JP2018090724A - Resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in impact resistance and also excellent in tensile strength, elastic modulus, and moldability.SOLUTION: The resin composition of the present invention contains 50-95 pts.mass of a polyester resin (A), 0.5-10 pts.mass of a tackifier (B), and 5-40 pts.mass of an inorganic filler (C). The polyester resin (A) satisfies the following (A-1) and (A-2): (A-1) the polyester resin (A) contains a structural unit (a1) derived from an aromatic dicarboxylic acid and a structural unit (a2) derived from a C2-10 diol; and (A-2) a melting point (Tm) measured by a differential scanning calorimeter (DSC) is in the range of 200-245°C.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition having a specific composition and a molded body obtained from the resin composition.

  Polyester resins such as polybutylene terephthalate are widely used for injection molding. Moreover, it is known that mechanical strength and heat resistance will improve by containing inorganic fillers, such as glass fiber (for example, refer patent document 1).

Japanese Patent Laid-Open No. 10-60242

  The polyester resin composition containing an inorganic filler such as glass fiber has a tendency that a stress-concentrated portion tends to brittlely break depending on the shape of the molded product and particularly when the blending amount of the filler is relatively high. Therefore, it has been studied to add a resin having an impact-modifying effect to the polyester resin composition. An ethylene / methyl acrylate / glycidyl methacrylate copolymer or the like is known as a resin having an impact resistance-modifying effect, but there are cases where the impact-resistance-modifying effect is not sufficient. Moreover, in order to improve the modification | reformation effect of the said resin, the compounding quantity had to be increased, and there existed a case where tensile strength, an elasticity modulus, and moldability were sacrificed.

  The subject of this invention is providing the polyester resin composition excellent in impact resistance, and also excellent in tensile strength, an elasticity modulus, and moldability, and a molded object obtained from this.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by using a resin composition having a specific composition, and the present invention has been completed.

That is, this invention relates to the following resin compositions and the molded object obtained from this.
[1] A polyester resin (A), a tackifier (B), and an inorganic filler (C) are contained, and the total content of the (A), (B), and (C) is 100 masses. When (A) is 50 to 95 parts by mass, (B) is 0.5 to 10 parts by mass, (C) is 5 to 40 parts by mass, and (A) is the following (A-1) ) And (A-2).
(A-1) including a structural unit (a1) derived from an aromatic dicarboxylic acid and a structural unit (a2) derived from a diol having 2 to 10 carbon atoms (A-2) a differential scanning calorimeter (DSC) The melting point (Tm) due to is in the range of 200-245 ° C.

[2] The (B) is at least one selected from natural rosin, modified rosin, polyterpene resin, synthetic petroleum resin, coumarone resin, phenol resin, xylene resin, styrene resin, and isoprene resin. The resin composition as described in [1].
[3] The resin composition according to [1] or [2], wherein (B) satisfies the following (B-1), (B-2), and (B-3).
(B-1) Melt viscosity at 160 ° C. is 10 to 500,000 mP · s (B-2) Softening point is in the range of 60 to 180 ° C. (B-3) Measured with a differential scanning calorimeter (DSC) The glass transition temperature (Tg) in the range of 0 to 100 ° C. [4] The above (B) satisfies the following (B-4), [1] to [3] Resin composition.
(B-4) The molecule contains 50 to 100% by mass of a structural unit derived from at least one selected from the group consisting of styrene, α-methylstyrene, indene, vinyltoluene and isopropenyltoluene.

[5] The resin composition according to any one of [1] to [4], which contains glass fiber as (C).
[6] The resin composition according to any one of [1] to [5], which contains polybutylene terephthalate as (A).
[7] When the total content of (A), (B) and (C) is 100 parts by mass, (A) is 55 to 80 parts by mass, (B) is 2 to 5 parts by mass, ( The resin composition according to any one of [1] to [6], comprising 20 to 40 parts by mass of C).
[8] A molded article comprising the resin composition according to any one of [1] to [7].

  According to the present invention, it is possible to provide a polyester resin composition which is excellent in impact resistance and further excellent in tensile strength, elastic modulus and moldability, and a molded body obtained therefrom.

  Hereinafter, the resin composition of the present invention and the molded product obtained therefrom will be described in detail.

(Resin composition)
The resin composition of the present invention contains a polyester resin (A), a tackifier (B), and an inorganic filler (C).

  In the resin composition of the present invention, when the total content of the polyester resin (A), the tackifier (B), and the inorganic filler (C) is 100 parts by mass, the content of (A) is 50 It is -95 mass parts, Preferably it is 50-94.5 mass parts, More preferably, it is 55-80 mass parts. Content of (B) is 0.5-10 mass parts, Preferably it is 2-5 mass parts. Moreover, content of an inorganic filler (C) is 5-40 mass parts, Preferably it is 20-40 mass parts.

  When the amount of the tackifier (B) is within this range, the impact resistance of the resulting resin composition can be increased, and the molding processability of the resin composition can be improved. The tackifier (B) increases the impact resistance of the resin composition as described later, but the effect of increasing the impact resistance can be obtained without increasing the amount in the composition. Therefore, the loss of the tensile strength and elastic modulus of the resin composition due to the addition of the tackifier (B) can be reduced.

  Hereinafter, each component and each requirement will be described.

1. Polyester resin (A)
Although the resin composition of this invention may contain only 1 type of polyester resins (A) and may contain 2 or more types, it satisfies the following requirements (A-1) and (A-2).

  Requirement (A-1): including a structural unit (a1) derived from an aromatic dicarboxylic acid and a structural unit (a2) derived from a diol having 2 to 10 carbon atoms

  A polyester resin that satisfies the requirement (A-1) is preferable because it is excellent in mechanical properties, heat resistance, processability, and electrical properties.

  The structural unit (a1) derived from the aromatic dicarboxylic acid (hereinafter sometimes simply referred to as “structural unit (a1)”) is formally converted to —OH from two carboxyl groups contained in the aromatic dicarboxylic acid. It is a structural unit having a structure excluding. The polyester resin may contain only one type of structure (a1) derived from aromatic dicarboxylic acid, or may contain two or more types. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2-methyl terephthalic acid, naphthalenedicarboxylic acid and the like. Among these, terephthalic acid is preferable from the viewpoint of further improving mechanical properties and processability.

  On the other hand, the structural unit (a2) derived from a diol having 2 to 10 carbon atoms (hereinafter sometimes simply referred to as “structural unit (a2)”) is formally converted to a diol having 2 to 10 carbon atoms. It is a structural unit having a structure in which -H is removed from two contained hydroxyl groups. The polyester resin may contain only 1 type of the structure (a2) derived from a C2-C10 diol, and may contain 2 or more types.

  Specific examples of the diol having 2 to 10 carbon atoms include aliphatic diols having 2 to 10 carbon atoms. Examples of such aliphatic diols include 1,2-ethanediol (ethylene glycol: 2 carbon atoms), 1,3-propanediol (trimethylene glycol: 3 carbon atoms), 1,2-propanediol ( Propylene glycol: 3 carbon atoms, 1,4-butanediol (tetramethylene glycol: 4 carbon atoms), 1,6-hexanediol (hexamethylene glycol: 6 carbon atoms), 1,8-octanediol ( And octamethylene glycol: 8 carbon atoms), 1,3-nonanediol (9 carbon atoms), 1,9-nonanediol (nonamethylene glycol: 9 carbon atoms), and the like.

  The diol having 2 to 10 carbon atoms may be a diol having an alkyl group in the side chain (hereinafter also referred to as “side-chain alkyl group-containing glycol”). Examples of the side chain alkyl group-containing glycol include 2-methyl-1,3-propanediol (4 carbon atoms), 2-ethyl-1,3-propanediol (4 carbon atoms), 2-hexyl-1,3. -Propanediol (9 carbon atoms), 2-hexyl-1,6-propanediol (9 carbon atoms), 2,2-dimethylpropane-1,3-diol (neopentyl glycol: 5 carbon atoms), 2-ethyl-2-methyl-1,3-propanediol (6 carbon atoms), 2,2-diethyl-1,3-propanediol (7 carbon atoms), 2-methyl-2-n-butyl- 1,3-propanediol (8 carbon atoms), 2-methyl-1,8-octanediol (9 carbon atoms) and the like can be mentioned. Among these, 1,4-butanediol is preferable from the viewpoint of increasing the crystallization rate.

  From the viewpoint of further improving mechanical properties, heat resistance, workability, and electrical properties, the molar ratio ((a1) / (a2)) of the structural unit (a1) to the structural unit (a2) is from 0.9 to It is preferable to be in the range of 1.1.

  The polyester resin (A) is preferably composed only of the structural units (a1) and (a2). However, the polyester resin (A) is derived from other polycarboxylic acid or polyhydric alcohol as long as the effects of the present invention are not significantly impaired. It may contain a structural unit. Other polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and undecadicarboxylic acid; -Various dicarboxylic acids such as furandicarboxylic acids such as furandicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid; and carboxylic acid esters thereof. The other polycarboxylic acid may be a trivalent or higher polyvalent carboxylic acid such as butanetricarboxylic acid or trimellitic acid, or may be an oxydicarboxylic acid such as 4-hydroxyphthalic acid. . Examples of other polyhydric alcohols include trihydric or higher polyhydric alcohols such as aromatic diols, trimethylolethane, and glycerin.

  The amount of other structural units (structural units derived from other polyvalent carboxylic acids or other polyhydric alcohols) is 100 mol% of the total of the structural units (a1) and (a2) and other structural units. Is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

Requirement (A-2): Melting | fusing point (Tm) by a differential scanning calorimeter (DSC) exists in the range of 200-245 degreeC.
The melting point (Tm) of the polyester resin (A) is preferably 210 to 240 ° C, more preferably 215 to 235 ° C.

  When the melting point (Tm) is 245 ° C. or lower, there is no need to increase the processing temperature of the resin composition, and a decrease in molecular weight due to heat during kneading and / or molding of the resin composition can be suppressed. On the other hand, when the melting point (Tm) is 200 ° C. or higher, the thermal deformation temperature of the polyester resin (A) is increased, and the heat resistance is improved.

  As an example of a method for adjusting the melting point (Tm) of the polyester resin (A) to the above temperature range, as the above-mentioned other polyvalent carboxylic acid or other polyhydric alcohol, a trihydroxy or higher polyhydroxy such as triol or tricarboxylic acid. A method using a small amount of a compound, polycarboxylic acid or the like can be mentioned.

  Specific examples of the polyester resin (A) satisfying the requirements (A-1) and (A-2) include polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polybutylene naphthalate (PBN), polyethylene iso Examples include phthalate / terephthalate copolymers. Of these, polybutylene terephthalate (PBT) is preferable from the viewpoint of further improving the mechanical properties, heat resistance, processability, and electrical properties of the resin composition.

  The polyester resin (A) preferably satisfies the following requirement (A-3).

Requirement (A-3): The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 10,000 to 50,000, and the weight average molecular weight (Mw) is 60000 to 300,000.
A polyester resin that satisfies the requirement (A-3) is preferable because it is excellent in mechanical properties, heat resistance, and processability.

2. Tackifier (B)
The resin composition of this invention may contain only 1 type of tackifiers (B), and may contain 2 or more types. A tackifier is a substance that can impart tackiness by blending with a high molecular weight compound, and generally an oligomer having a molecular weight of several hundred to several thousand and a softening point of about 60 to 160 ° C. It is. The tackifier (B) is preferably a resin having 5 carbon atoms and a plurality of diene having two double bonds bonded thereto; or a resin having a cyclic structure based on a carbon skeleton bonded thereto. The tackifier (B) having such a structure is easily compatible with the polyester resin (A) and is easily finely dispersed in the polyester resin (A).

  Specific examples of the tackifier (B) include natural rosin, modified rosin, polyterpene resin, synthetic petroleum resin, coumarone resin, phenol resin, xylene resin, styrene resin, and isoprene resin.

More specific examples of the tackifier (B) include C ₄ fraction obtained by cracking petroleum, naphtha, etc., C ₅ fraction, a mixture thereof, or any component (for example, C ₅₎ contained therein. Aliphatic hydrocarbon resins made mainly of isoprene and 1,3-pentadiene in the fraction;
Petroleum, aromatic hydrocarbon resin to the styrene derivatives and indenes contained in C ₉ fraction obtained by decomposition of naphtha as a main material;
C ₄ fraction and C ₅ fraction to any component and copolymerized with aliphatic aromatic copolymer hydrocarbon resin contained in any component and C ₉ fraction contained;
An alicyclic hydrocarbon resin obtained by hydrogenating an aromatic hydrocarbon resin;
Synthetic terpene-based hydrocarbon resins including aliphatic, alicyclic and aromatic hydrocarbon resins;
Terpene hydrocarbon resin made from α, β-pinene in turpentine oil;
Coumarone indene hydrocarbon resin made from indene and styrene in coal tar naphtha;
Low molecular weight styrenic resin;
Rosin hydrocarbon resin; and the like.

  Alternatively, it is obtained by copolymerizing a plurality of types of monomers selected from terpene monomers, chroman monomers, styrene monomers, or phenol monomers as disclosed in JP-A-2005-194488. May be.

The tackifier (B) preferably satisfies the following requirement (B-1).
Requirement (B-1): The melt viscosity at 160 ° C. is 10 to 500,000 mP · s The melt viscosity at 160 ° C. of the tackifier (B) is preferably 500 to 300,000 mP · s, more preferably Is 1,000 to 250,000 mP · s, particularly preferably 10,000 to 20,000.

  When the melt viscosity at 160 ° C. of the tackifier (B) is within the above range, the tackifier (B) is easily compatible with the polyester resin (A). Therefore, the tackifier (B) is more easily dispersed more uniformly in the resin composition, and a resin composition having more sufficient impact resistance can be obtained. In addition, the molding processability of the resin composition, specifically, the kneadability and the molding processability during injection molding, etc. are improved.

  The tackifier (B) preferably satisfies the following requirements (B-2) and (B-3) in addition to the requirement (B-1).

Requirement (B-2): The softening point measured according to JIS K2207 is 60 to 180 ° C. The softening point of the tackifier (B) is preferably 100 to 160 ° C., more preferably 110 ° C. ~ 150 ° C. When the softening point of the tackifier (B) is in the above range, the tackifier (B) is easily compatible with the polyester resin (A) and more easily dispersed more uniformly. Therefore, it is preferable at the point from which the resin composition which has more sufficient impact resistance and is excellent in workability is obtained.

Requirement (B-3): The glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is in the range of 0 to 100 ° C. The glass transition temperature (Tg) of the tackifier (B) is preferably It is 20-95 degreeC, More preferably, it is 40-90 degreeC, More preferably, it is 50-85 degreeC. When the glass transition temperature (Tg) of the tackifier (B) is equal to or higher than the lower limit, it is preferable in terms of improving the heat resistance of the resin composition, and when it is equal to or lower than the upper limit, workability when compounding the resin composition. This is preferable.

  The tackifier (B) preferably satisfies the following requirement (B-4) in addition to the requirement (B-1), and particularly preferably satisfies all the requirements (B-1) to (B-4). .

  Requirement (B-4): Containing 50 to 100% by mass of a structural unit derived from at least one selected from the group consisting of styrene, α-methylstyrene, indene, vinyltoluene and isopropenyltoluene in the molecule.

  Content of the structural unit chosen from the said group becomes like this. Preferably it is 60-100 mass%, More preferably, it is 80-100 mass%. In addition, when a tackifier (B) contains the some structural unit chosen from the said group, the said content is these total amounts.

  When the tackifier (B) has the above structural unit in the molecule, the reason is not clear, but the polyester resin (A) and the tackifier (B) are particularly easily compatible with each other. B) is easily finely dispersed in the polyester resin (A). The tackifier (B) containing a structural unit selected from the above group has an aromatic ring in the molecule. Therefore, the volumetric shrinkage rate of the resin composition when the resin composition is injection-molded becomes lower. Accordingly, when the molded body is formed, it is estimated that the polyester resin (A) and the inorganic filler (C) are difficult to peel off, that is, their interface strength is easily maintained, and the impact resistance of the resin composition is increased. .

  In the resin composition of the present invention, the flowability of the resin composition is improved and the moldability is improved by the compatibility of the tackifier (B) having a relatively low molecular weight with the polyester resin (A). Is expected to increase. In addition, when the resin composition is injection-molded or the like, the fluidity of the resin composition is increased, so that the moldability is improved. In addition, breakage of the inorganic filler (C) due to the shearing force in the mold is suppressed. That is, when the inorganic filler (C) is a fiber, it is presumed that the tensile strength and the elastic modulus are improved by maintaining the fiber length.

The content of each structural unit can be calculated from the ratio of the supply amount of each monomer to the total monomer supply amount during polymerization. Further, when the tackifier (B) has a structural unit selected from the above group, the content of each structural unit is the amount of the peak derived from ethylene and the peak derived from styrene in the analysis of ¹³ C-NMR spectrum. It can be calculated from the ratio.

The tackifier (B) preferably satisfies the following physical properties.
Density measured with a density gradient tube method of the tackifier (B) is preferably 900~1200kg / ^{m 3,} more preferably from 950~1150kg / ^{m 3,} more preferably at 1000~1130kg / ^{m 3} Yes, particularly preferably 1010 to 1100 kg / m ³ . When the density is in the above range, the tackifier (B) is easily compatible with the polyester resin (A) and more easily dispersed more uniformly. As a result, a resin composition having more sufficient impact resistance and excellent workability can be obtained.

  The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) of the tackifier (B) is preferably 500 to 2500, and more preferably 600 to 2300. More preferably, it is 700-2000. Moreover, Preferably a weight average molecular weight (Mw) is 800-4000, More preferably, it is 900-3800. More preferably, it is 1000-3500. Furthermore, the weight average molecular weight / number average molecular weight (Mw / Mn) is preferably 1.1 to 2.5, more preferably 1.2 to 2.0, and still more preferably 1.3 to 1. Nine. When the number average molecular weight and weight average molecular weight of the tackifier (B) are in the above ranges, the fluidity of the resin composition is improved and the molding processability is improved.

  The tackifier (B) can be produced by a known method. For example, when the tackifier (B) satisfies the above requirement (B-4), the production method is selected from the group consisting of styrene, α-methylstyrene, indene, vinyltoluene and isopropenyltoluene as raw materials. A method of homopolymerizing at least one type of monomer or copolymerizing two or more types, a method of copolymerizing these monomers and other monomers (vinyl aromatic compounds and unsaturated aliphatic compounds other than the above), and the like. Can be mentioned.

  Examples of other aromatic vinyl compounds used in the above method include substituted styrene having a substituent on the aromatic ring; and styrene monomers such as substituted α-methylstyrene having a substituent on the aromatic ring. Can be mentioned. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen atom.

  Specific examples of the substituted styrene include methyl styrene (excluding α-methyl styrene), ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, p -N-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene be able to.

On the other hand, as an unsaturated aliphatic compound which is another monomer, a C4-C5 unsaturated aliphatic hydrocarbon etc. can be mentioned as a specific example. The unsaturated aliphatic hydrocarbons having 4 to 5 carbon atoms include C ₄ and C ₅ fractions containing, as a main component, unsaturated aliphatic hydrocarbons having 4 to 5 carbon atoms that are by-produced during petroleum refining and decomposition. Any compound selected can be used. By using these compounds in combination with styrene or the like, it is possible to adjust each physical property such as the softening point of the tackifier (B) according to the use.

The C ₄ fraction and the C ₅ fraction are fractions having a boiling range of usually −15 to + 45 ° C. under normal pressure, and are 1-butene, isobutene, 2-butene, 1,3-butadiene, 1-pentene, It contains polymerizable monomers such as 2-methyl-1-butene, 3-methyl-1-butene, 2-pentene, isoprene, 1,3-pentadiene and cyclopentadiene. As the unsaturated aliphatic compound, any polymerizable monomer selected from C ₄ fraction and C ₅ fraction can be used, but the unsaturated aliphatic compound does not have a conjugated double bond, or the content thereof. Is preferably low. Specifically, it is preferable that 1,3-butadiene, isoprene, 1,3-pentadiene, cyclopentadiene or the like is not contained or the content thereof is low.

  The oil fraction as described above is, for example, a light oil fraction containing a gas fraction by-produced at the time of atmospheric distillation (topping) of crude oil or the like in a refinery or the like; it is by-produced in oil cracking and reforming processes. Similar light oil fractions; or light oil fractions containing gas obtained in petroleum naphtha cracking in petrochemical plants; etc., as desired, or optionally with distillation, extraction or other treatment It can be obtained as a fraction.

  Here, the homopolymerization reaction or copolymerization reaction of a monomer selected from the above group, and the copolymerization reaction of the monomer with other monomers are mainly cationic polymerization, more specifically in the presence of Friedel-Crafts catalyst. To be done. As the Friedel-Crafts catalyst, known Friedel-Crafts catalysts can be used, and specifically, aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride, boron trifluoride, trifluoride. Examples thereof include various complexes such as an ether complex and a phenol complex of boron bromide. Among these, it is preferable to use a phenol complex of boron trifluoride. The usage-amount of Friedel-Crafts catalyst is 0.05-5 mass parts normally with respect to a total of 100 mass parts of a raw material monomer, Preferably it is 0.1-2 mass parts.

  The polymerization reaction is performed using a solvent so that the concentration of the polymerizable monomer as a raw material is about 10 to 60% by mass in order to remove reaction heat generated during the polymerization reaction, suppress the viscosity of the reaction solution, adjust the molecular weight, and the like. It is preferable. Examples of suitable solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and mesitylene. Can be mentioned. These may be used alone or in combination.

  In the polymerization step, a polymerizable monomer that is a raw material in the reactor is subjected to a polymerization reaction in the solvent in the presence of the catalyst. The polymerization step can be carried out in a single stage, but is preferably carried out in a plurality of stages. The polymerization temperature varies depending on the raw material composition, the target molecular weight region, and the like, but is usually preferably in the range of −50 to + 50 ° C. The reaction time is preferably in the range of usually 10 minutes to 10 hours. After completion of the polymerization, the catalyst is decomposed using a basic compound such as a basic aqueous solution or an alcohol such as methanol, then washed with water, and removed by stripping unreacted raw materials and solvents. The tackifier (B) is obtained.

  The tackifier (B) may be a solid such as a powder, a tablet, or a block, and may be dispersed in a solvent or dissolved.

3. Inorganic filler (C)
As an inorganic filler (C), a well-known inorganic filler can be used without being specifically limited. Specific examples of the inorganic filler (C) include talc, mica, calcium carbonate, hydrotalcite, wollastonite, zonotlite, barium sulfate, calcium sulfate, calcium silicate, clay, glass fiber, glass beads, glass flake, and carbon fiber. , Carbon black, graphite, gypsum, magnesium carbonate, magnesium oxide, titanium oxide, potassium titanate and other titanates, iron oxide, alumina, metal powder (eg zinc, copper, iron, aluminum, magnesium, silicon, titanium, etc.) , And metal fibers. Furthermore, pumice powder, pumice balun, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium titanate, calcium sulfite, asbestos, montmorillonite, bentonite, molybdenum sulfide and the like can also be used. The resin composition may contain only one type of inorganic filler (C), or may contain two or more types. Of these, talc, mica, calcium carbonate, glass fiber and the like are preferable, and glass fiber is particularly preferable.

  The inorganic filler (C) may have any shape such as a granular shape, a plate shape, a rod shape, a fiber shape, and a whisker shape. Moreover, the inorganic filler (C) may be a commercially available filler for polymer. For example, it may be commercially available in any form such as powder form, roving form, chopped strand form, compressed soul form, pellet (granulated) form, granule form and the like. When the inorganic filler (C) is talc, it is preferably processed into a powder form, a compressed soul form, or a granular form.

  The average particle diameter of the inorganic filler (C) when it is granular is preferably 1 to 15 μm, more preferably 3 to 14 μm. The average particle diameter is a value measured by a laser diffraction method.

  The inorganic filler (C) is produced by various known production methods. For example, talc is manufactured by pulverizing the raw stone with an impact pulverizer or micron mill type pulverizer, or further pulverizing with a jet mill or the like and then adjusting the classification with a cyclone or micron separator. be able to.

  In addition, the inorganic filler (C) may be untreated or may be a surface-treated at least part of it. Examples of the surface treatment agent include an organic titanate coupling agent, an organic silane coupling agent, a modified polyolefin grafted with an unsaturated carboxylic acid or an anhydride thereof, a fatty acid, a fatty acid metal salt, a fatty acid ester, and the like. Moreover, these surface treating agents may be used individually by 1 type, and may be used in combination of 2 or more type.

4). Other resins The resin composition of the present invention may further contain a resin other than the polyester resin (A) and the tackifier (B) as long as the effects of the present invention are not significantly impaired. Although content in particular of said other resin is not restrict | limited, It is preferable that it is about 0.1-30 mass parts with respect to 100 mass parts of polyester resins (A).

5. Other Fillers The resin composition of the present invention may contain fillers other than inorganic fillers, that is, fillers made of organic substances (hereinafter also referred to as “organic fillers”). Examples of organic fillers include lignin, starch, wood flour, wood fibers, bamboo, cotton, cellulose, natural fibers such as nanocellulosic fibers, and products containing them.

  The resin composition may contain only 1 type of these organic fillers, and may contain 2 or more types. The content of these organic fillers is not particularly limited, but is preferably 70 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass in total of the polyester resin (A) and the tackifier (B). It is 20 parts by mass or less, more preferably 20 parts by mass or less.

6). Other Additives The resin composition of the present invention may contain additives other than fillers. Other additives include those known in the polyolefin field. Examples of additives include nucleating agents, anti-blocking agents, pigments, dyes, lubricants, foaming agents, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antibacterial agents, surfactants, antistatic agents Agent, weather stabilizer, heat stabilizer, anti-slip agent, foaming agent, crystallization aid, anti-fogging agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent, co-crosslinking agent, crosslinking aid, adhesive Agents, softeners, processing aids and the like.

  The resin composition may contain only one type of additive or may contain two or more types. The content of these additives is not particularly limited as long as it does not impair the object of the present invention, but 0.05% each for a total of 100 parts by mass of the polyester resin (A) and the tackifier (B). It is preferably about 70 parts by mass. The upper limit is more preferably 30 parts by mass.

7). Method for Producing Resin Composition The resin composition of the present invention can be produced by dry blending or melt blending using any of various methods. As a specific method, for example, a polyester resin (A), a tackifier (B), an inorganic filler (C), and other optional components can be used simultaneously, or in any order, in a tumbler, V-type blender, or now. A blending method can be used with a turmixer, Banbury mixer, kneading roll, single-screw or twin-screw extruder. Alternatively, after the polyester resin (A), tackifier (B), inorganic filler (C), and other optional components are once dispersed or dissolved in an arbitrary solvent, natural drying, heat forced drying, etc. It may be blended by appropriately drying.

  In general, melt blending is preferable to dry blending from the viewpoint of improving the appearance and impact resistance of the resulting molded article. In particular, by sufficiently kneading with melt blending, the appearance and impact resistance of the resulting molded product tend to be increased. In particular, when two or more kinds of compounds are used in combination as the tackifier (B), it is preferable for handling that two or more kinds of tackifiers (B) are dry blended or melt blended in advance. As a method of melt blending, the above method, a method using a batch kettle, or the like is appropriately used.

B. Molded body The molded body of the present invention can be produced by molding the resin composition into a desired shape by a conventionally known method such as injection molding, coating, extrusion molding, compression molding or the like. The shape of the molded body is not particularly limited, and is, for example, a film shape, a plate shape, a prismatic shape, a columnar shape, or the like. The molded product of the present invention can be used for the same applications as conventionally known polyester resins. Specifically, it can be used for automobile parts, home appliance parts, and the like.

  EXAMPLES Although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

[Sample preparation]
1. Polyester resin (A)
As the polyester resin (A), DURANEX 2002 manufactured by Wintech Polymer Co., Ltd., which is a polybutylene terephthalate resin, was used. As a result of measuring each physical property by the following method, the melting point (Tm) of the polyester resin (A) was 225 ° C., the number average molecular weight (Mn) was 28300, and the weight average molecular weight (Mw) was 83300. The melting point, number average molecular weight (Mn), and mass average molecular weight (Mw) were measured by the following methods.

<Melting point>
It measured using DSC-20 (made by Seiko Denshi Kogyo Co., Ltd.) by differential scanning calorimetry (DSC). About 10 mg of a sample was sealed in an aluminum pan, heated from 0 ° C. to 280 ° C. at 10 ° C./min, and the endothermic peak of the obtained curve was determined as the melting point. Before the temperature rise measurement, the sample was once heated to about 280 ° C., held for 5 minutes, and then lowered to 0 ° C. at 10 ° C./min to unify the thermal history of the sample. Moreover, in the obtained curve, when there are a plurality of endothermic peaks, the endothermic peak temperature having the largest endothermic amount was defined as the melting point (Tm).

<Number average molecular weight (Mn) and weight average molecular weight (Mw)>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined from GPC measurement. The measurement was performed under the following conditions. And the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated | required from the calibration curve using a commercially available monodisperse standard polystyrene.
Apparatus: 515 pump, 717plus automatic injection device (manufactured by Waters)
Solvent: Chloroform Column: PLgel 5μ MIXED-D 7.5 × 300 mm × 2 (manufactured by Polymer Laboratories)
Flow rate: 1.0 ml / min Sample: 1.2 mg / mL Chloroform Temperature: 40 ° C

2. Tackifier (B)
In the examples, tackifiers W1 to W3 prepared by the method described later were used as the tackifier (B). On the other hand, in the comparative example, the polymer W4 prepared by the method described later, which does not correspond to the tackifier (B), or the impact modifier (D) (Arkema Rotada AX8900, ethylene / methyl acrylate / glycidyl methacrylate copolymer) )It was used.

  Moreover, the physical property was analyzed with the following method about the tackifiers W1-W3 and the polymer W4 which were prepared by the below-mentioned method. The results are shown in Table 1. In Table 1, “IPT” is a structural unit derived from isopropenyltoluene, “St” is a structural unit derived from styrene, “αMS” is a structural unit derived from α-methylstyrene, and “IND”. Represents a structural unit derived from indene, “C2” represents a structural unit derived from ethylene, and “C3” represents a structural unit derived from propylene. In addition, “C2: 94% by mass” means that 94% by mass of a structural unit derived from ethylene is contained in the molecule.

<Composition>
About the content rate (mass ratio) of each structural unit which comprises tackifier W1-W3, it calculated | required from the supply amount of each component with respect to the total monomer supply amount at the time of superposition | polymerization. On the other hand, the amount of each structural unit constituting the polymer W4 (composition ratio of ethylene and α-olefin) was determined by analyzing a ¹³ C-NMR spectrum measured under the following conditions.

Measurement conditions for ¹³ C-NMR Apparatus: AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by Bruker BioSpin Corporation Measurement nucleus: ¹³ C (125 MHz)
Measurement mode: Single pulse proton broadband decoupling Pulse width: 45 ° (5.00 microseconds)
Number of points: 64k
Measurement range: 250 ppm (-55 to 195 ppm)
Repetition time: 5.5 seconds Integration number: 128 Measurement solvent: orthodichlorobenzene / benzene-d ₆ (4/1 (volume ratio))
Sample concentration: 60 mg / 0.6 mL
Measurement temperature: 120 ° C
Window function: exponential (BF: 1.0 Hz)
Chemical shift standard: δδ signal 29.73 ppm

<Melt viscosity at 160 ° C.>
Using a Brookfield digital viscometer, the sample amount was about 8 g and the measurement temperature was 160 ° C.

<Number average molecular weight (Mn), weight average molecular weight (Mw), and Mw / Mn>
About W1-W3, the number average molecular weight (Mn), the weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were calculated | required from GPC measurement. The measurement was performed under the following conditions. And the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated | required from the analytical curve using a commercially available monodisperse standard polystyrene, and Mw / Mn was computed.
Apparatus: GPC HLC-8320 (manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran Column: TSKgel G7000 × 1, TSKgel G4000 × 2, TSKgel G2000 × 1 (all manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: 20 mg / mL tetrahydrofuran solution Temperature: room temperature

On the other hand, also for W4, the number average molecular weight Mn, the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were determined from GPC measurement. The measurement was performed under the following conditions. And the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated | required from the analytical curve using a commercially available monodisperse standard polystyrene, and Mw / Mn was computed.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene Column: TSKgel GMH6-HT × 2, TSKgel GMH6-HTL column × 2 (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution Temperature: 140 ° C.

<Softening point>
Based on JIS K2207, it measured by the ring and ball method.

<Glass transition temperature>
The DSC curve was analyzed in accordance with JIS K7121 when the sample heated up to 200 ° C was cooled and crystallized to -20 ° C at a rate of 10 ° C / min, and again heated at a rate of 10 ° C / min. The glass transition temperature was determined.

<Density>
Measured according to JIS K7112.

<Production Example 1>
W1 in the first stage of the autoclave the real volume 1270ml, equipped with a stirring wing (isopropenyltoluene · C ₅ fraction copolymer), C ₅ fraction obtained isopropenyltoluene, by thermal decomposition of petroleum naphtha, and A mixture of dehydrated and purified toluene (total of monomers / toluene = 1/1 (volume ratio)), boron trifluoride phenolate complex (phenol 1.7 times equivalent) diluted 10-fold with dehydrated and purified toluene, Was continuously fed to cause a polymerization reaction at 5 ° C. Mass ratio of isopropenyl toluene and C ₅ fraction ₍₅ fraction isopropenyltoluene / C) is 90/10 and then, the supply amount of the mixture of monomers and toluene was 1.0 l / hr, the supply amount of diluted catalyst Was 80 ml / hour.

The reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C. When the total residence time in the first and second stage autoclaves reaches 2 hours, the reaction mixture is continuously discharged from the autoclave and three times the residence time (6 hours) has elapsed. At that time, 1 liter of reaction mixture was collected to complete the polymerization reaction. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Furthermore, after washing five times and the reaction mixture obtained in a large amount of water, the solvent and unreacted monomer was distilled off under reduced pressure by an evaporator to obtain isopropenyl toluene · C ₅ fraction copolymer (W1).

<Production Example 2> Production of W2 (α-methylstyrene / styrene copolymer) A mixture of α-methylstyrene, styrene, and dehydrated and purified toluene in the first stage of an autoclave having a real capacity of 1270 ml equipped with a stirring blade ( Monomers / toluene = 1/1 (volume ratio)) and boron trifluoride phenolate complex (phenol 1.7 times equivalent) diluted 10-fold with dehydrated and purified toluene were continuously fed at 5 ° C. The polymerization reaction was carried out. The mass ratio of α-methylstyrene to styrene (α-methylstyrene / styrene) is 60/40, the supply amount of the monomer and toluene mixture is 1.0 liter / hour, and the supply amount of the diluted catalyst is 90 milliliters / hour. It was time.

  The reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C. When the total residence time in the first and second stage autoclaves becomes 2 hours, the reaction mixture is continuously discharged from the autoclave, and when the residence time becomes 3 times, 1 liter The reaction mixture was collected to complete the polymerization reaction. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an α-methylstyrene / styrene copolymer (W2).

<Production Example 3> Production of W3 (isopropenyltoluene / indene copolymer) Isopropenyltoluene (IPT), indene (IND) and dehydrated and purified in the first stage of an autoclave having a real capacity of 1270 ml equipped with a stirring blade A mixture of toluene (volume ratio: total monomer / toluene = 1/1) and a boron trifluoride phenolate complex (1.6 times equivalent of phenol) diluted 10-fold with dehydrated and purified toluene were continuously fed. The polymerization reaction was carried out at 5 ° C. The mass ratio (IPT / IND) of isopropenyltoluene (IPT) to indene (IND) was 55/45, the feed rate of the monomer and toluene mixture was 1.0 liter / hour, and the feed rate of the diluted catalyst was 75 Milliliter / hour.

  The reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C. Thereafter, when the total residence time in the first and second stage autoclaves is 2 hours, the reaction mixture is continuously discharged from the autoclave. The reaction mixture was collected to complete the polymerization reaction. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomer were distilled off under reduced pressure using an evaporator to obtain an isopropenyltoluene-indene copolymer (W3).

<Production Example 4> Production of W4 (ethylene / propylene copolymer) Catalyst preparation 25 g of commercially available anhydrous magnesium chloride was suspended in 500 ml of hexane in a 1.5-liter glass autoclave. To the suspension maintained at 30 ° C., 92 ml of ethanol was added dropwise over 1 hour with stirring, and the reaction was further continued for 1 hour. After completion of the reaction, 93 ml of diethylaluminum monochloride was added dropwise over 1 hour, and the reaction was further continued for 1 hour. After completion of the reaction, 90 ml of titanium tetrachloride was added dropwise, and the reaction vessel was heated to 80 ° C. and reacted for 1 hour. After completion of the reaction, the solid part was washed with hexane until no free titanium was detected by decantation. The titanium concentration of the hexane suspension of the obtained compound (catalyst) was quantified by titration.

・ Preparation of ethylene / propylene copolymer (olefin wax W4) A stainless steel autoclave with an internal volume of 2 liters sufficiently purged with nitrogen was charged with 930 ml of hexane and 70 ml of propylene, and 20.0 kg / cm ^{2 of} hydrogen (gauge) It was introduced until pressure was reached. Subsequently, after raising the temperature in the system to 170 ° C., 0.1 mmol of triethylaluminum and 0.4 mmol of ethylaluminum sesquichloride were supplied. Furthermore, the hexane suspension of the above catalyst was injected with ethylene so that the amount of the titanium component was 0.008 mmol in terms of atoms, and polymerization was started.

Thereafter, only ethylene was continuously supplied to keep the total pressure at 40 kg / cm ² (gauge pressure), and polymerization was carried out at 170 ° C. for 40 minutes. Thereafter, the polymerization was stopped by adding a small amount of ethanol into the system, and unreacted ethylene and propylene were purged. The obtained polymer solution was dried overnight under reduced pressure at 100 ° C. to obtain an ethylene / propylene copolymer (W4).

3. Inorganic filler (C)
Glass fiber (CSF3PE-941S manufactured by Nittobo Co., Ltd.) was used as the inorganic filler (C).

[Examples 1-3, Comparative Examples 1-3]
1. Production of Resin Composition The polyester resin (A) and the tackifier (B) or polymer or impact resistance modifier (D) were dry blended at the blending ratio shown in Table 2. And the said mixture is thrown in from the hopper of Parker Corporation same direction rotation twin-screw extruder, HK25D (phi25mm, L / D = 41), and inorganic filler (C) (glass fiber) is thrown in from a side feeder. These were melt-kneaded. At this time, the screw rotation speed was 120 rpm, the feed rate was 10 kg / h, and the outlet temperature was 260 ° C. The obtained melt-kneaded product was water-cooled to obtain a strand. Further, the melt-kneaded product was cut to produce pellets.
The obtained resin composition was evaluated according to the following criteria. The results are shown in Table 2.

2. Preparation of Test Pieces After the obtained pellet-shaped resin composition was dried at 120 ° C. for 5 hours, it was injection molded using an injection molding machine (Niigata NN100, manufactured by Niigata Machine Techno Co., Ltd.) to produce a test piece. . The cylinder temperature of the injection molding machine was 250 ° C., the screw rotation speed was 75 rpm, the injection pressure was 140 MPa, and the mold temperature was 75 ° C.

3. Evaluation of Test Pieces The obtained test pieces were subjected to Charpy impact test (23 ° C. and −30 ° C.), tensile test (tensile strength, elongation), and bending test (bending strength, flexural modulus) as follows. . The evaluation results are shown in Table 2.

<Charpy impact test>
About the said test piece, based on JISK7111, the Charpy impact test in 23 degreeC and -30 degreeC was done. The notch was machined, and the test piece was 10 mm (width) × 4 mm (thickness) × 80 mm (length).

<Tensile test (tensile strength, elongation)>
About the said test piece, based on JISK-7162, the tensile strength and the tensile elongation rate were measured on conditions with a load range of 2 kN and a test speed of 50 mm / min.

<Bending test (bending strength, flexural modulus)>
About the said test piece, based on JISK-7171, bending strength and a bending elastic modulus were measured on the conditions of load range 200N, test speed 2mm / min, and bending span 64mm.

<Fluidity test (spiral flow)>
Using a EC60NII type injection machine manufactured by Toshiba Machine Co., Ltd., a spiral test piece having a thickness of 2 mm was produced under the following conditions. The length of the spiral shape at this time was measured as the flow length. The injection conditions were a cylinder temperature of 260 ° C., a mold temperature of 80 ° C., an injection pressure of 100 MPa, an injection time of 5 seconds, and a cooling time of 15 seconds.

  As shown in Table 2, the resin composition containing the polyester resin (A), the tackifier (B), and the inorganic filler (C) in a predetermined ratio has impact resistance (Charpy impact strength) and tensile strength. And the flexural modulus were both high (Examples 1 to 3). Moreover, the torque (spiral flow) of the resin composition containing the polyester resin (A), the tackifier (B), and the inorganic filler (C) in a predetermined ratio was sufficiently low. That is, the resin composition of the present invention was excellent in mechanical properties and molding processability.

  On the other hand, in Comparative Example 1 not including the tackifier (B), the impact resistance (Charpy impact strength) was low (Comparative Example 1). Moreover, in the resin composition containing the polymer W4 that does not correspond to the tackifier (B) instead of the tackifier (B), it was difficult to sufficiently increase the impact resistance (Comparative Example 2). Furthermore, in the resin composition containing the impact modifier (D) instead of the tackifier (B), although the impact resistance is increased, the tensile strength and the flexural modulus are reduced (Comparative Example 3).

  The resin composition of the present invention has high impact resistance, tensile strength, elastic modulus and moldability. Therefore, the resin composition of the present invention can be applied to various resin molded products.

Claims (8)

Containing a polyester resin (A), a tackifier (B), and an inorganic filler (C),
When the total content of (A), (B) and (C) is 100 parts by mass, (A) is 50 to 95 parts by mass, (B) is 0.5 to 10 parts by mass, (C 5-40 parts by mass,
The (A) satisfies the following (A-1) and (A-2).
Resin composition.
(A-1) including a structural unit (a1) derived from an aromatic dicarboxylic acid and a structural unit (a2) derived from a diol having 2 to 10 carbon atoms (A-2) a differential scanning calorimeter (DSC) The melting point (Tm) due to is in the range of 200-245 ° C.   The (B) includes at least one selected from natural rosin, modified rosin, polyterpene resin, synthetic petroleum resin, coumarone resin, phenol resin, xylene resin, styrene resin, and isoprene resin. Item 2. The resin composition according to Item 1. The resin composition according to claim 1 or 2, wherein (B) satisfies the following (B-1), (B-2), and (B-3).
(B-1) Melt viscosity at 160 ° C. is 10 to 500,000 mP · s (B-2) Softening point is in the range of 60 to 180 ° C. (B-3) Measured with a differential scanning calorimeter (DSC) Glass transition temperature (Tg) in the range of 0 to 100 ° C. The resin composition according to any one of claims 1 to 3, wherein the (B) satisfies the following (B-4).
(B-4) The molecule contains 50 to 100% by mass of a structural unit derived from at least one selected from the group consisting of styrene, α-methylstyrene, indene, vinyltoluene, and isopropenyltoluene.   The resin composition according to any one of claims 1 to 4, comprising glass fibers as the (C).   The resin composition as described in any one of Claims 1-5 containing a polybutylene terephthalate as said (A).   When the total content of (A), (B) and (C) is 100 parts by mass, (A) is 55 to 80 parts by mass, (B) is 2 to 5 parts by mass, and (C) is The resin composition according to any one of claims 1 to 6, comprising 20 to 40 parts by mass.   The molded object containing the resin composition as described in any one of Claims 1-7.