.
Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediiso (Ropyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.
In the present invention, in addition to a general-purpose polycarbonate, which is a bisphenol A-based polycarbonate, a special polycarbonate manufactured using other dihydric phenols can be used as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.
In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component B constituting the polycarbonate resin composition is the following copolymeric polycarbonate (1) to (3). It is.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is a copolymer polycarbonate having a content of 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is a copolycarbonate having a content of 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate having a TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production methods and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.
Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) a polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and a Tg of 120 to 180 ° C., or
(Ii) Tg is 160 to 250 ° C., preferably 170 to 230 ° C., and water absorption is 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to Polycarbonate which is 0.27%.
Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. And a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.
Branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.
The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is 0.1% in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. The amount is from 01 to 1 mol%, preferably from 0.05 to 0.9 mol%, particularly preferably from 0.05 to 0.8 mol%.
In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction. However, the amount of the branched structural unit is also 0.1% in a total of 100 mol% with a structural unit derived from a dihydric phenol. A content of 001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol% is preferred. Regarding the ratio of such branched structures¹It is possible to calculate by H-NMR measurement.
The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Furthermore, it is possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units.
The polycarbonate resin can be produced by an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, a ring-opening polymerization method of a cyclic carbonate compound, or the like. These reaction formats are well known in various documents and patent publications.
The viscosity average molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 14,000 to 30,000, and further preferably 14,000 to 26,000. With a polycarbonate resin having a viscosity average molecular weight of less than 10,000, good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 50,000 is inferior in versatility in that it is inferior in fluidity during injection molding.
The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the range (50,000) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more preferred embodiment, a polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-1-1) and a polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 (A Polycarbonate resin having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter sometimes referred to as “high molecular weight component-containing polycarbonate resin”).
In such a high molecular weight component-containing polycarbonate resin, the molecular weight of the A-1-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably 100,000 to 200,000, Particularly preferred is 100,000 to 160,000. The molecular weight of the A-1-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.
The high molecular weight component-containing polycarbonate resin can be obtained by mixing the A-1-1 component and the A-1-2 component at various ratios and adjusting so as to satisfy a predetermined molecular weight range. Preferably, in 100% by weight of the high molecular weight component-containing polycarbonate resin, the A-1-1 component is 2 to 40% by weight, more preferably the A-1-1 component is 3 to 30% by weight, The A-1-1 component is preferably 4 to 20% by weight, and particularly preferably the A-1-1 component is 5 to 20% by weight.
As a method for preparing a polycarbonate resin containing a high molecular weight component, (1) a method in which the A-1-1 component and the A-1-2 component are polymerized independently and mixed, (2) In the same system, a polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method shown in JP-A-306336 is used. And (3) a polycarbonate resin obtained by such a production method (production method (2)), a separately produced A-1-1 component and / or A-1- Examples include a method of mixing two components.
The viscosity average molecular weight referred to in the present invention is first determined by the specific viscosity (η_SP) At 20 ° C. using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride,
Specific viscosity (η_SP) = (T−t₀) / T₀
[T₀Is the drop time of methylene chloride, t is the drop time of the sample solution]
Calculated specific viscosity (η_SP) To calculate the viscosity average molecular weight M by the following formula.
Η_SP/C=[η]+0.45×[η]²c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10^-4M^0.83
C = 0.7
The viscosity average molecular weight of the polycarbonate resin in the resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve soluble components in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.
(B component: polyester resin)
The polyester resin used as the component B of the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof.
As the aromatic dicarboxylic acid here, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether Dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid Acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylene dicarboxylic acid, aromatic dicarboxylic acid such as 2,5-pyridinedicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ether Dicarboxylic acid and β-hydroxyethoxy It is preferably used selected from Ikiko acid, particularly terephthalic acid, 2,6-naphthalenedicarboxylic acid can be preferably used. Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. together with the dicarboxylic acid. .
Examples of the diol that is a component of the polyester resin include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, and 2-methyl-1,3-propanediol. , Aliphatic diols such as diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, diols containing aromatic rings such as 2,2-bis (β-hydroxyethoxyphenyl) propane, and the like A mixture thereof may be mentioned. If the amount is smaller, one or more long chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.
The polyester resin can be branched by introducing a small amount of a branching agent. Although there is no restriction | limiting in the kind of branching agent, A trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, etc. are mentioned.
Specific polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2- In addition to bis (phenoxy) ethane-4,4′-dicarboxylate, a copolymer polyester resin such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like can be given. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof having a good balance of mechanical properties and the like can be preferably used.
Further, the terminal group structure of the polyester resin is not particularly limited, and the ratio of the hydroxyl group and the carboxyl group in the terminal group may be large, in addition to the case where the ratio is large. Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.
Such a polyester resin is produced by polymerizing a dicarboxylic acid component and the diol component while heating in the presence of a specific titanium-based catalyst and discharging by-product water or lower alcohol out of the system according to a conventional method. It is preferable.
The above titanium-based catalyst includes a reaction product of the following titanium compound component (A) and phosphorus compound component (B).
The titanium compound component (A) includes a titanium compound (1) represented by the following general formula (I), an aromatic polyvalent carboxylic acid represented by the titanium compound (1) and the following general formula (II), or anhydrous It is at least one titanium compound component selected from the group consisting of a titanium compound (2) obtained by reacting with a product.

[However, in formula (I), R¹, R², R³And R⁴Each independently represents an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, and when k is 2 or 3, 2 or 3 R²And R³May be the same as or different from each other. ]

[In the formula (II), m represents an integer of 2 to 4. ]
The phosphorus compound component (B) is a phosphorus compound component composed of at least one of the phosphorus compounds (3) represented by the following general formula (III).

[In the formula (III), R⁵Represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. ]
The polyester resin produced by using the above-mentioned specific titanium-based catalyst is superior in thermal stability and wet heat resistance compared to the case of using germanium, antimony and other titanium-based catalysts. When the above specific titanium-based catalyst is used, the quality is stable even if the amount of additives such as hue stabilizer and heat stabilizer during production is less than when other catalysts are used. Since decomposition of the additive in a thermal environment or a moist heat environment is reduced, it is presumed that the thermal stability and the heat and humidity resistance are excellent.
In the reaction product of the titanium compound component (A) and the phosphorus compound component (B), the titanium compound equivalent molar amount (mTi) of the titanium compound component (A) and the phosphorus atom equivalent molar amount of the phosphorus compound component (B) The reaction molar ratio (mTi / mP) with (mP) is preferably in the range of 1/3 to 1/1, and more preferably in the range of 1/2 to 1/1.
The molar amount in terms of titanium atom of the titanium compound component (A) is the product of the molar amount of each titanium compound contained in the titanium compound component (A) and the number of titanium atoms contained in one molecule of the titanium compound. It is a total value, and the phosphorus atom equivalent molar amount of the phosphorus compound component (B) is the molar amount of each phosphorus compound contained in the phosphorus compound component (B) and the phosphorus atoms contained in one molecule of the phosphorus compound. It is the total value of the product with the number. However, since the phosphorus compound represented by the formula (III) contains one phosphorus atom per molecule, the phosphorus atom equivalent molar amount of the phosphorus compound is equal to the molar amount of the phosphorus compound.
When the reaction molar ratio (mTi / mP) is greater than 1/1, that is, when the amount of the titanium compound component (A) is excessive, the color tone of the polyester resin obtained using the resulting catalyst (b value is too high). ) And its heat resistance may be reduced. Further, when the reaction molar ratio (mTi / mP) is less than 1/3, that is, when the amount of the titanium compound component (A) becomes too small, the catalytic activity of the resulting catalyst for the polyester formation reaction may be insufficient. is there.
Examples of the titanium compound (1) represented by the general formula (I) used for the titanium compound component (A) include titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxide. Examples include tetraalkoxides, and alkyl titanates such as octaalkyltrititanates and hexaalkyldititanates, and among these, titanium having good reactivity with the phosphorus compound component used in the present invention. It is preferable to use tetraalkoxides, and it is particularly preferable to use titanium tetrabutoxide.
The titanium compound (2) used for the titanium compound component (A) is obtained by reacting the titanium compound (1) with the aromatic polyvalent carboxylic acid represented by the general formula (II) or an anhydride thereof. The aromatic polyvalent carboxylic acid of the general formula (II) and its anhydride are preferably selected from the group consisting of phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their anhydrides. In particular, it is more preferable to use trimellitic anhydride having good reactivity with the titanium compound (1) and high affinity with the polyester of the resulting polycondensation catalyst.
The reaction between the titanium compound (1) and the aromatic polyvalent carboxylic acid of the general formula (II) or its anhydride is carried out by mixing the aromatic polyvalent carboxylic acid or its anhydride in a solvent and partially or entirely Is dissolved in a solvent, and the titanium compound (1) is dropped into this mixed solution and heated at a temperature of 0 ° C. to 200 ° C. for 30 minutes or more, preferably at a temperature of 30 to 150 ° C. for 40 to 90 minutes. Is called. The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. The catalyst can be appropriately selected from those capable of dissolving a required amount of the compound of the formula (II) or part or all of its anhydride, preferably ethanol, ethylene glycol, trimethylene It is selected from glycol, tetramethylene glycol, benzene, xylene and the like.
There is no limitation on the reaction molar ratio between the titanium compound (1) and the compound represented by the formula (II) or its anhydride. However, if the proportion of the titanium compound (1) is too high, the color tone of the resulting polyester resin may be deteriorated or the softening point may be lowered. On the contrary, if the proportion of the titanium compound (1) is too low, it is heavy. The condensation reaction may be difficult to proceed. Therefore, the reaction molar ratio between the titanium compound (1) and the compound of the formula (II) or its anhydride is preferably controlled within the range of 2/1 to 2/5. The reaction product obtained by this reaction may be directly subjected to the reaction with the above-mentioned phosphorus compound (3) or recrystallized using a solvent comprising acetone, methyl alcohol and / or ethyl acetate. Then, this may be reacted with the phosphorus compound (3).
In the phosphorus compound (3) of the general formula (III) used for the phosphorus compound component (B), R⁵The aryl group having 6 to 20 carbon atoms or the alkyl group having 1 to 20 carbon atoms represented by the formula may be unsubstituted or substituted by one or more substituents May be. Examples of the substituent include a carboxyl group, an alkyl group, a hydroxyl group, and an amino group.
The phosphorus compound (3) of the general formula (III) includes, for example, monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, Monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4 -Ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolylphosphate Monoalkyl phosphates and monoaryl phosphates such as phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, and monoanthryl phosphate, which may be used alone or in combination As the above mixture, for example, a mixture of a monoalkyl phosphate and a monoaryl phosphate may be used. However, when the above phosphorus compound is used as a mixture of two or more kinds, it is preferable that the proportion of monoalkyl phosphate occupies 50% or more, more preferably 90% or more, particularly 100%. More preferably.
In order to prepare a catalyst from the titanium compound component (A) and the phosphorus compound component (B), for example, a phosphorus compound component (B) comprising at least one phosphorus compound (3) of the formula (III) and a solvent are prepared. After mixing, a part or all of the phosphorus compound component (B) is dissolved in a solvent, and the titanium compound component (A) is dropped into this mixed solution, and the normal reaction system is preferably 50 ° C to 200 ° C, more preferably Is carried out by heating at a temperature of 70 ° C. to 150 ° C., preferably for 1 minute to 4 hours, more preferably for 30 minutes to 2 hours. In this reaction, the reaction pressure is not particularly limited, and may be any of under pressure (0.1 to 0.5 MPa), normal pressure, or reduced pressure (0.001 to 0.1 MPa). Usually performed under normal pressure.
The solvent for the phosphorus compound component (B) of the formula (III) used in the catalyst preparation reaction is not particularly limited as long as at least a part of the phosphorus compound component (B) can be dissolved. For example, ethanol, ethylene A solvent consisting of at least one selected from glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene and the like is preferably used. In particular, it is preferable to use, as a solvent, the same compound as the glycol component constituting the polyester to be finally obtained.
After the reaction product of the titanium compound component (A) and the phosphorus compound component (B) is separated from the reaction system by means such as centrifugal sedimentation or filtration, the polyester resin is purified without purification. It may be used as a production catalyst, or the separated reaction product is purified by recrystallization from a recrystallization agent such as acetone, methyl alcohol and / or water, and the purified product obtained thereby. May be used as a catalyst. Moreover, you may use the reaction product containing reaction mixture as a catalyst containing mixture as it is, without isolate | separating the said reaction product from the reaction system.
As a titanium-based catalyst, a titanium compound component (A) comprising at least one titanium compound (1) of the above formula (I) (where k represents 1), that is, titanium tetraalkoxide, and the above formula (III) It is preferable that the reaction product with the phosphorus compound component (B) comprising at least one phosphorus compound is used as a catalyst.
Furthermore, a compound represented by the following general formula (IV) is preferably used as the titanium-based catalyst.

[R in the above formula⁶And R⁷Each independently represents an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.
The catalyst containing the titanium / phosphorus compound represented by the formula (IV) has high catalytic activity, and the polyester resin produced using the catalyst has a good color tone (low b value) and is practically sufficient. In addition, it has a low content of acetaldehyde, a residual metal and a cyclic trimer of an ester of an aromatic dicarboxylic acid and an alkylene glycol, and has practically sufficient polymer performance.
In the titanium-based catalyst, the titanium / phosphorus compound of the general formula (IV) is preferably contained in an amount of 50% by weight or more, and more preferably 70% by weight or more.
The amount of the titanium-based catalyst used is preferably an amount such that the mmol amount in terms of titanium atom is 2 to 40 mm% with respect to the total mmol amount of the aromatic dicarboxylic acid component contained in the polymerization starting material. It is more preferably ~ 35 mm%, and even more preferably 10-30 mm%. If it is less than 2 mm%, the catalyst's promotion effect on the polycondensation reaction of the polymerization starting material becomes insufficient, the polyester production efficiency becomes insufficient, and a polyester resin having a desired degree of polymerization cannot be obtained. There is. On the other hand, if it exceeds 40 mm%, the color tone (b value) of the resulting polyester resin becomes insufficient and becomes yellowish, and its practicality may be lowered.
There is no limitation on the production method of the alkylene glycol ester of aromatic dicarboxylic acid and / or its low polymer, but usually, the aromatic dicarboxylic acid or its ester-forming derivative and the alkylene glycol or its ester-forming derivative are heated. Produced by reacting. For example, an ethylene glycol ester of terephthalic acid and / or a low polymer thereof used as a raw material for polyethylene terephthalate may be obtained by directly esterifying terephthalic acid and ethylene glycol, or by converting a lower alkyl ester of terephthalic acid and ethylene glycol It is produced by a method of transesterification or an addition reaction of terephthalic acid with ethylene oxide. In addition, the above-described aromatic dicarboxylic acid alkylene glycol ester and / or a low polymer thereof may contain other dicarboxylic acid ester copolymerizable therewith as an additional component, so that the effect of the method of the present invention is not substantially impaired. It may be contained in an amount within the range, specifically, 10 mol% or less, preferably 5 mol% or less, based on the total molar amount of the acid components.
The copolymerizable additional component is preferably an acid component such as aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic acids such as One or more of β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and the like and a glycol component, for example, alkylene glycol having 2 or more carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A , An ester with one or more of aliphatic, cycloaliphatic, aromatic diol compounds such as bisphenol S and polyoxyalkylene glycol, or anhydrides thereof. The postscript component ester may be used alone or in combination of two or more thereof. However, the copolymerization amount is preferably within the above range.
When terephthalic acid and / or dimethyl terephthalate is used as a starting material, recovered dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate or recovered terephthalic acid obtained by hydrolyzing this is used as polyester. It is also possible to use 70% by weight or more based on the weight of the total acid component. In this case, it is preferable that the target polyalkylene terephthalate is polyethylene terephthalate. In particular, recovered PET bottles, recovered fiber products, recovered polyester film products, polymer waste generated in the manufacturing process of these products, etc. It is preferable to use as a raw material source for producing polyester from the viewpoint of effective utilization of resources. Here, the method for depolymerizing the recovered polyalkylene terephthalate to obtain dimethyl terephthalate is not particularly limited, and any conventionally known method can be employed. For example, after the recovered polyalkylene terephthalate is depolymerized with ethylene glycol, the depolymerized product is subjected to a transesterification reaction with a lower alcohol such as methanol, and the reaction mixture is purified to recover the lower alkyl ester of terephthalic acid. The polyester resin can be obtained by subjecting this to an ester exchange reaction with alkylene glycol and polycondensing the resulting phthalic acid / alkylene glycol ester. Further, the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method may be used. For example, dimethyl terephthalate can be recovered from the reaction mixture obtained by the transesterification reaction by recrystallization and / or distillation, and then hydrolyzed with water at high temperature and high pressure to recover terephthalic acid. In impurities contained in terephthalic acid obtained by this method, the total content of 4-carboxybenzaldehyde, p-toluic acid, benzoic acid and dimethyl hydroxyterephthalate is preferably 1 ppm or less. The content of monomethyl terephthalate is preferably in the range of 1 to 5000 ppm. A polyester resin can be produced by directly esterifying the terephthalic acid recovered by the above-described method with an alkylene glycol and polycondensing the resulting ester.
In the polyester resin used in the present invention, the timing of adding the catalyst to the polymerization starting material is any stage before the start of the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its low polymer. Moreover, there is no limitation on the addition method. For example, an aromatic dicarboxylic acid alkylene glycol ester may be prepared and a polycondensation reaction may be initiated by adding a catalyst solution or slurry to the reaction system, or the aromatic dicarboxylic acid alkylene glycol ester may be A catalyst solution or slurry may be added to the reaction system together with the starting material during preparation or after its preparation.
The production reaction conditions for the polyester resin used in the present invention are not particularly limited. In general, the polycondensation reaction is preferably performed at a temperature of 230 to 320 ° C. under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa) or a combination of these conditions for 15 to 300 minutes. .
In the polyester resin used in the present invention, if necessary, a reaction stabilizer such as trimethyl phosphate may be added to the reaction system at any stage in the production of the polyester. One or more of an agent, a flame retardant, a fluorescent brightening agent, a matting agent, a color adjusting agent, an antifoaming agent, and other additives may be blended. In particular, the polyester resin preferably contains an antioxidant containing at least one hindered phenol compound, but the content thereof is 1% by weight or less based on the weight of the polyester resin. preferable. When the content exceeds 1% by weight, there may be a disadvantage that the quality of the obtained product is deteriorated due to thermal deterioration of the antioxidant itself.
The hindered phenol compound for antioxidant used in the polyester resin used in the present invention is pentaerythritol-tetra extract [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3.9. -Bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 5] It is also preferably practiced to use these hindered phenolic antioxidants in combination with thioether secondary antioxidants selected from undecane and the like. The method for adding the hindered phenolic antioxidant to the polyester resin is not particularly limited, but preferably at any stage between the completion of the ester exchange reaction or the esterification reaction and the completion of the polymerization reaction. Added.
Furthermore, in order to finely adjust the color tone of the obtained polyester resin, in the production stage of the polyester resin, organic blue pigments such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine and the like are included in the reaction system. A color adjusting agent composed of one or more blue pigments can be added. In the production method of the present invention, as a matter of course, it is not necessary to use an inorganic blue pigment containing cobalt or the like which lowers the melt heat stability of the polyester resin as a color adjusting agent. Therefore, the polyester resin used in the present invention is substantially free of cobalt.
The polyester resin used in the present invention preferably contains 0.001 ppm to 100 ppm of the titanium element derived from the catalyst. The content is more preferably 0.001 ppm to 50 ppm, and further preferably 1 ppm to 50 ppm. If the content of titanium element is more than 100 ppm, thermal stability and heat-and-moisture resistance may be deteriorated. If the content is less than 0.001 ppm, the remaining amount of catalyst of the polyester resin used is significantly lower, making it difficult to produce the polyester resin. In some cases, good mechanical strength, thermal stability and wet heat stability may not be obtained.
The intrinsic viscosity of the polyester resin is preferably 0.4 to 1.2. A more preferable range of the intrinsic viscosity is 0.45 to 0.95, and further preferably 0.50 to 0.9. If the intrinsic viscosity of the polyester resin is less than 0.4, sufficient impact characteristics and chemical resistance may not be obtained. If it is greater than 1.0, the fluidity at the time of injection molding decreases, and flow marks and coloring Appearance defects such as defects may occur.
The polyester resin is a polyethylene terephthalate resin (PET) and a polybutylene terephthalate resin (PBT), and the blending ratio (weight ratio) (PET / PBT) is preferably 1/7 to 7/8. The blending ratio is more preferably 1/7 to 1/2, and even more preferably 1/7 to 1/4. When the blending ratio is larger than 7/8, the chemical resistance is lowered, and when it is smaller than 1/7, the fluidity may be lowered.
The content of component B is 20 to 50 parts by weight, preferably 20 to 45 parts by weight, more preferably 25 to 40 parts by weight, per 100 parts by weight of the resin component. If the content is less than 20 parts by weight, the chemical resistance improving effect is not observed, and if it exceeds 50 parts by weight, the heat and humidity resistance is lowered and the impact strength is lowered.
(C component: core-shell polymer)
The core-shell polymer used in the present invention is a crosslinked acrylate ester elastic body composed of an acrylate ester having 1 to 4 carbon atoms in the alkyl group and an acrylate ester having 5 to 8 carbon atoms in the alkyl group. A core-shell polymer comprising a core (component C-1) and a shell (component C-2) containing methacrylic acid ester as a main component. When a core-shell polymer other than those described above is used as the C component, sufficient impact characteristics and rigidity cannot be obtained, and chemical resistance is lowered depending on the compound.
Examples of the acrylic acid ester having 1 to 4 carbon atoms in the alkyl group, which is a constituent monomer of the C-1 component, include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples of the acrylate ester having 5 to 8 carbon atoms in the alkyl group include hexyl acrylate, heptyl acrylate, and 2-ethylhexyl acrylate. The most preferred combination is a crosslinked alkyl acrylate elastic body composed of butyl acrylate and 2-ethylhexyl acrylate. Moreover, you may contain components other than alkyl acrylate in the range which does not inhibit the effect of this invention.
The C-2 component is derived from a (meth) acrylic acid ester (for example, methyl methacrylate). You may copolymerize the other vinyl monomer which can be copolymerized as needed, such as a monomer mixture of a vinyl aromatic compound or a vinyl cyanide compound, and (meth) acrylic acid ester.
In the core-shell polymer used for the C component, the content of the C-1 component is preferably 50 to 99% by weight, more preferably 65 to 95% by weight, and more preferably 75 to 90% of 100% by weight of the C component. Most preferred is wt%. If the content of the C-1 component is less than 50% by weight, sufficient impact characteristics may not be obtained. On the other hand, if it exceeds 99% by weight, sufficient impact characteristics may not be obtained, which is not preferable.
Further, the content of the acrylate ester having 5 to 8 carbon atoms in the alkyl group in the C-1 component is preferably 10 to 99% by weight, and 25 to 90% by weight in 100% by weight of the C-1 component. More preferred is 35 to 80% by weight, and most preferred is 40 to 70% by weight. If the amount is less than 10% by weight, sufficient impact characteristics may not be obtained. If the amount is more than 99% by weight, the heat resistance may decrease, which is not preferable.
The content of the core-shell polymer is 1 to 10 parts by weight, preferably 2 to 9 parts by weight, and more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the resin component. If it is less than 1 part by weight, sufficient impact characteristics cannot be obtained, and if it is more than 10 parts by weight, rigidity and chemical resistance are lowered.
(D component: filler)
Conventionally known fillers can be used as the filler used in the present invention, and preferred fillers include fibrous glass filler, plate-like glass filler, fibrous carbon filler, and non-fibrous carbon. It is at least one filler selected from the group consisting of fillers and silicate minerals.
(D-1; fibrous glass filler)
Examples of the fibrous glass filler suitably used in the present invention include glass fibers (including metal-coated glass fibers) and glass milled fibers. The glass fiber which becomes the base of the fibrous glass filler is obtained by rapidly cooling molten glass while drawing it by various methods to obtain a predetermined fiber shape. In such a case, the rapid cooling and stretching are not particularly limited. Further, the cross-sectional shape may be other than a perfect circle such as an ellipse, a cane, a flat shape, and a three-leaf shape in addition to a perfect circle. Further, it may be a mixture of a perfect circle and a shape other than a perfect circle. The flat shape means that the average value of the major axis of the fiber cross section is 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and the average value of the ratio of major axis to minor axis (major axis / minor axis) is 1.5. The shape is 8 to 8, preferably 2 to 6 and more preferably 2.5 to 5.
The average fiber diameter of the fibrous glass filler having a high aspect ratio such as glass fiber is preferably 1 to 25 μm, and more preferably 3 to 17 μm. When a filler having an average fiber diameter in this range is used, good mechanical strength can be expressed without impairing the appearance of the molded product. The fiber length of the high aspect ratio fibrous glass filler is preferably 60 to 500 μm, more preferably 100 to 400 μm, and particularly preferably 120 to 350 μm as the number average fiber length in the resin composition. The number-average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of the filler collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical, using an optical microscope. It is. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that. The aspect ratio of the high aspect ratio fibrous glass filler is preferably 10 to 200, more preferably 15 to 100, and still more preferably 20 to 50. The aspect ratio of the filler is a value obtained by dividing the average fiber length by the average fiber diameter.
Glass milled fiber is usually produced by shortening glass fiber using a pulverizer such as a ball mill. The aspect ratio of the fibrous glass filler having a low aspect ratio such as glass milled fiber is preferably 2 to 10, more preferably 3 to 8. The fiber length of the low aspect ratio fibrous glass filler is preferably 5 to 150 μm, more preferably 9 to 80 μm as the number average fiber length in the resin composition. The average fiber diameter is preferably 1 to 15 μm, more preferably 3 to 13 μm.
(D-2; plate glass filler)
Examples of the plate-like glass filler suitably used in the present invention include glass flakes including metal-coated glass flakes and metal oxide-coated glass flakes.
The glass flake used as the base of the plate-like glass filler is a plate-like glass filler produced by a method such as a cylindrical blow method or a sol-gel method. Various kinds of glass flake raw materials can be selected depending on the degree of pulverization and classification. The average particle size of the glass flakes used as the raw material is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and still more preferably 30 to 300 μm. This is because the above range is excellent in both handleability and moldability. Usually, a plate-like glass filler is cracked by melt-kneading with a resin, and its average particle size is reduced. The number average particle size of the plate-like glass filler in the resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and still more preferably 20 to 80 μm. The number average particle size is calculated by an image analyzer from an image obtained by observing the residue of the sheet glass filler collected by high temperature ashing of the molded product, dissolution with a solvent, decomposition with chemicals, etc. with an optical microscope. Is the value to be Further, when calculating such a value, the flake thickness is used as a guide and the length of the flake is not counted. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and further preferably 1.5 to 6 μm. The plate-shaped glass filler having the above-mentioned number average particle diameter and thickness achieves good mechanical strength, appearance, and moldability.
Various glass compositions represented by A glass, C glass, E glass and the like are applied to the glass composition of the above-described fibrous glass filler and plate glass filler, and is not particularly limited. Such glass fillers are optionally made of TiO₂, SO₃, And P₂O₅And the like. Among these, E glass (non-alkali glass) is more preferable. The glass filler is preferably subjected to a surface treatment with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength. Glass fibers (including those coated with metal or metal oxide) and glass flakes (including those coated with metal or metal oxide) are olefin resins, styrene resins, acrylic resins, Those that have been converged with a polyester resin, an epoxy resin, a urethane resin, or the like are preferably used. The amount of sizing agent adhering to the sizing agent is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight in 100% by weight of the filler.
Furthermore, the fibrous glass filler and the plate-like glass filler of the present invention include those in which different materials are surface-coated. Preferred examples of such dissimilar materials include metals and metal oxides. Examples of the metal include silver, copper, nickel, and aluminum. Examples of the metal oxide include titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide. There are no particular limitations on the method of surface coating of such different materials, for example, various known plating methods (for example, electrolytic plating, electroless plating, hot dipping, etc.), vacuum deposition methods, ion plating methods, CVD methods (For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned.
(D-3; fibrous carbon filler)
Examples of the fibrous carbon filler suitably used in the present invention include carbon fibers (including metal-coated carbon fibers), carbon milled fibers, vapor grown carbon fibers, and carbon nanotubes. The carbon nanotube may be any one of a fiber diameter of 0.003 to 0.1 μm, a single layer, a double layer, and a multilayer, and a multilayer (so-called MWCNT) is preferable. Among these, carbon fibers (including metal-coated carbon fibers) are preferable in that they are excellent in mechanical strength and can impart good electrical conductivity. Good electrical conductivity has become one of important characteristics required for resin materials in recent digital precision equipment (represented by, for example, a digital still camera).
As the carbon fiber, any of cellulose, polyacrylonitrile, pitch and the like can be used. In addition, it is obtained by a method in which a raw material composition comprising a polymer and a solvent due to a methylene bond of aromatic sulfonic acids or their salts is prevented or molded, and then subjected to spinning without passing through an infusibilization step typified by carbonization. It is also possible to use those that have been used. Furthermore, any of general-purpose type, medium elastic modulus type, and high elastic modulus type can be used. Among these, polyacrylonitrile-based high elastic modulus type is particularly preferable.
The average fiber diameter of the carbon fiber is not particularly limited, but is usually 3 to 15 μm, preferably 5 to 13 μm. A carbon fiber having an average fiber diameter in such a range can exhibit good mechanical strength and fatigue characteristics without impairing the appearance of the molded product. The preferred fiber length of the carbon fiber is preferably 60 to 500 μm, more preferably 80 to 400 μm, particularly preferably 100 to 300 μm as the number average fiber length in the resin composition. The number average fiber length is a value calculated by an image analyzer from an optical microscope observation from the carbon fiber residue collected by high temperature ashing of the molded product, dissolution with a solvent, and decomposition with a chemical. is there. Further, when calculating such a value, a value having a length equal to or shorter than the fiber length is a value obtained by a method not counting. The aspect ratio of the carbon fiber is preferably in the range of 10 to 200, more preferably in the range of 15 to 100, and still more preferably in the range of 20 to 50. The aspect ratio of the fibrous carbon filler is a value obtained by dividing the average fiber length by the average fiber diameter.
Furthermore, it is preferable that the surface of the carbon fiber is oxidized for the purpose of improving the adhesion with the matrix resin and improving the mechanical strength. Although the oxidation treatment method is not particularly limited, for example, (1) a method in which a fibrous carbon filler is treated with an acid or alkali or a salt thereof, or an oxidizing gas, (2) a fiber that can be converted into a fibrous carbon filler, or A method of firing the fibrous carbon filler at a temperature of 700 ° C. or higher in the presence of an inert gas containing an oxygen-containing compound; and (3) after the fibrous carbon filler is oxidized and then in the presence of the inert gas. The method of heat-treating with is suitably exemplified.
Metal coated carbon fiber is a carbon fiber surface coated with a metal layer. Examples of the metal include silver, copper, nickel, and aluminum, and nickel is preferable from the viewpoint of the corrosion resistance of the metal layer. As the method of metal coating, various methods described above for the surface coating with different materials in the glass filler can be employed. Of these, the plating method is preferably used. In addition, in the case of such metal-coated carbon fiber, as the original carbon fiber, those mentioned as the above carbon fiber can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably, it is 0.2 to 0.35 μm.
Such carbon fibers (including metal-coated carbon fibers) are preferably those that are converged with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, a fibrous carbon filler treated with a urethane resin or an epoxy resin is suitable in the present invention because of its excellent mechanical strength.
(D-4; non-fibrous carbon filler)
Examples of the non-fibrous carbon filler preferably used in the present invention include carbon black, graphite, fullerene and the like. Among these, carbon black and graphite are preferable from the viewpoint of mechanical strength, heat and humidity resistance, and thermal stability. As the carbon black, carbon black having a DBP oil absorption of 100 ml / 100 g to 500 ml / 100 g is preferable from the viewpoint of conductivity. Such carbon black is generally acetylene black or ketjen black. Specific examples include Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd., Vulcan XC-72 and BP-2000 manufactured by Cabot Corporation, Ketjen Black EC and Ketjen Black EC-600JD manufactured by Lion Corporation.
As graphite, either natural graphite, which is made of graphite under the mineral name, or various artificial graphites can be used. As natural graphite, any of earth-like graphite, scale-like graphite (Vein Graphite also called massive graphite), and scale-like graphite (Flake Graphite) can be used. Artificial graphite is obtained by heat-treating amorphous carbon and artificially aligning irregularly arranged fine graphite crystals. In addition to artificial graphite used for general carbon materials, Kish graphite, cracked graphite, And pyrolytic graphite. Artificial graphite used for general carbon materials is usually produced by graphitization treatment using petroleum coke or coal-based pitch coke as a main raw material.
The graphite of the present invention may contain expanded graphite that can be thermally expanded by treatment represented by acid treatment, or graphite that has been expanded. The particle size of the graphite of the present invention is preferably in the range of 2 to 300 μm. The particle size is more preferably 5 to 200 μm, further preferably 7 to 100 μm, and particularly preferably 7 to 50 μm. By satisfying such a range, good mechanical strength and molded product appearance are achieved. On the other hand, if the average particle size is less than 2 μm, the effect of improving the rigidity may be reduced, and if the average particle size exceeds 300 μm, the impact resistance is significantly reduced, and so-called graphite floats on the surface of the molded product. This is not preferable.
The amount of fixed carbon in the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98% by weight or more. The volatile content of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less.
In the present invention, the average particle diameter of graphite refers to the particle diameter before becoming a resin composition, and the particle diameter is determined by a laser diffraction / scattering method.
Further, the surface of graphite is subjected to surface treatment such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment in order to increase the affinity with the thermoplastic resin as long as the characteristics of the composition of the present invention are not impaired. It may be given.
(D-5; silicate mineral)
As the filler in the present invention, a silicate mineral can be mentioned. D-5 component is at least a metal oxide component and SiO₂It is a silicate mineral composed of components, and orthosilicate, disilicate, cyclic silicate, chain silicate, and the like are suitable. Silicate minerals take a crystalline state, and the crystals may be in any transformation that each silicate mineral can take, and the shape of the crystals may take various forms such as fibers and plates. Can do.
Silicate minerals may be complex oxides, oxyacid salts (consisting of ionic lattices), or solid solution compounds, and complex oxides are combinations of two or more single oxides, and single oxides and oxygen acids. Any of two or more combinations with a salt may be used, and also in a solid solution, any of a solid solution of two or more metal oxides and a solid solution of two or more oxyacid salts may be used. Hydrates may also be used. The form of water of crystallization in the hydrate is that which enters as hydrogen silicate ion as Si—OH, and hydroxide ion (OH⁻) As ionic ions, and H in the gaps in the structure₂Any form of O molecules may be used.
As the silicate mineral, an artificial synthetic product corresponding to a natural product can be used. As the artificial compound, silicate minerals obtained from various conventionally known methods, for example, various synthetic methods using solid reaction, hydrothermal reaction, ultrahigh pressure reaction and the like can be used.
Specific examples of silicate minerals in each metal oxide component include the following. Here, the description in parentheses is the name of a mineral or the like mainly composed of such a silicate mineral, and means that the compound in parentheses can be used as the exemplified metal salt.
K₂As a component containing O in its component, K₂O ・ SiO₂, K₂O ・ 4SiO₂・ H₂O, K₂O ・ Al₂O₃・ 2SiO₂(Calcylite), K₂O ・ Al₂O₃・ 4SiO₂(White ryu), and K₂O ・ Al₂O₃・ 6SiO₂(Positive feldspar).
Na₂As the component containing O, Na₂O ・ SiO₂And its hydrate, Na₂O ・ 2SiO₂2Na₂O ・ SiO₂, Na₂O ・ 4SiO₂, Na₂O ・ 3SiO₂・ 3H₂O, Na₂O ・ Al₂O₃・ 2SiO₂, Na₂O ・ Al₂O₃・ 4SiO₂(Jadeite), 2Na₂O ・ 3CaO ・ 5SiO₂3Na₂O ・ 2CaO ・ 5SiO₂And Na₂O ・ Al₂O₃・ 6SiO₂(Sorite).
Li₂As a component containing O in its component, Li₂O ・ SiO₂2Li₂O ・ SiO₂, Li₂O ・ SiO₂・ H₂O, 3Li₂O ・ 2SiO₂, Li₂O ・ Al₂O₃・ 4SiO₂(Petalite), Li₂O ・ Al₂O₃・ 2SiO₂(Eucryptite), and Li₂O ・ Al₂O₃・ 4SiO₂(Spodumen).
Included BaO as a component of BaO / SiO₂2BaO · SiO₂, BaO · Al₂O₃・ 2SiO₂(Celsian) and BaO · TiO₂・ 3SiO₂(Bent eye).
As a component containing CaO, 3CaO · SiO₂(Celite clinker mineral alite), 2CaO · SiO₂(Belite of cement clinker mineral) 2CaO · MgO · 2SiO₂(Ochermanite), 2CaO · Al₂O₃・ SiO₂(Gelenite), solid solution of akermanite and Gelenite (Merilite), CaO · SiO₂(Wollastonite (including both α-type and β-type)), CaO · MgO · 2SiO₂(Diopside), CaO / MgO / SiO₂(Gray olivine) 3CaO · MgO · 2SiO₂(Melwinite), CaO · Al₂O₃・ 2SiO₂(Anosite) 5CaO · 6SiO₂・ 5H₂O (Tobermorite, other 5CaO · 6SiO₂・ 9H₂Tobermorite Group Hydrate such as 2CaO · SiO₂・ H₂Wollastonite group hydrates such as O (Hillebrandite), 6CaO · 6SiO₂・ H₂Zonotolite group hydrates such as O (zonotolite), 2CaO.SiO₂・ 2H₂Gyrolite group hydrates such as O (gyrolite), CaO.Al₂O₃・ 2SiO₂・ H₂O (Losonite), CaO · FeO · 2SiO₂(Hedenite), 3CaO · 2SiO₂(Chill coreite), 3CaO · Al₂O₃・ 3SiO₂(Grossula), 3CaO · Fe₂O₃・ 3SiO₂(Andradite), 6CaO · 4Al₂O₃・ FeO ・ SiO₂(Preocroite), clinozoite, olivine, olivine, vesuvite, onolite, scootite, and augite.
Furthermore, Portland cement can be mentioned as a silicate mineral containing CaO as its component. The type of Portland cement is not particularly limited, and any of normal, early strength, ultra-early strength, moderate heat, sulfate resistance, white, and the like can be used. Furthermore, various mixed cements such as blast furnace cement, silica cement, fly ash cement and the like can be used as the B component. Moreover, blast furnace slag, a ferrite, etc. can be mentioned as a silicate mineral which contains other CaO in the component.
Included ZnO as its component is ZnO.SiO₂2ZnO · SiO₂(Trostite) and 4ZnO · 2SiO₂・ H₂O (heteropolar ore) and the like.
Included as a component of MnO is MnO · SiO₂2MnO · SiO₂, CaO · 4MnO · 5SiO₂(Rhodonite) and cause light.
As a component containing FeO, FeO · SiO₂(Ferocilite), 2FeO · SiO₂(Iron olivine), 3FeO · Al₂O₃・ 3SiO₂(Almandin), and 2CaO · 5FeO · 8SiO₂・ H₂O (Tetsuakuchinosenite) and the like.
Include CoO as a component in CoO / SiO₂And 2CoO · SiO₂Etc.
As the component containing MgO, MgO / SiO₂(Steatite, enstatite), 2MgO · SiO₂(Forsterite), 3MgO · Al₂O₃・ 3SiO₂(Birop) 2MgO · 2Al₂O₃・ 5SiO₂(Cordierite), 2MgO · 3SiO₂・ 5H₂O, 3MgO · 4SiO₂・ H₂O (talc), 5MgO · 8SiO₂・ 9H₂O (attapulgite), 4MgO · 6SiO₂・ 7H₂O (Sepiolite), 3MgO · 2SiO₂・ 2H₂O (Chrysolite), 5MgO · 2CaO · 8SiO₂・ H₂O (Translucentite), 5MgO · Al₂O₃・ 3SiO₂・ 4H₂O (chlorite), K₂O ・ 6MgO ・ Al₂O₃・ 6SiO₂・ 2H₂O (phlogobyte), Na₂O ・ 3MgO ・ 3Al₂O₃・ 8SiO₂・ H₂Examples thereof include O (lanthanite), magnesium tourmaline, orthoxenite, camingtonite, vermiculite, and smectite.
Fe₂O₃As the component containing Fe₂O₃・ SiO₂Etc.
ZrO₂As a component containing ZrO,₂・ SiO₂(Zircon) and AZS refractories.
Al₂O₃As a component containing₂O₃・ SiO₂(Sillimanite, Andalusite, Kyanite), 2Al₂O₃・ SiO₂, Al₂O₃・ 3SiO₂3Al₂O₃・ 2SiO₂(Mullite), Al₂O₃・ 2SiO₂・ 2H₂O (Kaolinite), Al₂O₃・ 4SiO₂・ H₂O (Pyrophyllite), Al₂O₃・ 4SiO₂・ H₂O (bentonite), K₂O.3Na₂O · 4Al₂O₃・ 8SiO₂(Kasumi stone), K₂O · 3Al₂O₃・ 6SiO₂・ 2H₂O (mascobyte, sericite), K₂O ・ 6MgO ・ Al₂O₃・ 6SiO₂・ 2H₂O (phlogopite), various zeolites, fluorine phlogopite, biotite, and the like can be mentioned.
Among the above-mentioned silicate minerals, talc, mica, and the like are particularly suitable because they have an excellent balance between rigidity and impact resistance, are excellent in moisture and heat resistance, thermal stability and appearance, and are easily available. Wollastonite.
(D-5-i) Talc
Talc in the present invention is hydrous magnesium silicate in terms of chemical composition, and generally has the chemical formula 4SiO₂・ 3MgO ・ 2H₂It is represented by O and is usually a scaly particle having a layered structure.₂56 to 65% by weight, MgO 28 to 35% by weight, H₂O is composed of about 5% by weight. Fe as other minor components₂O₃0.03 to 1.2% by weight, Al₂O₃0.05 to 1.5% by weight, CaO 0.05 to 1.2% by weight, K₂O is 0.2 wt% or less, Na₂O contains 0.2% by weight or less. A more preferable composition of talc is SiO.₂: 62-63.5 wt%, MgO: 31-32.5 wt%, Fe₂O₃: 0.03-0.15 wt%, Al₂O₃: 0.05 to 0.25% by weight, and CaO: 0.05 to 0.25% by weight are preferable. Further, the ignition loss is preferably 2 to 5.5% by weight. With such a suitable composition, a resin composition having good thermal stability and hue can be obtained, and a good molded product can be produced by further increasing the molding processing temperature. As a result, the composition of the present invention can be further fluidized, and can be used for thin molded products having larger or complex shapes.
As for the particle size of talc, the average particle size measured by the sedimentation method is 0.1 to 50 μm (more preferably 0.1 to 10 μm, still more preferably 0.2 to 5 μm, particularly preferably 0.2 to 3.5 μm). ) Is preferable. Therefore, a more preferable talc of the present invention is a talc having the above-mentioned preferable composition and having an average particle diameter of 0.2 to 5 μm. Furthermore, the bulk density is 0.5 (g / cm³) It is particularly preferable to use the talc as described above as a raw material. As an example of talc satisfying such conditions, “Upn HS-T0.8” manufactured by Hayashi Kasei Co., Ltd. is exemplified. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.
In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).
Furthermore, talc is preferably in an aggregated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method using a sizing agent, and a method of compression. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.
(D-5-ii) Mica
Mica having an average particle size of 5 to 250 μm can be used. Preferably, mica having an average particle diameter (D50 (median diameter of particle diameter distribution)) measured by a laser diffraction / scattering method of 5 to 50 μm. If the average particle diameter of mica is less than 5 μm, it is difficult to obtain the effect of improving rigidity. On the other hand, a resin composition containing mica having an average particle size exceeding 250 μm is inferior in appearance and flame retardancy while its mechanical properties tend to be saturated. The average particle diameter of mica is measured by a laser diffraction / scattering method or a vibration sieving method. In the laser diffraction / scattering method, it is preferable that the 325 mesh pass is performed on 95% by weight or more of mica by the vibration sieving method. For mica having a larger particle size, the vibration sieving method is generally used. In the vibration sieving method of the present invention, first, sieving is carried out for 10 minutes using a JIS standard standard sieve in which 100 g of mica powder to be used is stacked in the order of openings using a vibration sieve device. This is a method of obtaining the particle size distribution by measuring the weight of the powder remaining on each sieve.
As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 0.3 μm. An aspect ratio of 5 to 200, preferably 10 to 100 can be used. The mica used is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and solves the problems of the present invention at a better level. Accordingly, a more preferred mica of the present invention is a mascobite having an average particle diameter of 5 to 250 μm, more preferably 5 to 50 μm. As such a suitable mica, for example, “A-21” manufactured by Yamaguchi Mica Industry Co., Ltd. is exemplified. The mica may be pulverized by either dry pulverization or wet pulverization. The dry pulverization method is more inexpensive and more general, but the wet pulverization method is effective for pulverizing mica more thinly and finely (the rigidity improvement effect of the resin composition becomes higher). In the present invention, the wet pulverized mica is more preferable.
(D-5-iii) Wollastonite
The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, still more preferably 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. For the fiber diameter, for the image obtained by observation with an electron microscope, the filler for which the fiber diameter is to be measured is randomly extracted, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter. The observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work). On the other hand, the measurement of average fiber length observes a filler with an optical microscope, calculates | requires individual length, and calculates a number average fiber length from the measured value. Observation with an optical microscope begins with the preparation of a dispersed sample so that the fillers do not overlap each other. Observation is performed under the condition of 20 times the objective lens, and the observed image is taken as image data into a CCD camera having about 250,000 pixels. The obtained image data is calculated by using a program for obtaining the maximum distance between two points of the image data using an image analysis device. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurement is 500 or more (600 or less is suitable for work). The wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible. By this magnetic separator processing, the iron content in wollastonite is Fe.₂O₃It is preferably 0.5% by weight or less in terms of Therefore, the more preferable wollastonite of the present invention has a fiber diameter of 0.1 to 10 μm, more preferably 0.1 to 5 μm, and further preferably 0.1 to 3 μm. The average particle size is 5 to 250 μm, more preferably 5 to 50 μm, and the iron content is Fe₂O₃Wollastonite in an amount of 0.5% by weight or less. Examples of such suitable wollastonite include “SH-1250” and “SH-1800” manufactured by Kinsei Matech Corporation, “KGP-H40” manufactured by Kansai Matec Corporation, “NYGLOS4” manufactured by NYCO Corporation, and the like.
The silicate mineral in the present invention is preferably not surface-treated, but a silane coupling agent (including alkylalkoxysilane and polyorganohydrogensiloxane), higher fatty acid ester, acid compound (for example, phosphorous acid, Surface treatment may be carried out with various surface treatment agents such as phosphoric acid, carboxylic acid, and carboxylic acid anhydride) and wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes. Among the silicate minerals in the present invention, talc and wollastonite are particularly suitable. Such talc and wollastonite are good in terms of both rigidity and impact resistance, and the deterioration of hue and appearance (for example, the occurrence of silver streak) when blended with a polycarbonate resin and a polyester resin are small.
In the resin composition of the present invention, the content of the component D is 0 to 15 parts by weight, preferably 8 to 15 parts by weight, more preferably 9 to 14 parts by weight with respect to 100 parts by weight of the resin component. More preferably, it is 10 to 12 parts by weight. If the upper limit is exceeded, the impact strength will decrease, and if it is less than the lower limit, the effect of improving the rigidity will be insufficient, such being undesirable.
(Other additives)
In addition to the above components A to D, the resin composition of the present invention includes various additives (flame retardants, fluorine-containing anti-dripping agents, stabilizers, ultraviolet absorbers, release agents, Dyes and pigments, compounds having heat ray absorbing performance, antistatic agents, acidity adjusting agents, and the like) (for details of various additives, refer to WO2011 / 088741).
Examples of the phosphorus stabilizer preferably used in the present invention include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.
Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and the like. Among these, trialkyl phosphate is preferable. The carbon number of the trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.
Examples of the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective for improving thermal stability, and the acid phosphate itself is preferable because of high stability.
Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl Intererythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.
Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and the like.
Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples include -4-phenyl-phenyl phosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenyl phosphonite. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite Knight and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.
Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, diphenylbenzylphosphine, and the like. A particularly preferred tertiary phosphine is triphenylphosphine.
Suitable phosphorus stabilizers are triorganophosphate compounds, acid phosphate compounds, and phosphite compounds represented by the following formula (XIII). It is particularly preferable to add a triorganophosphate compound.

In the formula (XIII), R and R ′ each represents an alkyl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkylaryl group, and may be the same or different from each other.
As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferred as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, CIBA SPECIALTY manufactured by CHEMICALS), both of which are available.
Among the above formulas (XIII), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.
The resin composition of the present invention contains thermoplastic resins other than the A component and B component, elastomers, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents and the like. can do.
Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polystyrene resins, acrylonitrile / styrene. Resins such as copolymer (AS resin), polymethacrylate resin, phenol resin, epoxy resin, cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, and thermoplastic fluororesin (for example, represented by polyvinylidene fluoride resin) Can be mentioned. Examples of the elastomer include acrylic elastomers, polyester elastomers, polyamide elastomers, and the like.
The content of the other thermoplastic resin or elastomer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the resin component.
(Production method of resin composition)
Arbitrary methods are employ | adopted for preparation of the resin composition of this invention. For example, there can be mentioned a method in which the A component, the B component, the C component, the D component and optionally other components are premixed and then melt-kneaded to form pellets.
Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like, if necessary. As another method, for example, when a component having a powder form is included as the component A, a master batch of an additive diluted with powder by blending a part of the powder and an additive to be blended is manufactured, and the master A method using a batch is mentioned. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred.
In addition, a method of supplying each component independently to a melt-kneader represented by a twin-screw extruder without premixing each component can also be used. Moreover, after premixing some components, the method of supplying to a melt-kneader independently of the remaining components is mentioned. In particular, when an inorganic filler is blended, the inorganic filler is preferably supplied from a supply port in the middle of the extruder into the molten resin using a supply device such as a side feeder. The premixing means and granulation are the same as described above. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.
As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing foreign substances and the like mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such screens include wire meshes, screen changers, sintered metal plates (disc filters, etc.) and the like.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.
Furthermore, it is preferable that the moisture contained in the A component and the B component is small before melt kneading. Therefore, it is more preferable to melt-knead after drying either component A or component B or both by various methods such as hot air drying, electromagnetic wave drying, or vacuum drying. The vent suction during melt-kneading is preferably in the range of 1 to 60 kPa, preferably 2 to 30 kPa.
The resin extruded as described above is directly cut into pellets, or after forming the strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust or the like during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.
(Molded product using the resin composition of the present invention)
A molded product using the resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, it is obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.
Also, in extrusion molding, various profile extrusion molded products, sheets, films, etc. are obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be formed into a molded product by rotational molding, blow molding or the like.
The form of the present invention considered to be the best by the present inventor is a collection of the preferred ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, parts in the examples are parts by weight and% is% by weight. In addition, evaluation and manufacture of the resin pellet were manufactured with the following method.
(I) Evaluation of resin composition (i) Titanium content analysis: Measured using an ICP mass spectrometer Agilent 7500cs manufactured by Agilent Technologies. In addition, after adding sulfuric acid to the weighed sample and ashing the resin by microwave decomposition, the sample was further added with nitric acid and subjected to microwave decomposition to constant volume of the residual metal with ultrapure water. The amount of element was measured.
(Ii) Rigidity: Various pellets obtained were dried at 120 ° C. for 5 hours, and then molded using an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. Was measured and the tensile modulus was measured in accordance with ISO527-1,2.
(Iii) Charpy impact strength: The various pellets obtained were dried at 120 ° C. for 5 hours, and then the cylinder temperature was 280 ° C. and the mold temperature was 70 ° C. using an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) A molded piece was molded, and the Charpy impact strength with a notch was measured according to ISO179.
(Iv) Heat-and-moisture resistance: After the obtained resin pellets are dried at 120 ° C. for about 5 hours to make the moisture content in the pellets 200 ppm or less, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: SG260M-HP) is used. A test piece of length 70 mm × width 50 mm × thickness 2 mm was continuously injection-molded under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 70 ° C., a molding cycle of 50 seconds, and an injection speed of 15 mm / sec. The test piece left for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50% was used as a test piece before the wet heat treatment, and the test piece before the wet heat treatment was kept at a constant temperature and humidity of 80 ° C. and a relative humidity of 95%. After leaving the test machine for 500 hours to perform wet heat treatment, a test piece left again for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50% was used as a test piece after the wet heat treatment.
The test specimens before and after the wet heat treatment were pulverized so that no foreign matter was mixed in, and dried at 120 ° C. for about 5 hours to reduce the moisture content to 200 ppm or less. MVR (melt volume rate) measurement was performed by a method based on ISO 1133 under the condition of 2.16 kgf. The measurement was performed with a semi-auto melt indexer 2A type manufactured by Toyo Seiki Co., Ltd. The wet heat resistance was calculated according to the following formula, and the rate of change (ΔMVR) before and after wet heat treatment was calculated. A larger ΔMVR means that the resin deterioration of the molded product is larger and the heat and moisture resistance is inferior, and ΔMVR is preferably 200 or less, more preferably 170 or less.
ΔMVR (moisture and heat resistance) = 100 × (MVR of test piece after wet heat treatment) / (MVR of test piece before wet heat treatment)
(V) Thermal stability: After the obtained resin pellets were dried at 120 ° C. for about 5 hours to reduce the moisture content in the pellets to 200 ppm or less, an injection molding machine (Sumitomo Heavy Industries, Ltd .: SG260M-HP) was used. Using a cylinder temperature of 280 ° C., a mold temperature of 70 ° C., a molding cycle of 50 seconds, and an injection speed of 15 mm / sec, a test piece of length 70 mm × width 50 mm × thickness 2.0 mm was continuously injection molded. The test piece of the continuous molded product was obtained (the quality of the test piece of the continuous molded product is substantially the same as the test piece before the wet heat treatment). After obtaining a test piece of a continuously molded product, the molding machine was stopped for 10 minutes, and the molten resin was retained in the molding machine cylinder. 10 minutes after the molding machine was stopped, molding was started again, and the second shot from the re-molding was used as a test piece for the retained molded product.
The continuously molded product and the retained molded product are pulverized so that no foreign matter is mixed in, dried at 120 ° C. for about 5 hours to reduce the moisture content to 200 ppm or less, and each pulverized sample has a temperature of 280 ° C. and a load of 2.16 kgf. Below, MVR (melt volume rate) measurement was performed by the method based on ISO1133. The measurement was performed with a semi-auto melt indexer 2A type manufactured by Toyo Seiki Co., Ltd. The thermal stability was calculated according to the following formula, and the MVR change rate (ΔMVR (thermal stability)) before and after residence was calculated. The larger this ΔMVR (thermal stability), the greater the deterioration of the resin during residence and the lower the thermal stability. ΔMVR is preferably 150 or less, more preferably 130 or less.
ΔMVR (thermal stability) = 100 × (MVR of test piece of staying molded product) / (MVR of test piece of continuous molded product)
(Vi) Chemical resistance: (iii) A test piece prepared by Charpy impact test was subjected to a bending strain of 6 MPa, and immersed in commercial regular gasoline for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The appearance was visually observed and evaluated. The evaluation was performed according to the following criteria.
○: No abnormality is observed. ×: Appearance changes such as cracks and whitening are observed in the molded products. Examples 1 to 12 and Comparative Examples 1 to 11
A polycarbonate resin, a polyester resin, a filler and various additives are mixed in the blending amounts shown in Tables 1 to 3 in a blender, and then melt-kneaded using a vent type twin screw extruder to obtain the resin composition of the present invention. A pellet consisting of Various additives other than the filler were preliminarily prepared with a polycarbonate resin powder with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin screw extruder used was TEX30α-31.5BW-2V (completely meshed, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The kneading zone was of one type before the vent opening. Extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 130 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 270 ° C. from the first supply port to the die part.
The components indicated by symbols in Tables 1 to 3 are as follows.
(A component)
A-1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 22,400 (component B)
(B-1 component)
PBT-1: Polybutylene terephthalate resin having an IV value of 0.87 (Polyplastics Corporation DURANEX 500FP (trade name))
(B-2 component)
PET-1: Polyethylene terephthalate resin prepared by the following production method (intrinsic viscosity = 0.53, titanium content 23 ppm)
(Production method)
While stirring a solution obtained by dissolving monolauryl phosphate in ethylene glycol heated to 100 ° C, a mixed solution of ethylene glycol and acetic acid containing titanium tetrabutoxide was slowly added to complete the reaction between the titanium compound and the phosphorus compound. A catalyst was prepared. After producing an ester oligomer from ethylene glycol and terephthalic acid, a polycondensation reaction was carried out in a polycondensation reaction tank together with a catalyst. The degree of progress of the polycondensation was checked by monitoring the load on the stirring blade in the reaction system, and the reaction was terminated when the desired degree of polymerization was reached. Thereafter, the reaction mixture in the system was continuously extruded in a strand form from the discharge part, cooled and solidified, and cut to prepare polyethylene terephthalate granular pellets having a particle size of about 3 mm.
(C component)
C-1: EXL2390: Acrylic core-shell polymer (Rohm and Haas Co., Ltd .: Paraloid EXL-2390 (trade name), core is about 50% by weight of butyl acrylate component and about 40% by weight of 2-ethylhexyl acrylate component, shell is Core-shell polymer that is about 10% by weight methyl methacrylate)
C-2 (Comparison): EXL2388: Acrylic core-shell polymer (Rohm and Haas Co., Ltd .: Paraloid EXL-2388 (trade name), core is about 90% by weight of butyl acrylate component, shell is about 10% by weight of methyl methacrylate A core-shell polymer)
C-3 (Comparison): EXL-2620: Styrenic rubber polymer (Rohm and Haas Co., Ltd .: Paraloid EXL-2620 (trade name), core is 70% polybutadiene, shell is styrene and methyl methacrylate 30% % Core-shell polymer)
C-4 (Comparison): S2001: Methyl methacrylate is grafted on 90% by weight of a composite rubber having a structure in which a polyorganosilicon rubber component and a polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated. Polymerized composite rubber graft copolymer (Metbrene S-2001 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)
(D component)
D-1: Wollastonite with an average particle size of 4 μm (Kansai Matec Co., Ltd .: KGP-H40)
D-2: Wollastonite having an average particle diameter of 5 μm (manufactured by Kinsei Matech Corporation: SH-1250)
D-3: Compressed fine powder talc (Hayashi Kasei Co., Ltd .: Upn HS-T0.8)
D-4: wet-pulverized mica having an average particle size of 22 μm (Yamaguchi Mica Co., Ltd .: A-21)
(Other ingredients)
AO-1: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (manufactured by Adeka: Adeka Stub PEP-24G)
AO-2: Trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP)

Advantages of the Invention As is clear from FIG. 1 comparing Example 2 using C-1 as the C component and Comparative Examples 6 to 8 using C-2, C-3, and C-4 as the C component. Example 2 is excellent in both tensile modulus and Charpy impact strength.
Similarly, as is clear from FIG. 2 comparing Example 12 using C-1 as the C component and Comparative Examples 9 to 11 using C-2, C-3, and C-4 as the C component. Example 11 is excellent in both tensile modulus and Charpy impact strength.
Thus, the resin composition of the present invention is excellent in both tensile elastic modulus and Charpy impact strength. Further, the resin composition of the present invention is excellent in thermal stability and further has good chemical resistance.

The resin composition of the present invention is widely useful in various fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electric / electronic devices, machines, and the like.

Claims

(A) Polycarbonate resin (component A) 80 to 50 parts by weight and (B) polyester resin (component B) 20 to 50 parts by weight of resin component 100 parts by weight,
(C) A core (C-1 component) comprising a cross-linked acrylate ester elastic body composed of an acrylate ester having 1 to 4 carbon atoms in the alkyl group and an acrylate ester having 5 to 8 carbon atoms in the alkyl group And 1 to 10 parts by weight of a core-shell polymer (component C) consisting of a shell (component C-2) containing methacrylic acid ester as the main component and 0 to 15 parts by weight of a filler (component D) (D) .
2. The resin according to claim 1, wherein the component B is a polyethylene terephthalate resin (PET) and a polybutylene terephthalate resin (PBT), and the blending ratio (weight ratio) (PET / PBT) is 1/7 to 7/8. Composition.
Polyester resin (component B)
Obtained by reacting the titanium compound (1) represented by the following general formula (I), and the titanium compound (1) with the aromatic polycarboxylic acid represented by the following general formula (II) or an anhydride thereof. At least one titanium compound component selected from the group consisting of titanium compounds (2),
A phosphorus compound component comprising at least one phosphorus compound (3) represented by the following general formula (III):
Reacts when the molar molar ratio (mTi / mP) of the titanium compound component in terms of titanium atom (mTi) and the phosphorus compound component in terms of phosphorus atom (mP) is 1/3 to 1/1. 2. The resin composition according to claim 1, wherein the resin composition is a polyester resin polymerized by using a compound containing a reaction product as a catalyst and satisfies the following (i) and (ii):
(I) The intrinsic viscosity is 0.4 to 1.2.
(Ii) The catalyst-derived titanium element content is 0.001 ppm to 100 ppm.

[In the formula (I), R 1, R 2, R 3 and R 4 each represent an alkyl group having 2 to 10 carbon atoms each independently, k is an integer of 1 to 3, And when k is 2 or 3, two or three R 2 and R 3 may be the same or different from each other. ]

[In the formula (II), m represents an integer of 2 to 4. ]

[In the formula (III), R 5 represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. ]
The resin composition according to claim 1, wherein the content of titanium element in the polyester resin (component B) is 0.001 to 50 ppm.
The resin composition according to claim 1, wherein the polyester resin (component B) is a polyester resin polymerized using a compound represented by the following formula (IV) as a catalyst.

[In the above formula, R 6 and R 7 each independently represent an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms]
The resin composition according to claim 1, wherein the polyester resin (component B) is polyethylene terephthalate.
The resin composition according to claim 1, wherein the polyester resin (component B) is polybutylene terephthalate.
2. The resin composition according to claim 1, wherein the C-1 component is a core composed of a crosslinked acrylate-based elastic body composed of butyl acrylate and 2-ethylhexyl acrylate.
The resin composition according to claim 1, wherein the component D is at least one filler selected from the group consisting of glass, talc, mica, wollastonite, zeolite, carbon fiber, and graphite.
The resin composition according to claim 9, wherein the D component is at least one inorganic filler selected from the group consisting of talc, mica and wollastonite.
A molded product formed by injection molding the resin composition according to any one of claims 1 to 10.
The injection molded product according to claim 11, wherein the injection molded product is a vehicle interior / exterior member.