JP2021138913A - Resin composition for molding - Google Patents

Abstract

To provide a resin composition for molding having excellent moldability.SOLUTION: A resin composition for molding (Y) contains a heat conductive filler dispersant (α) containing a polyamide (am) with an acid value (unit: mgKOH/g) of 20-100 and/or an acid-modified polyolefin (X) with an acid value (unit: mgKOH/g) of 20-100, at least one thermoplastic resin (D) selected from the group consisting of a polyolefin resin (D1) and a polyamide resin (D2), and a heat conductive filler (F).SELECTED DRAWING: None

Description

The present invention relates to a molding resin composition.

As a resin composition using a thermally conductive filler, for example, a polyimide resin composition in which boron nitride powder is dispersed in a polyimide resin to improve thermal conductivity has been proposed (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 10-87990

However, there is a concern that the boron nitride powder may fall off during molding, and there is a problem in moldability.
An object of the present invention is to provide a molding resin composition having excellent moldability.

The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention provides a polyamide (am) having an acid value (unit: mgKOH / g) of 20 to 100 and / or an acid-modified polyolefin (X) having an acid value (unit: mgKOH / g) of 20 to 100. A dispersant (α) for a heat conductive filler contained therein, at least one thermoplastic resin (D) selected from the group consisting of a polyolefin resin (D1) and a polyamide resin (D2), and a heat conductive filler ( A molding resin composition (Y) containing F) and.

The molding resin composition (Y) of the present invention has the following effects.
(1) The molded product has excellent thermal conductivity.
(2) Excellent moldability.

<Polyamide (am)>
Examples of the polyamide (am) in the present invention include the polyamide (a1) described later.
The acid value (unit: mgKOH / g) of the polyamide (am) is 20 to 100, preferably 30 to 90, and more preferably 40 to 80.
If the acid value is less than 20, the thermal conductivity tends to be inferior, and if it exceeds 100, the moldability tends to be inferior.
The acid value can be adjusted, for example, by the number average molecular weight (Mn) of (am) and the weight of the constituent raw material dicarboxylic acid (a04).

The acid value in the present invention is a value obtained by measuring according to the following procedures (i) to (iii) according to JIS K0070.
(I) Dissolve 1 g of (X) in 100 g of xylene whose temperature has been adjusted to 100 ° C.
(Ii) Titrate with 0.1 mol / L potassium hydroxide ethanol solution [trade name "0.1 mol / L ethanolic potassium hydroxide solution", manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator at the same temperature. I do.
(Iii) The acid value (unit: mgKOH / g) is calculated by converting the amount of potassium hydroxide required for titration into mg.

Examples of the polyamide (a1) include those obtained by ring-opening polymerization or polycondensation of an amide-forming monomer.
Examples of the amide-forming monomer include lactam (a01), aminocarboxylic acid (a02), and diamine (a03) / dicarboxylic acid (a04).
Examples of the lactam (a01) include lactams having 4 to 20 carbon atoms [hereinafter, may be abbreviated as C] (caprolactam, enantractam, laurolactam, undecanolactam, etc.).
Examples of the ring-opening polymer of (a01) include nylon 4, nylon 5, nylon 6, nylon 8 and nylon 12.

Examples of the aminocarboxylic acid (a02) include C6-12, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12. -Aminododecanoic acid and mixtures thereof can be mentioned.

Examples of the diamine (a03) include C2-40, for example, aliphatic, alicyclic and aromatic (aliphatic) diamines, and mixtures thereof.
Examples of the aliphatic diamine include C2-40, for example, ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine and 1,20-eicosanediamine.
Alicyclic diamines include C5-40, such as 1,3- and 1,4-cyclohexanediamine, isophoronediamine 4,4'-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) propane. ..
Aromatic aliphatic diamines include C7-20, such as xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene and bis (aminobutyl) benzene.
Aromatic diamines include C6-40, such as p-phenylenediamine 2,4- and 2,6-toluylenediamine and 2,2-bis (4,4'-diaminophenyl) propane.

Examples of the dicarboxylic acid (a04) include C2-40 dicarboxylic acids such as aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, and alicyclic dicarboxylic acids. Derivatives of dicarboxylic acids [eg acid anhydrides, lower (C1-4) alkyl esters and dicarboxylic acids [alkali metals (eg lithium, sodium and potassium)]] and mixtures of two or more of these can be mentioned.

Examples of the aliphatic dicarboxylic acid include C2 to 40 (preferably 4 to 20, more preferably 6 to 12), for example, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, and undecanedic acid. , Dodecanedioic acid, maleic acid, fumaric acid and itaconic acid.
The aromatic ring-containing dicarboxylic acid includes C8-40 (preferably 8-16, more preferably 8-14), such as ortho-, iso- and terephthalic acid, 2,6- and 2,7-naphthalenedicarboxylic acid, diphenyl-. Included are 4,4'-dicarboxylic acid, diphenoxyetanedicarboxylic acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid and alkali metal 5-sulfoisophthalate (same as above) salts.
Examples of the alicyclic dicarboxylic acid include C5 to 40 (preferably 6 to 18, more preferably 8 to 14), for example, cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4'. − Dicarboxylic acids and succinoic acids are included.

Of the amide-forming monomers, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferred, and caprolactam is even more preferred.

As a method for producing (a1), one or more of the above dicarboxylic acid (C2 to 40, preferably 4 to 20) or the above diamine (C2 to 40, preferably 4 to 20) or water is used as a molecular weight modifier. Examples thereof include a method of ring-opening polymerization or polycondensation of the amide-forming monomer in the presence of the amide-forming monomer.

(Am) number average molecular weight [hereinafter abbreviated as Mn. The measurement is by gel permeation chromatography (GPC) method. ] Is preferably 500 to 6,000, more preferably 700 to 5,000, and particularly preferably 1,000 to 4,000.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) in the present invention can be measured by gel permeation chromatography (GPC) under the following conditions.
Equipment (example): "HLC-8120" [manufactured by Tosoh Corporation]
Column (example): "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2)
"TSKgel Multipore HXL-M" [manufactured by Tosoh Corporation] (1 bottle)
Sample solution: 0.3 wt% orthodichlorobenzene solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 135 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970,
9,100,18,100,37,900,96,400,
190,000, 355,000, 1,090,000,
2,890,000) [manufactured by Tosoh Corporation]

The amine value (unit: KOHmg / g, primary amine value: JIS K7237) of the polyamide (am) is preferably 0 to 10, and more preferably 0.1 to 5.
The amine value can be adjusted by, for example, the weight of Mn (am) and the dicarboxylic acid (a04) which is a constituent raw material.

<Acid-modified polyolefin (X)>
Examples of the acid-modified polyolefin (X) in the present invention include those using the polyolefin (A) and the unsaturated (poly) carboxylic acid (B) described later as constituent raw materials.
The acid value (unit: mgKOH / g) of the acid-modified polyolefin (X) is 20 to 100, preferably 30 to 90, and more preferably 40 to 80.
If the acid value is less than 20, the thermal conductivity tends to be inferior, and if it exceeds 100, the moldability tends to be inferior.
The acid value can be adjusted, for example, by the weight ratio [(A) / (B)] of the polyolefin (A) and the unsaturated (poly) carboxylic acid (B).

The Mn of (X) is preferably 1,500 to 20,000, more preferably 2,000 to 15,000, and particularly preferably 2,500 to 10,000.

<Polyolefin (A)>
The polyolefin (A) in the present invention is a polyolefin having a double bond at the molecular end and / or in the molecular chain.
As for the polyolefin (A), preferably, the polyolefin (A0) described later is referred to as a thermal decomposing method (hereinafter, may be referred to as a thermal decomposing method. It is obtained by heat reduction according to the manufacturing method described).

Further, (A) has a double bond at the molecular end and / or in the molecular chain from the viewpoint of copolymerizability with the unsaturated (poly) carboxylic acid (anhydride) (B) described later.
The number of double bonds in the molecular terminal and / or the molecular chain per 1,000 carbons (also referred to as 1,000 carbons) of (A) is preferably 0.1 to 20, more preferably 0. .3 to 18, especially preferably 0.5 to 15.

Here, the number of double bonds ^{can be obtained from the spectrum of 1} H-NMR (nuclear magnetic resonance) spectroscopy of (A). That is, the peak in the spectrum is assigned, and from the integrated value derived from the double bond at 4.5 to 6 ppm of (A) and the integrated value derived from (A), the number of double bonds in (A) and (A) The relative value of the number of carbon atoms of (A) is obtained, and the number of double bonds in the molecular terminal and / or the molecular chain per 1,000 carbon atoms of (A) is calculated. The number of double bonds in the examples described below was in accordance with the method.

The heat-decomposing method includes (1) heat-decomposing polyolefin (A0) in the absence of organic peroxides at, for example, 300 to 450 ° C. for 0.5 to 10 hours, and (2) organic peroxide. A method of heat-decomposing in the presence of a substance [for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane] at 180 to 300 ° C. for 0.5 to 10 hours is included.
Of these, from the viewpoint of copolymerizability between the obtained (A) and (B), the method (1) is preferable because it is easy to obtain one having a larger number of double bonds at the molecular terminal and / or in the molecular chain. be.

The Mn of (A) is preferably 1,500 to 20,000, more preferably 2,000 to 15,000, and particularly preferably 2,200 to 9,500.

The polyolefin (A0) includes one or more (co) polymers of olefins, and copolymers of one or more olefins and one or more other monomers. Is included.
The olefins include alkenes having 2 to 30 carbon atoms [sometimes abbreviated as C in the present invention] such as ethylene, propylene, 1- and 2-butene, and isobutylene, and α-olefins having C5 to 30 (C). 1-hexene, 1-decene, 1-dodecene, etc.); Other monomers include C4-30 unsaturated monomers having copolymerizability with olefins, such as vinyl acetate.

Specific examples of (A0) include ethylene unit-containing (propylene unit-free) (co) polymers such as high-, medium- and low-density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1-). Butene, etc.), C5-30 α-olefin (1-hexene, 1-dodecene, etc.), vinyl acetate, etc.] (weight ratio is preferably 30/70 to 99/1, more preferably 50. / 50-95 / 5) etc .; propylene unit-containing (ethylene unit-free) (co) polymer, for example, a polymer (weight) of polypropylene, propylene and a C4-30 unsaturated monomer (same as above). The ratio is the same as above); ethylene / propylene copolymer (weight ratio is preferably 0.5 / 99.5 to 30/70, more preferably 2/98 to 20/80); Co) Polymers, such as polybutene, are included.
Of these, polyethylene, polypropylene, ethylene / propylene copolymer, and propylene / are preferable from the viewpoint of polymerizable properties with the polyolefin (A) described later and the unsaturated (poly) carboxylic acid (anhydrous) (B) described later. C4 to 30 unsaturated monomer copolymers, more preferably ethylene / propylene copolymers and propylene / C4 to 30 unsaturated monomer copolymers.

Number average molecular weight of (A0) [hereinafter abbreviated as Mn. The measurement is performed by the gel permeation chromatography (GPC) method described later. same as below. ] Is preferably 30,000 to 400,000, more preferably 50,000 to 200,000.

<Unsaturated (poly) carboxylic acid (anhydride) (B)>
The unsaturated (poly) carboxylic acid (anhydride) (B) in the present invention is a C3-30 (poly) carboxylic acid (anhydride) having one polymerizable unsaturated group. In the present invention, the unsaturated (poly) carboxylic acid (anhydrous) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride.

Among the (B), unsaturated monocarboxylic acids include aliphatic (C3 to 24, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid) and alicyclic (C6 to 24, For example, cyclohexenecarboxylic acid); unsaturated poly (2-3 or more) carboxylic acid (anhydrous) includes unsaturated dicarboxylic acid (anhydrous) [aliphatic dicarboxylic acid (anhydrous) (C4-24, eg malein). Acids, fumaric acids, itaconic acids, citraconic acids, mesaconic acids, and their anhydrides), alicyclic-containing dicarboxylic acids (anhydrous) (C8-24, eg cyclohexendicarboxylic acids, cycloheptenedicarboxylic acids, bicyclohep Tendicarboxylic acid, methyltetrahydrophthalic acid, and anhydrides thereof), etc.] and the like can be mentioned. (B) may be used alone or in combination of two.
Of these, unsaturated dicarboxylic acid anhydride is preferable from the viewpoint of polymerizable property with polyolefin (A), and maleic anhydride is more preferable.

The form of the acid-modified polyolefin (X) includes the following.
[1] A graft copolymer having (A) as a trunk and (B) as a branch.
[2] Random copolymers of (A) and (B).
The form of the above [1] is further required by heating and melting the radical polymerization initiator (d), preferably in the presence of a peroxide, or suspending or dissolving the (A) and (B) in a suitable organic solvent. It can be formed by adding the chain transfer agent (t) and the polymerization inhibitor (f) and heating and stirring.
In the form of the above [2], the radical polymerization initiator (d), preferably in the presence of an azo compound, (A) and (B) are heated and melted, or suspended or dissolved in a suitable organic solvent, and further described later if necessary. It can be formed by adding the chain transfer agent (t) and the polymerization inhibitor (f) of the above and heating and stirring.

<Dispersant for thermally conductive filler (α)>
The dispersant (α) for a heat conductive filler in the present invention contains the polyamide (am) and / or the acid-modified polyolefin (X).
Of the polyamide (am) and the acid-modified polyolefin (X), the combination of (am), (am) and (X) is preferable, and the combination of (am) and (X) is more preferable.
When the above (am) and (X) are used in combination, the weight ratio [(am) / (X)] of (am) and (X) is preferably 20/80 to 80/20, more preferably 40. It is / 60 to 60/40.

<Thermoplastic resin (D)>
The thermoplastic resin (D) in the present invention is at least one selected from the group consisting of the polyolefin resin (D1) and the polyamide resin (D2) described later.
Of the above (D), (D2), (D1) and (D2) are preferably used in combination.
When the above (D1) and (D2) are used in combination, the weight ratio [(D1) / (D2)] of (D1) and (D2) is preferably 20/80 to 80/20, more preferably 40. It is / 60 to 60/40.

Examples of the polyolefin resin (D1) include those exemplified as the polyolefin (A0), and one type may be used alone or two or more types may be used in combination.
Among the polyolefin resins (D1), polyethylene, polypropylene and ethylene / propylene copolymers are preferable, and polypropylene and ethylene / propylene copolymers are more preferable.
The number average molecular weight (Mn) of the polyolefin resin (D1) is preferably 30,000 to 400,000, more preferably 50,000 to 200,000.

Examples of the polyamide resin (D2) include nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12, and a mixture of two or more of these. Be done.
The number average molecular weight (Mn) of the polyamide resin (D2) is preferably 7,000 to 100,000, more preferably 10,000 to 50,000.

<Thermal conductive filler (F)>
Examples of the thermally conductive filler (F) in the present invention include the following (F1) to (F7).
(F1) Silicates (eg talc, clay, mica, glass);
(F2) Metal oxides (eg titanium oxide, alumina, silica, magnesium oxide);
(F3) Carbonates (eg calcium carbonate, magnesium carbonate, hydrotalcite);
(F4) Hydroxides (eg aluminum hydroxide, magnesium hydroxide, calcium hydroxide);
(F5) (sulfuric acid) sulfate (eg barium sulfate, calcium sulfate, calcium sulfite);
(F6) Borate (eg zinc borate, barium borate, aluminum borate, calcium borate, sodium borate);
(F7) Nitride (for example, aluminum nitride, boron nitride, silicon nitride).

Among the above-mentioned thermally conductive fillers (F), (F2) and (F7) are preferable, (F2) is more preferable, and alumina is particularly preferable.
The median particle size of (F) is preferably 0.1 to 150 μm, more preferably 0.2 to 50 μm.
In the above (F), it is preferable to use both a large particle size and a small particle size in combination from the viewpoint of thermal conductivity.

<Plastic composition for molding (Y)>
It contains the dispersant (α) for a thermally conductive filler, the thermoplastic resin (D), and the thermally conductive filler (F).
Based on the total weight of (α), (D) and (F) [(α) + (D) + (F)], the weight of (α) is preferably 1 to 10% by weight, more preferably 1 to 10% by weight. Is 2-7% by weight.
Further, based on the total weight of (α), (D) and (F) [(α) + (D) + (F)], the weight of (D) is preferably 20 to 70% by weight. More preferably, it is 35 to 60% by weight.
Further, based on the total weight of (α), (D) and (F) [(α) + (D) + (F)], the weight of (F) is preferably 20 to 70% by weight. More preferably, it is 35 to 60% by weight.

Of the combinations [(α) / (D)] of the dispersant (α) for the thermally conductive filler and the thermoplastic resin (D), the preferred one is (X) / [(D1) + (D2)]. , [(Am) + (X)] / (D1), [(am) + (X)] / (D2), [(am) + (X)] / [(D1) + (D2)], and more [(Am) + (X)] / [(D1) + (D2)] are preferable.

In addition to the above (α), (D), and (F), the composition may contain a colorant, a mold release agent, an antioxidant, a flame retardant, and an ultraviolet absorber, if necessary, as long as the effects of the present invention are not impaired. , At least one selected from the group consisting of antibacterial agents, compatibilizers, fillers and antistatic improvers, and other additives (G) shown below can be contained. Each of the (G) may be one kind or a combination of two or more kinds.

Coloring agents (G1) include inorganic pigments [white pigments, etc.], organic pigments [azo pigments, polycyclic pigments, etc.], dyes [azo-based, indigoid-based, sulfide-based, alizarin-based, acrydin-based, thiazole-based, nitro. System, aniline system, etc.] etc .;

Examples of the release agent (G2) include lower (C1 to 4) alcohol esters of higher fatty acids (the above) (butyl stearate, etc.) and polyvalent (divalent to tetravalent or higher) fatty acids (C2 to 18). ) Alcohol esters (hardened castor oil, etc.), glycols (C2-8) esters of fatty acids (C2-18) (ethylene glycol monostearate, etc.), liquid paraffins, etc.;

Examples of the antioxidant (G3) include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.)) and bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol). ) Etc.], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.], etc.], Sulfur compound (dilauryl 3) , 3'-thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.), etc.;

The flame retardant (G4) includes a halogen-containing flame retardant, a nitrogen-containing flame retardant, a sulfur-containing flame retardant, a silicon-containing flame retardant, a phosphorus-containing flame retardant, and the like;

Examples of the ultraviolet absorber (G5) include benzotriazole [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, etc.], benzophenone [2-hydroxy-4-methoxybenzophenone, etc.], salicylate [phenylsalicylate, etc.] Etc.], acrylate [2-ethylhexyl-2-cyano-3,3'1-diphenylacrylate, etc.], etc .;

Antibacterial agents (G6) include benzoic acid, sorbic acid, halogenated phenol, organic iodine, nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebisthianocyanate), N-halo. Alkylthioimide, copper agent (8-oxyquinolin copper, etc.), benzimidazole, benzthiazole, trihaloallyl, triazole, organic nitrogen-sulfur compound (Suraoff 39, etc.), quaternary ammonium compound, pyridine compound, etc.;

The compatibilizer (G7) includes a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group: for example. , The polymer described in JP-A-3-258850, the modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, and the block weight having a polyolefin moiety and an aromatic vinyl polymer moiety. Coalescence, etc .;

Examples of the filler (G8) include an inorganic filler (clay and the like) and an organic filler (urea, calcium stearate and the like) and the like.

Examples of the antistatic agent (G9) include an ethylene oxide (EO) adduct (molecular weight 158 or more and less than Mn 20,000) of a surfactant [higher alcohol (C8-18)) and a saturated fatty acid sodium salt of C8-22. , Lauryl trimethyl ammonium chloride] and the like.

The total content of (G) based on the weight of the thermoplastic resin (D) is, for example, 45% or less, preferably 0.001 to 40%, more preferably 0.001 to 40% from the viewpoint of the effect of each additive and the mechanical properties of the molded product. Is 0.01 to 35%; the content of each (G) is preferably 0.1 to 3%, more preferably 0.2 to 2%; (G2) is preferable from the same viewpoint. 0.01 to 3%, more preferably 0.05 to 1%; (G3) is preferably 0.01 to 3%, further preferably 0.05 to 1%; (G4) is preferably 0.5 to 20%, more preferably 1-10%; (G5) is preferably 0.01-3%, even more preferably 0.05-1%; (G6) is preferably 0.5-20%, even more preferably. 1-10%; (G7) is preferably 0.5-10%, more preferably 1-5%; (G8) is preferably 0.5-10%, even more preferably 1-5%; (G9). Is preferably 0.1 to 3%, more preferably 0.3 to 2%.

The molding resin composition (Y) of the present invention can be obtained, for example, by the following method.
(I): (α), (D), (F), and if necessary, other additive (G) are melt-mixed.
(Ii): (α), (D2), and (F) are melt-mixed in advance, and then components other than the above are melt-mixed.
(Iii): (α) and (F) are melt-mixed in advance, and then components other than the above are melt-mixed.
(Iv): (am), (D2), and (F) are melt-mixed in advance, and then components other than the above are melt-mixed.
Of the above (i) to (iv), from the viewpoint of thermal conductivity, (ii), (iii), (iv) are preferable, (ii), (iv) are more preferable, and (iv) is particularly preferable. iv).
As a method of melt-mixing, generally, a method of mixing pellet-shaped or powder-shaped components with an appropriate mixer (Henschel mixer, etc.) and then melting-mixing with an extruder to pelletize is applied. can.

<Molded product>
The molded product of the present invention is a molded product of the resin composition (Y). That is, it is obtained by molding the resin composition (Y).
Examples of the molding method include injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.) and the like.

The resin composition (Y) of the present invention and its molded product are excellent in moldability [affinity between filler and resin (adhesion)] and excellent in thermal conductivity. Therefore, it is extremely useful for various resin molded products, especially for electronic / electrical equipment, transport materials, and daily necessities.

Examples of the present invention will be described below, but the present invention is not limited thereto. In the following, parts indicate parts by weight.

<Manufacturing example 1>
In a stainless steel pressure resistant reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen introduction tube and decompression device, 79.4 parts of ε-caprolactam, 11.5 parts of terephthalic acid, antioxidant [“Irganox 1010” , Made by Caprolactam Chemicals Co., Ltd.] 0.3 parts and 6 parts of water were added, and after nitrogen replacement, the temperature was raised to 220 ° C. with stirring under sealing, and the same temperature (pressure: 0.2 to 0. The mixture was stirred with 3 MPa) for 4 hours to obtain a polyamide (am-1).
The acid value of (am-1) was 78, and Mn was 1,400.

<Manufacturing example 2>
Polyolefin (A0-1) containing 98 mol% of propylene and 2 mol% of ethylene as constituent units in a reaction vessel [trade name "SunAllomer PZA20A", manufactured by SunAllomer Ltd., Mn100,000, the same applies hereinafter. ] 100 parts were charged in a nitrogen atmosphere, heated and melted by a mantle heater while aerating nitrogen through the gas phase part, and heat-decomposed at 360 ° C. for 70 minutes while stirring to obtain polyolefin (A-1). .. In (A-1), the number of double bonds in the molecular terminal and / or the molecular chain per 1,000 carbons was 7.2, and Mn was 3,000.
Next, 100 parts of (A-1) was charged into the reaction vessel, and after nitrogen substitution, the temperature was raised to 180 ° C. under nitrogen aeration to uniformly melt the mixture. After adding 8 parts of maleic anhydride (B-1) and dissolving it, 2 parts of dicumylperoxide [trade name "Parkmill D", manufactured by NOF CORPORATION] (D-1) is added to 4 parts of xylene. The dissolved solution was added dropwise over 10 minutes and stirring was continued at 180 ° C. for 3 hours. Then, xylene was distilled off under reduced pressure (1.5 kPa, the same applies hereinafter) to obtain an acid-modified polyolefin (X-1). (X-1) had an acid value of 41 and Mn of 4,000.

<Examples 1 to 4, 7 to 9, Comparative Example 1>
According to the compounding composition (part) shown in Table 1, the dispersant (α) for the thermally conductive filler, the thermoplastic resin (D), and the thermally conductive feeler (F) are added and blended for 3 minutes with a Henschel mixer. Each resin composition (Y) was obtained by mixing for 5 minutes under the condition of 50 rpm with a plastic mill heated to 240 ° C. Each of the obtained resin compositions (Y) was evaluated by the <evaluation method> described later. The results are shown in Table 1.

<Examples 5 to 6>
According to the compounding composition (part) shown in Table 1, (am-1), (D2-1), and (F-1) were blended with a Henschel mixer for 3 minutes, and then heated to 240 ° C. with a plast mill. The mixture was mixed for 5 minutes under the condition of 50 rpm.
Further, (X-1) and (D1-1) are added and mixed for 5 minutes under the condition of 50 rpm with a plast mill heated to 240 ° C. to obtain each resin composition (Y). rice field. The obtained resin composition (Y) was evaluated by the <evaluation method> described later. The results are shown in Table 1.

<Example 10>
According to the compounding composition (part) shown in Table 1, (D1-1) and (X-1) were blended with a Henschel mixer for 3 minutes, and then heated to 240 ° C. under the condition of 50 rpm with a plast mill. Mix for 5 minutes.
Further, (D2-1) and (F-1) were added and mixed for 5 minutes under the condition of 50 rpm with a plast mill heated to 240 ° C. to obtain the resin composition (Y-10). Got The obtained resin composition (Y) was evaluated by the <evaluation method> described later. The results are shown in Table 1.

(D1-1): Polyolefin resin (polypropylene)
[Product name "SunAllomer PM600A", manufactured by SunAllomer Ltd., Mn43,000]
(D2-1): Polyamide resin [Product name "UBE Nylon 1013B", manufactured by Ube Industries, Ltd., Mn13,000]
(F-1): Alumina <[Product name "AKP-50", manufactured by Sumitomo Chemical Co., Ltd., median particle size 0.2 μm] 13 parts and [Product name "CL-310", manufactured by Sumitomo Chemical Co., Ltd., Median particle size 10 μm] Mixture with 87 parts>

<Evaluation method>
<1> Moldability Each of the obtained resin compositions (Y) was pressed with a heating press to obtain a test piece having a thickness of 1 mm. Each of the obtained test pieces was cut into 5 mm squares with a razor to obtain 1 mm × 5 mm × 5 mm test pieces. Next, the cross section of the obtained test piece was vapor-deposited with platinum, observed by SEM, and evaluated according to the following <evaluation criteria>.
<Evaluation criteria>
⊚: There is no gap between the filler and the thermoplastic resin ○: The gap between the filler and the thermoplastic resin is small △: The gap between the filler and the thermoplastic resin can be confirmed ×: The gap between the filler and the thermoplastic resin There is a lot of filler falling off

<2> Thermal Conductivity Each of the obtained resin compositions (Y) was pressed with a heating press to obtain test pieces having a length of 120 mm, a width of 40 mm, and a thickness of 5 mm. Each of the obtained test pieces was measured for thermal conductivity (unit: W / m · K) by the hot wire method using a thermal conductivity meter [“Kemtherm QTM-D3”, manufactured by Kyoto Denshi Kogyo Co., Ltd.].

From the results in Table 1, it can be seen that the molding resin composition (Y) of the present invention and its molded product are excellent in moldability and thermal conductivity as compared with the comparative ones.

The resin composition (Y) of the present invention and its molded product are excellent in moldability and thermal conductivity. Therefore, it is extremely useful for various resin molded products, especially for electronic / electrical equipment, transport materials, and daily necessities.

Claims (4)

Thermal conductivity comprising polyamide (am) having an acid value (unit: mgKOH / g) of 20 to 100 and / or an acid-modified polyolefin (X) having an acid value (unit: mgKOH / g) of 20 to 100. It contains a dispersant (α) for a sex filler, at least one thermoplastic resin (D) selected from the group consisting of a polyolefin resin (D1) and a polyamide resin (D2), and a heat conductive filler (F). Molding resin composition (Y). The resin composition according to claim 1, wherein the thermally conductive filler (F) is alumina. Based on the total weight of the dispersant (α) for the heat conductive filler, the thermoplastic resin (D), and the heat conductive filler (F), the weight of (α) is 1 to 10% by weight, and that of (D). The resin composition according to claim 1 or 2, wherein the weight is 20 to 70% by weight, and the weight of (F) is 20 to 70% by weight. A molded product obtained by molding the molding resin composition (Y) according to any one of claims 1 to 3.