JPH11315221A - Inorganic filler and resin composition filled therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-coated inorganic filler having excellent dispersibility and a thermoplastic resin composition filled therewith and being excellent in mechanical strengths, etc. SOLUTION: There is provided the rosin-acid-coated inorganic filler (C) comprising (A) an inorganic filler and (B) rosin acid and/or its derivative with which component A is surface-coated, wherein component B is used in an amount of 0.01-20 pts.wt. per 100 pts.wt. component A. It is desirable that component A is a compound of a group I, II or III metallic element (Mg, K, Na, or Al), especially, talc, magnesium carbonate, magnesium hydroxide, magnesium oxide, or hydrotalcite. It is desirable that component B is based on dehydroabietic acid, dihydroabietic acid, dihydropimaric acid or a derivative thereof. There is also provided a thermoplastic resin composition containing (D) a thermoplastic resin and component C, wherein component C is used in an amount of 0.01-100 pts.wt. 100 pts.wt. component D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an inorganic filler and a thermoplastic resin composition containing the inorganic filler.
More specifically, an inorganic filler which is surface-coated (coated) and has excellent dispersibility, and the inorganic filler is compounded,
The present invention relates to a thermoplastic resin composition having excellent mechanical strength and the like.

[0002]

BACKGROUND OF THE INVENTION Inorganic fillers have been widely used for the purpose of improving mechanical strength such as rigidity and surface hardness, dimensional stability of a thermoplastic resin molded article, dimensional stability, and cost reduction. .

However, when a large amount of an inorganic filler is incorporated into a thermoplastic resin composition, the inorganic filler generally has poor dispersibility, so that an aggregate is formed in the thermoplastic resin composition, and the thermoplastic resin inherently has In many cases, appearance and the like were remarkably impaired, for example, the mechanical strength and surface gloss of the thermoplastic resin molded product were reduced.

[0004] Therefore, conventionally, a method of surface-treating an inorganic filler with a silane coupling agent, a higher fatty acid, a metal salt of a higher fatty acid, an organic titanate or the like has been widely used.

[0005] However, even when such a surface-treated inorganic filler is mixed with a thermoplastic resin, a thermoplastic resin composition having satisfactory mechanical strength may not be obtained in some cases.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems associated with the prior art, and has an excellent dispersibility and, in a crystalline resin, an inorganic material capable of greatly improving the crystallinity. It is intended to provide a filler.

Another object of the present invention is to provide a thermoplastic resin composition capable of obtaining a molded article having excellent appearance, mechanical strength, and the like by blending such an inorganic filler with the thermoplastic resin. The purpose is.

[0008]

SUMMARY OF THE INVENTION The rosin acid-coated inorganic filler (C) according to the present invention comprises (A) an inorganic filler and (B) a resin acid (hereinafter referred to as "rosin") which covers the surface of the inorganic filler (A). Rosin acid) and / or a derivative thereof. The amount of the rosin acid and / or its derivative (B) is 0.01 to 100 parts by weight of the inorganic filler (A). It is characterized by being 20 parts by weight.

In the present invention, the inorganic filler (A)
Is preferably at least one compound containing a metal element of Group I, II, or III of the periodic table, and at least one compound containing at least one metal element selected from Mg, K, Na, and Al. One compound is more preferable, and a magnesium compound is further preferable. At least one compound selected from talc, magnesium carbonate, magnesium hydroxide, magnesium oxide, and hydrotalcite is particularly preferable. .

The rosin acid and / or its derivative (B) may contain at least one rosin acid and / or its derivative selected from dehydroabietic acid, dihydroabietic acid and dihydropimaric acid as a main component. Preferably, the rosin acid and / or its derivative (B) is at least one rosin acid selected from rosin acids represented by the following formula (Ia) and rosin acids represented by the following formula (Ib): And / or a derivative containing a derivative thereof as a main component.

[0011]

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[In the formulas (Ia) and (Ib), R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, which may be the same or different. ].

The thermoplastic resin composition according to the present invention comprises:
(D) It contains a thermoplastic resin and the above-mentioned rosin acid-coated inorganic filler (C), and the rosin acid-coated inorganic filler (C) is 0.01 to 100 parts by weight of the thermoplastic resin (D). ~ 1
It is characterized by being blended in an amount of 00 parts by weight.

In the present invention, the thermoplastic resin (D) is preferably one or more crystalline thermoplastic resins selected from polyolefins, polyesters, polyamides and polyacetals.

In the present invention, the thermoplastic resin (D) and the rosin acid-coated inorganic filler (C) are melt-kneaded at a temperature not lower than the melting point of the thermoplastic resin (D). It is characterized by producing a composition.

The above-mentioned rosin acid-coated inorganic filler according to the present invention is excellent in dispersibility, and a molded article made of a thermoplastic resin composition containing the inorganic filler is hard to obtain mechanical properties such as rigidity and surface hardness. Excellent strength, excellent appearance, surface gloss, dimensional stability, etc.

[0017]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the rosin acid-coated inorganic filler according to the present invention and the thermoplastic resin composition containing the inorganic filler will be described in detail.

[Rosinic acid-coated inorganic filler (C)] The rosin-acid-coated inorganic filler (C) according to the present invention coats (A) the inorganic filler and the surface of the inorganic filler (A) ( B) rosin acid (resin acid contained in rosin) and / or a derivative thereof (collectively referred to as a surface coating agent), and the amount of rosin acid and / or its derivative (B) is changed by the amount of the inorganic filler 0.01 to 100 parts by weight of agent (A)
To 20 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight.

When the amount of the rosin acid and / or the derivative thereof is in the above range, the dispersibility of the rosin acid-coated inorganic filler is improved, and the properties of the inorganic filler powder are improved, resulting in excellent handling. Become like

In the state where the surface of the inorganic filler (A) is coated with (B) rosin acid and / or a derivative thereof, the entire surface or a part of the surface of the inorganic filler (A) is coated with rosin acid. And / or rosin acid derivatives are present.

Hereinafter, the inorganic filler (A), rosin acid and / or rosin acid constituting such rosin acid-coated inorganic filler (C) will be described.
Alternatively, the derivative (B) will be described sequentially. <(A) Inorganic filler> As the inorganic filler, conventionally known inorganic fillers can be used, and the inorganic filler is not particularly limited.
The compound is preferably a compound containing a metal element of group III, II, or III, and more preferably a compound containing at least one metal element selected from Mg, K, Na, and Al.

Specifically, natural silicic acids or silicates such as talc, kaolinite, calcined clay, pyrophyllite, sericite, wollastonite, and montmorillonite; precipitated carbonic carbonate, heavy calcium carbonate, and carbonated carbonate such as magnesium carbonate. Salts, hydroxides such as aluminum hydroxide and magnesium hydroxide, oxides such as zinc oxide, zinc oxide and magnesium oxide, hydrotalcite, hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, synthetic silicic acid such as silicic anhydride or Powdered filler such as silicate; flake-like filler such as mica; basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Proces
sed Mineral Fiber), zonotrite, potassium titanate,
Fibrous fillers such as elestadite; balun fillers such as glass balun, silas balun, and fly ash balun; and the like.

Of these, talc, magnesium carbonate, magnesium hydroxide, magnesium oxide and hydrotalcite are preferably used. In the present invention, talc is preferably used among these, and particularly, fine powder talc having an average particle size of 0.01 to 20 μm is preferably used. <(B) Rosin acid and / or its derivative> Among the rosin acid and / or its derivative (B), rosin acid may be pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietin Resin acids such as acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, and tetrahydroabietic acid.

The rosin acid derivatives include those in which a part or all of the contained acids are chemically modified by the reaction of the above-mentioned rosin acids with metal compounds, alcohols, amines, amides and the like. Rosin acid metal salts, rosin acid esters, rosin acid amides,
And rosin imide.

Rosin acid and / or its derivative (B)
As rosins containing, natural rosins such as gum rosin, tall oil rosin, wood rosin; disproportionated rosin,
Hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α, β-
Various modified rosins such as an ethylenically unsaturated carboxylic acid modified rosin; a purified product of the natural rosin; a purified product of the modified rosin;

The unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin is, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid. , Acrylic acid, methacrylic acid and the like.

Among these, natural rosin, modified rosin, purified products of natural rosin and purified products of modified rosin are preferred. In the present invention, the following formula (I) is used as the rosin acid.
It is preferable to use a compound [compound (Ia)] represented by a) or a compound [compound (Ib)] represented by the following formula (Ib).

[0028]

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In the formulas (Ia) and (Ib), R ¹ and R ²
And R ³ may be the same or different and are a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

The alkyl group may be linear or branched. Examples of such an alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, pentyl, heptyl,
Examples thereof include an alkyl group having 1 to 8 carbon atoms such as octyl, and these groups include a hydroxyl group, a carboxyl group,
An alkoxy group (eg, C _n H _{2n + 1} O-, n = 1 to 10, preferably about 1 to 6; the same applies hereinafter), a halogen (eg, F,
Cl, Br, I, etc.).

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl. These groups include hydroxyl, carboxyl, alkoxy, and halogen. May have a substituent.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. These groups include a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen. May be provided.

In such compounds (Ia) and (Ib), R ¹ , R ² and R ³ are each
Compounds that are the same or different alkyl groups are preferred,
Compounds in which R ¹ is an i-propyl group and R ² and R ³ are methyl groups are more preferred. When the inorganic filler (C), which has been surface-coated (surface treated, coated) with such rosin acid and / or its derivative, is blended into the thermoplastic resin composition, it can be favorably incorporated into the composition. Dispersed, rigid, obtained a composition excellent in mechanical strength such as surface hardness,
The composition has excellent dimensional stability during molding and the like, and a molded article formed from the composition has excellent surface gloss.

Specific examples of the compound (Ia) include dehydroabietic acid, and specific examples of the compound (Ib) include dihydroabietic acid.
Among such compounds (Ia) and (Ib), for example, dehydroabietic acids represented by the formula (Ia) disproportionate or dehydrogenate natural rosins such as gum rosin, tall oil rosin and wood rosin, Then, it is obtained by purification. In addition, natural rosin includes pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid,
Usually, a plurality of resin acids such as tetrahydroabietic acid are contained.

In the present invention, the rosin acid derivative, that is, the derivative of the resin acid contained in the rosin, is obtained by reacting the above-mentioned rosin acid with a metal compound, alcohol, amine, amide, etc. Or all chemically modified rosin acid metal salts, rosin esters, rosin amides, rosin imides, and the like,
The rosin acid metal salt is a reaction product of rosin acid and a metal compound.

Examples of the metal compound which forms a metal salt by reacting with the rosin acid include compounds having a metal element such as sodium, potassium, magnesium and the like, and forming a salt with the rosin acid. Specific examples include chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides, and the like of the above-mentioned metals.

In the present invention, the rosin acid metal salt is preferably a rosin acid metal salt selected from the group consisting of the rosin acid sodium salt, the rosin acid potassium salt and the rosin acid magnesium salt. Further, the rosin acid metal salt is preferably a rosin acid metal salt selected from the group consisting of a metal salt of hydrogenated rosin, a metal salt of disproportionated rosin, and a metal salt of dehydrogenated rosin. It is preferable that the metal salt is a metal salt of rosin acid selected from the group consisting of metal salts, metal salts of dihydroabietic acid and metal salts of dihydropimaric acid.

As a method for producing such a metal salt of rosin acid, for example, Japanese Patent Application Laid-Open No.
A conventionally known method as shown in JP 9968 can be employed.

In the present invention, when synthesizing a metal salt of rosin acid, the compound represented by formula (Ia) [compound (Ia)] or the compound represented by formula (Ib) is used as rosin acid. Compound (Ib)] is preferably used.

That is,

[0041]

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[In the formulas (Ia) and (Ib), R ¹ ,
R ² and R ³ may be the same or different from each other,
It is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. ].

Among the compounds (Ia) and (Ib), those in which R ¹ , R ² and R ³ are the same or different alkyl groups are preferable, R ¹ is an isopropyl group, R ² and R ² Compounds in which ³ is a methyl group are more preferred. The inorganic filler whose surface is coated with the metal salt of such a compound contributes to improving the physical properties of the resin composition in which the inorganic filler is blended.

Specific examples of such a compound (Ia) include dehydroabietic acid and the like.
Specific examples of b) include dihydroabietic acid and the like.

The metal salt of the compound (Ia) includes a compound represented by the following formula (IIa) [compound (II
a)], and as the metal salt of the compound (Ib), a compound represented by the following formula (IIb) [compound (II
b)).

[0046]

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In the formulas (IIa) and (IIb), R ¹ , R ² and R ³ are the same as in the above formulas (Ia) and (Ib). M is a 1-3 valent metal ion, and specifically,
Monovalent metal ions such as lithium, sodium, potassium, rubidium and cesium; divalent metal ions such as beryllium, magnesium, calcium, strontium, barium and zinc; and trivalent metal ions such as aluminum. Among these, a monovalent or divalent metal ion is preferable, and a sodium ion, a potassium ion, and a magnesium ion are more preferable.

N is the same integer as the valence of the metal ion M, and is an integer of 1 to 3. Among the compounds (IIa) and (IIb), a compound in which R ¹ , R ² and R ³ are the same or different alkyl groups or a compound in which M is a monovalent or divalent metal ion is preferable. , R ¹ is an i-propyl group, R ² and R ³
Is a methyl group (ie, a compound of the dehydroabietic acid type or dihydroabietic acid type) or a compound in which M is a sodium ion, potassium ion or magnesium ion, and R ¹ is i
-Propyl, R ² and R ³ are methyl,
Compounds in which M is a sodium ion, potassium ion or magnesium ion are particularly preferred.

Specific examples of the compound (IIa) include, for example, lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, zinc dehydroabietic acid, dehydroabietic acid. Examples thereof include metal salts of dehydroabietic acid such as aluminum abietic acid, and sodium dehydroabietic acid, potassium dehydroabietic acid, and magnesium dehydroabietic acid are preferably used.

Specific examples of the compound (IIb) include lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, zinc dihydroabietic acid, and dihydroabietic acid. Examples thereof include metal salts of dihydroabietic acid such as aluminum abietic acid, and sodium dihydroabietic acid, potassium dihydroabietic acid, and magnesium dihydroabietic acid are preferably used.

In the present invention, at least two kinds of metal rosinates may be used as the surface coating agent (surface treatment agent) for the inorganic filler (A) as described above. The at least two kinds of rosin acid metal salts may contain at least two kinds of rosin acid metal salts obtained by reacting the same rosin acid with different metals, and a rosin obtained by reacting different rosin acids with the same metal. It may contain at least two kinds of acid metal salts, and may contain at least two kinds of rosin acid metal salts obtained by reacting different rosin acids with different metals.

The amount ratio of the metal rosinate in the at least two metal rosinates is arbitrary, but is based on the total amount (100 mol%) of the metal rosinates in the at least two metal rosinates. One rosin metal salt in an amount of more than 0 mol%, preferably 5 to 95 mol%, and one or more (remaining) rosin metal salt in an amount of less than 100 mol%, preferably 95 to 95 mol%. It is desirable to combine them in a ratio of 5 mol%.

As a combination of at least two kinds of metal rosinates, a combination of magnesium rosinate and sodium rosinate and / or potassium rosinate is preferred. Further, the total amount (100 mol%) of the metal rosinate in at least two kinds of metal rosinates
The rosin acid magnesium salt is at least 20 mol%, preferably 40 to 95 mol%, more preferably 45 to 80 mol%, and the rosin acid sodium salt and / or rosin potassium salt is at most 80 mol%, preferably Is 60-5
It is desirable to combine them in a ratio of mol%, more preferably 55 to 20 mol%.

Other rosin acid derivatives include:
Examples include rosin acid ethylene glycol ester, rosin acid glycerin ester, rosin acid pentaerythritol ester, rosin acid higher alkyl ester, and rosin acid higher alkyl amide.

Among these, the ethylene glycol rosinate may be ethylene glycol monorosinate, ethylene glycol dirosine, or polyethylene glycol rosinate.

The rosin acid glycerin ester may be a monorosin acid glycerin ester, a dirosin acid glycerin ester, a trirosin acid glycerin ester, or a rosin acid polyglycerin ester.

Further, the pentaerythritol rosin acid ester is a pentaerythritol monorosin acid ester, a pentaerythritol dirosine acid ester, a pentaerythritol ester of trirosin acid or a pentaerythritol ester of tetrarosin acid. Or monorosin acid polypentaerythritol ester.

Specifically, for example, ethylene glycol dehydroabietic acid ester, glycerin dehydroabietic acid ester, pentaerythritol dehydroabietic acid ester, higher alcohol ester dehydroabietic acid, higher alkyl amide dehydroabietic acid, ethylene glycol didehydroabietic acid Esters, glycerin didehydroabietic acid ester, pentaerythritol dihydroabietic acid ester, higher alkyl dihydroabietic acid ester, higher alkyl amide dihydroabietic acid, and the like.

These rosin acid derivatives may be used alone or in combination of two or more. The rosin acid and / or derivative (B) thereof of the present invention preferably contains at least rosin acid. The content of rosin acid is preferably 20 mol% or more,
More preferably, the content is 40 mol% or more, and 60 mol%
It is particularly preferable to contain the above. When the rosin acid is contained in such an amount, a molded article made of the resin composition obtained by melt-kneading is excellent in mechanical strength such as rigidity and surface hardness, appearance, surface gloss, dimensional stability and the like. Tend to be excellent.

In the present invention, the rosin acid and / or
Alternatively, the derivative (B) is mainly composed of at least one rosin acid selected from dehydroabietic acid, dihydroabietic acid and dihydropimaric acid and / or a derivative thereof, that is, the total amount of the rosin acid and the derivative thereof. (100 mol%), usually 5 to 100 mol% of dehydroabietic acid, dihydroabietic acid, dihydropimaric acid and / or a derivative thereof,
Preferably 20 to 100 mol%, particularly preferably 40 to 100 mol%
Desirably, it is contained in an amount of 100 mol%. When a resin acid such as dehydroabietic acid and / or a derivative thereof is contained in such an amount, a molded article made of the resin composition obtained by melt-kneading has a high mechanical strength such as rigidity and surface hardness. It tends to be excellent in appearance, surface gloss, dimensional stability and the like.

In the present invention, the rosin acid and / or its derivative (B) include the above-mentioned rosin acid (Ia) and / or rosin acid (Ib) or a derivative thereof in the amount described above. It is particularly preferred that the <Production of rosin acid-coated inorganic filler> In order to obtain such a rosin acid-coated inorganic filler, any conventionally known method may be used. For example, a method of coating the surface of the inorganic filler (A) with a softened / melted product of rosin acid and / or its derivative (B) or a liquid containing resin acid or the like,
A method in which the inorganic filler is mixed with rosin acid and / or a derivative thereof at a predetermined ratio and mixed at an appropriate temperature at a high speed may be used.

As a coating method, more specifically, for example, rosin acid is dissolved in an organic solvent,
A method in which an arbitrary amount of an inorganic filler is added to the rosin acid solution, and after sufficiently stirring, a solid component is filtered and dried. In addition, a rosin acid derivative may be used instead of the rosin acid, and the derivative may be used together with the rosin acid. As the organic solvent, when coating rosin acid, toluene and xylene are preferably used. When such an inorganic filler is coated on the surface, rosin acid and / or its derivative (B) is used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the inorganic filler (A). It is used in an amount of from 0.5 to 15 parts by weight, more preferably from 0.1 to 10 parts by weight.

[ Thermoplastic Resin Composition] The thermoplastic resin composition according to the present invention contains the following (D) thermoplastic resin and the above-mentioned rosin acid-coated inorganic filler (C).

The thermoplastic resin composition of the present invention contains 0.01 to 100 parts by weight of the rosin acid-coated inorganic filler (C) based on 100 parts by weight of the thermoplastic resin (D).
Preferably, it is contained in an amount of 0.1 to 30 parts by weight.

When the rosin acid-coated inorganic filler (C) is contained in the above-mentioned amount, the mechanical strength such as rigidity, surface hardness and impact resistance of the molded article comprising the thermoplastic resin composition obtained; Stability; appearance of molded article such as surface gloss; <(D) Thermoplastic resin> Examples of the thermoplastic resin include polyolefin, polyester, polyamide, polyacetal, polystyrene, acrylonitrile-styrene-butadiene copolymer (ABS), polymethacrylate, polycarbonate, polyphenylene oxide, and polyvinyl chloride. Can be

The polyolefin may be a homopolymer of one kind of olefin (usually having 2 or more carbon atoms, preferably about 2 to 15 carbon atoms) or a copolymer of two or more kinds of olefins. And any of a block copolymer, a random copolymer and the like.

Examples of such polyolefins include polyethylene, polypropylene, poly-1-butene,
Olefin homopolymers such as polymethylpentene and polymethylbutene; ethylene / α-olefin random copolymer, propylene / ethylene random copolymer, propylene / α-olefin random copolymer, propylene /
Olefin copolymers such as ethylene block copolymers and propylene / α-olefin block copolymers; and the like, and polyethylene, polypropylene, propylene / ethylene block copolymers, propylene / α
-Olefin block copolymers are preferred. When the polyolefin is a polyolefin obtained from an olefin having 3 or more carbon atoms, it may be an isotactic polymer or a syndiotactic copolymer. Among these, a polymer mainly composed of polypropylene is particularly preferable. Such polyolefins may be used alone or in combination of two or more.

In the production of the above-mentioned polyolefin, either a Ziegler-Natta type catalyst or a metallocene catalyst can be used as a catalyst. Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycaprolactone, and polyhydroxybutyrate, and polyethylene terephthalate is particularly preferred. Such polyesters may be used alone or in combination of two or more.

Examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12 and nylon-46; aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines; Nylon-6 is particularly preferred. Such polyamides may be used alone or in combination of two or more.

Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like, with polyformaldehyde being particularly preferred. Such polyacetals may be used alone or in combination of two or more.

The polystyrene may be a homopolymer of styrene or a binary copolymer of styrene with acrylonitrile, methyl methacrylate, α-methylstyrene, etc., for example, an acrylonitrile-styrene copolymer. Good.

The ABS contains a structural unit derived from acrylonitrile in an amount of 20 to 30 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and is derived from styrene. Structural unit 40 ~
Those containing in an amount of 60 mol% are preferably used (provided that the total of all the constituent units is 100 mol%).

As the polymethacrylate, polymethyl methacrylate (PMMA) is preferable. As polycarbonate, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) Examples include those obtained from butane and the like, and polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is preferable.

As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferable. The polyvinyl chloride may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride with vinylidene chloride, acrylate, acrylonitrile, propylene, or the like.

The above-mentioned thermoplastic resins can be used alone or in combination of two or more. Among these, polyolefins, polyesters, polyamides and polyacetals are preferred, polyolefins are more preferred, polypropylene, propylene / ethylene random copolymer, propylene / α-olefin random copolymer, propylene / ethylene block copolymer, propylene / propylene. α-Olefin block copolymers are preferred because they have a large effect of improving mechanical properties. <Production of thermoplastic resin composition> In order to produce the thermoplastic resin composition according to the present invention, a conventionally known method can be used. The thermoplastic resin composition comprises, for example, an extruder comprising the thermoplastic resin (D), the surface-coated inorganic filler (C) in the above-described amount, and a compounding agent such as a crosslinking agent, if necessary. Using a kneader or the like, at a temperature equal to or higher than the melting point of the thermoplastic resin and equal to or lower than the decomposition temperature, preferably at a temperature of + 10 ° C. to 100 ° C.
It is obtained by melt-kneading for 20 minutes, preferably for about 0.5 to 10 minutes.

Specifically, for example, the thermoplastic resin (D)
Is a polyolefin, usually 170 to 300
° C, preferably at a temperature of 180-250 ° C, usually 0.2
The polyolefin of the thermoplastic resin (D) and the rosin acid-coated inorganic filler (C) may be melt-kneaded for up to 20 minutes, preferably 0.5 to 10 minutes.

The thermoplastic resin composition of the present invention thus obtained can be prepared by (a) an inorganic filler having no surface coating or (b) surface treatment by a conventionally known method (eg, silane coupling). Compared to a thermoplastic resin blended with an inorganic filler that has undergone surface treatment, its mechanical properties such as rigidity and heat resistance are superior.

This is because, by applying a surface coating to the inorganic filler with rosin acid and / or its derivative (B), its dispersibility is improved as compared with the inorganic filler (A) having no surface coating. In addition, when rosin acid is contained in the rosin acid and / or its derivative (B), a part of the rosin acid reacts with metal ions in the inorganic filler to improve the crystallization rate of the resin. This is probably due to the fact that

The thermoplastic resin composition according to the present invention contains various compounding agents such as a crosslinking agent, a heat stabilizer, a weather stabilizer, a lubricant, a release agent, an inorganic filler, a pigment dispersant, a pigment or a dye, It may be included in a range that does not impair the object of the present invention.

The thermoplastic resin composition of the present invention can be used in a wide variety of applications from household goods to industrial goods, for example, various moldings for food containers, electric parts, electronic parts, automobile parts, mechanical parts, films, sheets, fibers and the like. It is suitably used as a material for body production.

[0081]

Industrial Applicability The rosin acid-coated inorganic filler according to the present invention comprises a filler whose surface is coated with rosin acid and / or a derivative thereof. Compared to conventional fillers surface-treated with fatty acids, higher fatty acid metal salts, organic titanates, etc.
It has excellent dispersibility and can improve crystallinity.

The thermoplastic resin composition according to the present invention contains an inorganic filler whose surface is coated with a rosin acid and / or a derivative thereof on the surface of the filler. According to the thermoplastic resin composition, the surface of the inorganic filler is a silane coupling agent, higher fatty acid, higher fatty acid metal salt, compared with a thermoplastic resin composition containing a conventional filler surface-treated with an organic titanate, etc. Alternatively, as compared with a thermoplastic resin composition obtained by directly blending a filler, rosin acid and a thermoplastic resin and melt-kneading, a molded article excellent in the above-mentioned various properties such as appearance and mechanical properties can be obtained.

[0083]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The meanings of the abbreviations in the examples and comparative examples are as follows. (A) rosin acid: dehydroabietic acid (b) inorganic filler (C-1): talc (average particle size 15 μm) coated with rosin acid in an amount of 2% by weight of talc.

(C) Inorganic filler (C-2): talc (average particle size: 15 μm) coated with rosin acid in an amount of 5% by weight of talc. (D) Inorganic filler (C-3): talc (average particle size 15 μm)
Coated with a partial magnesium salt of rosin acid (magnesium salt content: 25%) in an amount of 5% by weight of talc.

(E) Inorganic filler (CX): talc (average particle size 15 μm), no coating. <Evaluation Items> (a) Crystallization temperature (Tc): The obtained pellets were converted from a molten state to a constant speed (10%) by a differential scanning calorimeter (DSC).
(° C./min), and the crystallization rate was evaluated by measuring the crystallization exothermic peak temperature [crystallization temperature (Tc)]. The higher the effect of increasing the crystallization rate (Tc), the faster the crystallization rate.

(B) Flexural modulus (FM): 5 inches long
Using an injection molded test piece having a width of 1/2 inch and a thickness of 1/8 inch, the flexural modulus was measured according to ASTM D638.

(C) Heat deformation temperature (HDT): The heat deformation temperature was measured in accordance with ASTM D648 using an injection molded test piece having a length of 5 inches, a width of 1/4 inch and a thickness of 1/2 inch. . The higher the heat distortion temperature, the greater the heat resistance.

(D) Surface hardness (HR): AS was measured using an injection molded square plate having a length of 12 cm, a width of 12 cm, and a thickness of 3.0 mm.
Rockwell hardness (R scale) was measured according to TM D-785. The higher the value, the higher the hardness.

(E) Surface gloss (gloss): length 12c
The central part of an injection-molded square plate having a width of 12 cm, a width of 12 cm and a thickness of 3.0 mm was measured for gloss at 60 ° in accordance with JIS K 7105, and the appearance was evaluated. The greater the value, the greater the surface gloss.

[0091]

Example 1 Propylene block copolymer (abbreviation: b
-PP, M measured at 230 ° C under a load of 2.16 kg
FR: 27 g / 10 min) 100 parts by weight of inorganic filler
10 parts by weight of (C-1) and Irganox 1010 ^™ (Irg
anox1010 ^™ , manufactured by Ciba-Geigy, 0.1 parts by weight of antioxidant) and 0.1% of calcium stearate (CaSt).
One part by weight was added, and the mixture was melt-kneaded at a resin temperature of 220 ° C. using a 30 mmφ twin-screw extruder to produce pellets.

Using the obtained propylene block copolymer pellets, a cylinder temperature of 200 ° C. and a mold temperature of 40
Various test pieces were prepared by injection molding at ℃. Using these test pieces, various physical properties were measured by the test methods described above.

Table 1 shows the results.

[0094]

Example 2 Test pieces were prepared in the same manner as in Example 1 except that 20 parts by weight of the inorganic filler (C-1) was used, and various physical properties were measured.

Table 1 shows the results.

[0096]

Example 3 A test piece was prepared in the same manner as in Example 1 except that 10 parts by weight of the inorganic filler (C-2) was used instead of the inorganic filler (C-1). And various physical properties were measured.

Table 1 shows the results.

[0098]

Example 4 A test piece was prepared in the same manner as in Example 1 except that 10 parts by weight of the inorganic filler (C-3) was used instead of the inorganic filler (C-1). And various physical properties were measured.

Table 1 shows the results.

[0100]

Comparative Example 1 In Example 1, except that 10 parts by weight of an inorganic filler (CX) was used instead of the inorganic filler (C-1).
Test pieces were prepared in the same manner as in Example 1, and various physical properties were measured.

Table 1 shows the results.

[0102]

Comparative Example 2 In Example 1, except that 20 parts by weight of an inorganic filler (CX) was used instead of the inorganic filler (C-1).
Test pieces were prepared in the same manner as in Example 1, and various physical properties were measured.

Table 1 shows the results.

[0104]

Comparative Example 3 Example 1 was repeated except that the inorganic filler (C-1) was replaced with 10 parts by weight of the inorganic filler (CX) and 0.2 parts by weight of rosin acid. Test pieces were prepared in the same manner, and various physical properties were measured.

Table 1 shows the results.

[0106]

Comparative Example 4 Example 1 was repeated except that the inorganic filler (C-1) was replaced with 10 parts by weight of the inorganic filler (CX) and 0.5 parts by weight of rosin acid. Test pieces were prepared in the same manner, and various physical properties were measured.

Table 1 shows the results.

[0108]

[Table 1]

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI C08L 77/00 C08L 77/00 101/00 101/00 C09C 1/02 C09C 1/02 1/28 1/28 (72) Invention Person Masao Maeda 1-19-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka Inside Arakawa Chemical Industry Co., Ltd. (72) Inventor Eisuke Natsuhara 1-1-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka Arakawa Chemical Co., Ltd. In company

Claims (10)

[Claims] (A) an inorganic filler, and the inorganic filler (A)
And (B) rosin acid and / or a derivative thereof, which covers the surface of (b), wherein the amount of rosin acid and / or its derivative (B) is 0.01 to 100 parts by weight of the inorganic filler (A). A rosin acid-coated inorganic filler, which is 20 parts by weight. 2. The method according to claim 1, wherein the inorganic filler (A) is of Group I of the periodic table,
The rosin acid-coated inorganic filler according to claim 1, which is at least one compound containing at least one metal element selected from Group II and Group III. 3. The method according to claim 1, wherein the inorganic filler (A) is Mg, K, Na,
The rosin acid-coated inorganic filler according to any one of claims 1 to 2, wherein the inorganic filler is at least one compound containing at least one metal element selected from Al. 4. The rosin acid-coated inorganic filler according to claim 1, wherein said inorganic filler (A) is a magnesium compound. 5. The method according to claim 1, wherein said inorganic filler (A) is at least one compound selected from talc, magnesium carbonate, magnesium hydroxide, magnesium oxide and hydrotalcite. A rosin acid-coated inorganic filler according to any one of the above. 6. The method according to claim 1, wherein the rosin acid and / or its derivative (B) comprises at least one rosin acid or a derivative thereof selected from dehydroabietic acid, dihydroabietic acid and dihydropimaric acid. The rosin acid-coated inorganic filler according to any one of claims 1 to 5, characterized in that: 7. The rosin acid and / or its derivative (B) is at least one selected from the group consisting of a rosin acid represented by the following formula (Ia) and a rosin acid represented by the following formula (Ib): The rosin acid-coated inorganic filler according to any one of claims 1 to 5, wherein the rosin acid or a derivative thereof is used as a main component. [In the formulas (Ia) and (Ib), R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different.] 8. A thermoplastic resin (D) containing the rosin acid-coated inorganic filler (C) according to any one of claims 1 to 7, and 100 parts by weight of the thermoplastic resin (D). A rosin acid-coated inorganic filler (C) in an amount of 0.01 to 100 parts by weight. 9. The thermoplastic resin composition according to claim 8, wherein said thermoplastic resin (D) is at least one crystalline thermoplastic resin selected from the group consisting of polyolefins, polyesters, polyamides and polyacetals. 10. A thermoplastic resin composition characterized by melt-kneading (D) a thermoplastic resin and the rosin acid-coated inorganic filler (C) according to any one of claims 1 to 7. Method of manufacturing a product.