JP6034202B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a thermoplastic resin composition comprising a polycarbonate resin, a polyolefin-based resin, a polymerizable monomer, and a curing agent, and having excellent properties such as ductility, heat resistance, and solvent resistance, and a molded product thereof.

  Polycarbonate resins are widely used as molding resins for office equipment exterior parts and electrical / electronic parts. The resin is excellent in mechanical strength and thermal properties, but has a high melt viscosity and is difficult to be molded at a relatively high molding temperature and molding pressure. Moreover, the solvent resistance is low, and the use is limited. On the other hand, crystalline polyolefin resins such as polypropylene and polyethylene are excellent in molding processability, solvent resistance, etc., and are inexpensive. Therefore, electrical and electronic parts, home appliances, housings, packaging materials, automobiles, etc. Widely used industrially, such as parts. However, the fact that the heat resistance is not so high is an obstacle to the use in engineering plastics.

  Thus, attempts have been made to provide a material having good heat resistance and solvent resistance and improved moldability by blending a polycarbonate resin and a polyolefin resin. However, simply blending will cause a significant decrease in strength due to delamination, so the polyolefin resin can be modified to improve compatibility or contain a small amount of thermoplastic elastomer to suppress delamination. I am trying.

  For example, a resin composition using an elastomer graft-modified with a hydroxyl group-containing vinyl monomer as a compatibilizing agent has been proposed. (Refer to Patent Documents 1 and 2) However, although the impact resistance is good in this composition, since the compatibilizing effect is not sufficient, it is necessary to improve heat resistance and mechanical strength. In addition, a resin composition has been proposed in which polypropylene modified with a hydroxyl group-containing vinyl monomer is used as a compatibilizing agent, and an ethylene-α-olefin copolymer composed of ethylene and an α-olefin having 4 or more carbon atoms is used as an impact resistance agent. Yes. However, although this composition is excellent in impact resistance and rigidity, there is no description about compatibility. Furthermore, a resin composition using a styrene-ethylene / butylene-styrene block copolymer as a compatibilizing agent has been proposed. However, although this composition is excellent in compatibility, the ratio of the melt flow rate between the polypropylene resin and the styrene-ethylene-butylene-styrene block copolymer is large, and the impact property and tensile property are high. Improvement effect is insufficient.

JP-A-7-330972 JP-A-8-134277 JP 2005-132937 A Japanese Patent Laid-Open No. 5-17633

  As described above, although there is a demand for a resin composition having no delamination and having ductility, heat resistance, and solvent resistance, there is currently no disclosure of a method for obtaining such a resin composition. . Accordingly, an object of the present invention is to provide such a resin composition.

  As a result of intensive investigations in view of the above-mentioned problems of the prior art, the present inventor obtained high heat resistance by polymerizing a polymerizable monomer with a curing agent, and at the interface between a polycarbonate resin and a polyolefin resin. By forming a reaction product of a polymerizable monomer and a polyolefin-based resin, it was found that layer peeling was eliminated and high ductility was obtained.

  According to the present invention, the above-mentioned problems are as follows: (1) Polycarbonate resin (component A) 95 to 5 parts by weight, and polyolefin resin (component B) 5 to 95 parts by weight of resin component 100 parts by weight (C component) 0.5 to 95 parts by weight, and 100 parts by weight of polymerizable monomer, a thermoplastic resin composition obtained by melt-kneading 0.5 to 10 parts by weight of a curing agent (D component), This is achieved by a thermoplastic resin composition characterized in that the polymerizable monomer is compatible with the polycarbonate resin before melt kneading and polymerizes during melt kneading.

One of the preferred embodiments of the present invention is the resin composition having the above constitution (1), wherein (2) the polymerizable monomer contains two or more allyl groups.
One of the preferred embodiments of the present invention is that (3) the content of the polymerizable monomer is 10 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin. ) Resin composition.
One of the preferred embodiments of the present invention is (4) any one of the above constitutions (1) to (3), wherein the viscosity average molecular weight of the polycarbonate resin is 1.4 × 10 ^{4 to} 3 × 10 ^4. This resin composition.
One of the preferred embodiments of the present invention is the resin composition according to any one of the above constitutions (1) to (4), wherein (5) the curing agent is an organic peroxide.
One of the preferred embodiments of the present invention is (6) a molded article for electric / electronic parts, a molded article for automobile parts, and a household appliance using the thermoplastic resin composition according to any one of the above constitutions (1) to (5). A molded product selected from the group consisting of molded products.

Hereinafter, the present invention will be described in more detail.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of excellent toughness and deformation characteristics, and is widely used.

  In the present invention, in addition to the general-purpose polycarbonate bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used as the A component. For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and A copolymeric polycarbonate in which the BCF component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPA component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), and A copolymeric polycarbonate in which the BCF component is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and Copolymer polycarbonate in which the Bis-TMC component is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. And a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained.

  Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6- Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1 , 1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1- Trisphenol such as bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol is preferably exemplified. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is preferably in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. Is 0.03 to 1 mol%, more preferably 0.07 to 0.7 mol%, particularly preferably 0.1 to 0.4 mol%.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.

In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.4 × 10 ^{4 to} 3 × 10 ⁴ , more preferably 1.8 ×. 10 ^{4 to} 3 × 10 ⁴ , and more preferably 1.8 × 10 ^{4 to} 2.4 × 10 ⁴ . A polycarbonate resin having a viscosity average molecular weight of less than 1.4 × 10 ⁴ may not provide practically sufficient toughness and crack resistance. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 3 × 10 ⁴ generally has a low versatility because it generally requires a high molding temperature or requires a special molding method. A high molding temperature tends to cause deterioration of the deformation characteristics and rheological characteristics of the resin composition.

The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above value (3 × 10 ⁴ ) increases the melt tension of the resin composition of the present invention, and molding in extrusion molding, foam molding and blow molding based on such characteristics. Processability can be improved. Such an improvement effect is even better than the branched polycarbonate.

As a more suitable aspect, the A component is a polycarbonate resin (A-3-1 component) having a viscosity average molecular weight of 7 × 10 ⁴ to 2 × 10 ^{6, and} a polycarbonate resin having a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ Polycarbonate resin (A-3 component) consisting of (A-3-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3 × 10 ⁴ (hereinafter referred to as “high molecular weight component-containing polycarbonate resin”). May also be used.

In such a high molecular weight component-containing polycarbonate resin (A-3 component), the molecular weight of the A-3-1 component is preferably 7 × 10 ^{4 to} 3 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ⁵ , preferably ^{1 × 10 5 ~2 × 10 5} , particularly preferably ^{1 × 10 5 ~1.6 × 10 5} . The molecular weight of the A-3-2 component is preferably 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 × 10 ^4. to 2.4 × 10 ^4, particularly preferably ^{1.2 × 10 4 ~2.3 × 10 4} .

  The high molecular weight component-containing polycarbonate resin (component A-3) can be obtained by mixing the components A-3-1 and A-3-2 in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight and the A-3-2 component is 60 to 98% by weight, more preferably the A-3-1 component is 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually, the molecular weight distribution of the polycarbonate resin is in the range of 2-3. Therefore, it is preferable that the A-3-1 component and the A-3-2 component of the present invention satisfy the molecular weight distribution range. The molecular weight distribution is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC (gel permeation chromatography) measurement. And Mw is based on standard polystyrene conversion.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in the molecular weight distribution chart by GPC method represented by the method shown in the publication No. 1 in the same system, such an aromatic polycarbonate resin is represented by B- of the present invention. A method of producing so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a production method (production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., with a specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The calculation of the viscosity average molecular weight in the resin composition of the present invention is performed as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

(B component: polyolefin resin)
The resin composition of the present invention contains a polyolefin resin as the B component. The polyolefin resin is a synthetic resin obtained by polymerizing or copolymerizing an olefin monomer having a radical polymerizable double bond. The olefin-based monomer is not particularly limited, and examples thereof include α- such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. Examples thereof include olefins and conjugated dienes such as butadiene and isoprene. Olefinic monomers may be used alone or in combination of two or more.

  The polyolefin-based resin is not particularly limited. For example, a homopolymer of ethylene, a copolymer of ethylene and an α-olefin other than ethylene, a homopolymer of propylene, and a copolymer of propylene and an α-olefin other than propylene. Examples include polymers, butene homopolymers, homopolymers or copolymers of conjugated dienes such as butadiene and isoprene, and propylene homopolymers and copolymers of propylene and α-olefins other than propylene are preferred. . More preferred is a homopolymer of propylene. Polyolefin resins may be used alone or in combination of two or more.

  The amount of component B is 5 to 95 parts by weight, preferably 10 to 90 parts by weight, more preferably 20 to 90 parts by weight, in a total of 100 parts by weight of component A and component B. If the component B exceeds 95 parts by weight, the effect of improving the heat resistance is small, and if it is less than 5 parts by weight, the fluidity, peelability and solvent resistance are poor.

(C component: polymerizable monomer)
The resin composition of the present invention contains a polymerizable monomer as the C component. The polymerizable monomer used in the present invention must be compatible with the polycarbonate resin before melt kneading and polymerized during melt kneading. If the resin is not compatible with the polycarbonate resin before melt kneading, the kneadability between the polycarbonate resin and the polyolefin resin is deteriorated, delamination occurs, and the strength is lowered. When polymerization is not performed during melt-kneading, the glass transition temperature of the polycarbonate resin is lowered, so that the heat resistance is deteriorated.

  The polymerizable monomer is characterized by having two or more double bonds in one molecule. Some effects can be obtained with acrylic and methacrylic monomers such as 1,6-hexanediol diacrylate and trimethylolpropane trimethacrylate. However, in order to obtain a high degree of crosslinking at a relatively low concentration, a monomer containing an allyl group, particularly a monomer containing two or more allyl groups is preferred.

  Examples of the monomer containing an allyl group include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, trialmethallyl cyanurate, diallylamine, triallylamine, diallyl chlorentate Diallyl acetate, triallyl acetate, diallyl benzene, triallyl benzene, diallyl dipropyl isocyanurate, diallyl octyl oxalate, diallyl adipate, diallyl carbonate, diallyl dimethyl ammonium chloride, diallyl fumarate, diallyl malonate, diallyl oxalate, Diallyl sebanate, diallyl succinate, diallyl tartrate, diallyl isocyanurate, dimethyl diallyl Tallates, ethyl allyl malate, methyl allyl fumarate, and the like. Among these, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and triallyl cyanurate are preferable, and diallyl phthalate and triallyl cyanurate are particularly preferable.

  The content of component C is 0.5 to 95 parts by weight, preferably 0.6 to 70 parts by weight, more preferably 1.0 to 50 parts by weight, based on 100 parts by weight of the total of component A and component B. . When the content is less than 0.5 parts by weight, delamination occurs and the effect of improving ductility becomes insufficient. When the content exceeds 95 parts by weight, the polymerizable monomer gels, resulting in poor appearance and mechanical strength. .

  Furthermore, the content of the polymerizable monomer in the resin composition of the present invention is preferably 10 to 100 parts by weight, more preferably 10 to 80 parts by weight, and still more preferably 10 parts by weight with respect to 100 parts by weight of the polycarbonate resin. ~ 50 parts by weight. If the content of the polymerizable monomer is less than 10 parts by weight, delamination may occur and the effect of improving ductility may be insufficient. When the amount exceeds 100 parts by weight, the polymerizable monomer is gelled, so that pelletization by extrusion cannot be performed, or appearance defects and mechanical strength are reduced.

(D component: curing agent)
The resin composition of the present invention contains a curing agent as the D component. An organic peroxide is preferably used as the curing agent. Specific examples of the organic peroxide include cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1 -Di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t -Butylperoxy) butane, n-butyl 4,4-di- (t-butylperoxy) halate, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, p- Methane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Dropper oxide, cumene hydroperoxide, t-butyl hydroperoxide, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, diisobutylene Ruperoxide, di (3,3,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, disuccinic acid peroxide, di- (3-methyl) Benzoyl peroxide), dibenzoyl peroxide Di (4-methylbenzoyl) peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethoxyethyl) peroxydi Carbonate, di (3-methoxybutyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, α, α′-di (t-butylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1, 1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, , 1,3,3-Tetramethylbutylperoxy-2 -Ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl Hexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,3,5-trimethylhexanoate, t- Butyl peroxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t- Hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (ben Ylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate, t-butylperoxybenzoate, t-butylperoxyallylmonocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ′, Examples include 4,4′-tetra (t-butylperoxycarbonylbenzophenone) and 2,3-dimethyl-2,3-dienylbutane. Among these, dicumyl peroxide, α, α′-di (t-butylperoxy) diisopropylbenzene, and t-butylperoxybenzoate are preferable, and dicumyl peroxide is particularly preferable.

  Content of D component is 0.5-10 weight part with respect to 100 weight part of C component, Preferably it is 0.5-5 weight part, More preferably, it is 1-5 weight part. When the component A is a matrix, if the content of the component D is less than 0.5 parts by weight, delamination occurs and the fluidity is improved by the plasticizing effect of the component C, but the heat resistance is significantly reduced. On the other hand, in the case where the component B is a matrix, delamination occurs in the same manner, and the effect of improving fluidity and heat resistance cannot be obtained. When the content of the component D exceeds 10 parts by weight, the reaction with the polymerizable monomer is accelerated, so that the polymerizable monomer is gelled, resulting in poor appearance and mechanical strength.

(Other additives)
Further, the composition of the present invention may further include an inorganic filler, an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic colorant, if necessary. Additives such as a rust preventive agent, a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, a surface gloss improving agent, and a mold release improving agent such as a fluororesin may be included.

(Manufacture of thermoplastic resin composition)
The composition of the present invention is obtained by melt-kneading each component, and is particularly preferably produced by melt-kneading using a high-kneading biaxial extruder. Hereinafter, the manufacturing method will be described.

The composition of the present invention comprises:
1) Step of supplying various components to a twin screw extruder using a feeder (Step 1),
2) Step of melt kneading while setting the cylinder and die set temperature of 180 to 300 ° C. of the twin screw extruder while vacuum degassing the inside of the twin screw extruder (step 2)
It is preferable to be manufactured through.

  In step 1, the components may be mixed uniformly in advance with an apparatus such as a tumbler or a Henschel mixer, or may be omitted and supplied to a feeder if necessary. The feeder is a device that can supply a certain amount of raw material to a twin-screw extruder (hereinafter referred to as “kneading device”), and is equipped in the kneading device. Examples of the feeder include a twin screw extruder different from a metering feeder, a single screw extruder, or a kneading apparatus.

  In the melt kneading in step 2, the set temperature of the cylinder and die of the kneading apparatus is preferably 180 to 300 ° C, more preferably 190 to 270 ° C. The melt-kneading time varies depending on the blending ratio of each component, the melt-kneading temperature, and the like, and is not limited to one, but is preferably about 1 to 30 minutes. The kneading apparatus in this step is preferably a high-kneading twin screw extruder.

(About a molded article made of the resin composition of the present invention)
The resin composition in the present invention is produced by injection molding, extrusion molding, blow molding, by a known processing method such as injection molding, extrusion molding, blow molding, hollow molding, rotational molding, transfer molding, hot press molding, tube molding, and the like. Can be formed into a molded body, a hollow molded body, a rotational molded body, a transfer molded body, a press molded body, a tube molded body, and the like. The resin composition of the present invention is, for example, a T-die method for extruding and winding a molten resin from a T-die, an inflation film-forming method for extruding a molten resin into a cylindrical shape from an extruder provided with an annular die, and cooling and winding it. Alternatively, a molded product can be obtained as a film or a sheet by a hot press method or a solvent casting method.

  The composition of the present invention is excellent in ductility, heat resistance and solvent resistance, and is inexpensive. Therefore, the composition of the present invention is suitable as an electric / electronic device part, a home appliance part, an OA equipment part, or an automobile interior / exterior part. Examples of automotive interior and exterior parts include automotive skins, doors, door trims, quarter trims, bumpers, instrument panels, front end modules, airbag peripheral components, cockpits, fan shrouds, radiator cooling fans, reserve tanks, automotive wheel covers Automobile parts such as cowling, window washer fluid tank, spoiler, instrument panel, bonnet, fuel pump housing, air cleaner, slot body, intake manifold, heater housing, bonnet, pillar, safety belt parts. Among these, automobile outer plates, doors, bumpers, automobile wheel covers, doors, door trims, pillars, instrument panels, and airbag peripheral parts are particularly preferable. In addition, the composition of the present invention can be widely applied to electric / electronic parts, home appliance parts, packaging materials, architectural interior materials, containers, films, sheets, bottles, housings, mechanical parts, and the like.

  The thermoplastic resin composition of the present invention has no delamination and is excellent in ductility, heat resistance, solvent resistance, and the like. Therefore, the thermoplastic resin composition of the present invention is widely useful in automobile applications, electrical and electronic applications, and other various fields. Therefore, the industrial effect of the present invention is extremely great.

  The form of the invention that the present inventor considers to be the best is an aggregation of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

Hereinafter, examples will be described further. Evaluation was carried out by the following method.
(I) Melt flow rate (MFR)
Based on ISO1133, MFR (g / 10min) was measured at 230 ° C. and a load of 5 kg. In addition, what dried the pellet for 8 hours at 100 degreeC was used for the measurement.
(Ii) Tensile properties (fracture strain, fracture strength)
Measurement was performed at a tensile speed of 100 mm / min in accordance with ISO 527. The test piece was a dumbbell-type test piece, and the parallel part shape was 25 mm long × 4 mm wide × 2 mm thick.
(Iii) Deflection temperature under load The deflection temperature under load (° C.) was measured at a load of 0.45 MPa in accordance with ISO75. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick.
(Iv) Peeling test Sample surface when 50 mm long x 45 mm wide x 2 mm thick test pieces were cut into 100 grids of 1 mm square with a cutter, and then cellophane tape was applied to the grids and peeled off. It was evaluated by the presence or absence of peeling.
(V) Solvent resistance test A test piece having a length of 80 mm, a width of 10 mm and a thickness of 4 mm was immersed in a solvent (acetone) at 23 ° C. for 12 hours, then removed from the solvent, and the solvent adhering to the test piece was used as a waste. Soaked. The surface of the immersed test specimen was visually observed, and “O” indicates that no abnormality was observed in the appearance, and “X” indicates abnormality in the appearance.

[Examples 1-8, Comparative Examples 1-8]
The resin composition which consists of a mixture ratio of Table 1 and Table 2 was created in the following ways. A polycarbonate resin, a polyolefin resin, a polymerizable monomer, and a curing agent having the composition shown in Table 1 and Table 2 are supplied to a vent type twin-screw extruder having a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works, Ltd.], and the cylinder temperature. It was melt-extruded and pelletized at 250 ° C., a screw rotation speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa. The screw configuration consists of a first-stage kneading zone (2 feed kneading discs, 1 feed rotor, 1 return rotor, and 1 return kneading disc) before the side feeder. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided.

In addition, D-1 of the curing agent was supplied from the second supply port using a side feeder, and the remaining components were premixed with a tumbler and supplied from the first supply port.
The obtained pellets were dried with a hot air circulating dryer at 100 ° C. for 8 hours, and then a test piece for evaluation was molded using an injection molding machine. The injection molding machine used was a NP7 type Real Mini manufactured by Nissei Plastic Industry Co., Ltd., and the molding conditions were a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. The evaluation results are shown in Tables 1 and 2.

In addition, each component of symbol description in Table 1 and Table 2 is as follows.
(Component A)
A-1: Polycarbonate resin [Teijin Chemicals Ltd. Panlite L-1225WX (product name), Mv = 19,700]
A-2: Polycarbonate resin [Panlite L-1250WP (product name) manufactured by Teijin Chemicals Ltd., Mv = 23,900]
(B component)
B-1: Homopolypropylene resin [Nobrene H501 (product name) manufactured by Sumitomo Chemical Co., Ltd., MFR (230 ° C., 2.16 kg load) = 2.0 g / 10 min, specific gravity 0.9]
(C component)
C-1: Diallyl phthalate [Daiso Dup (product name) manufactured by Daiso Corporation]
C-2: Triallyl cyanurate [Reagent manufactured by Wako Pure Chemical Industries, Ltd.]
(D component)
D-1: Dicumyl peroxide [Parkmill D (product name) manufactured by NOF Corporation, 1 minute half-life temperature = 175 ° C.]
D-2: α, α′-di (t-butylperoxy) diisopropylbenzene [Perbutyl P (product name) manufactured by NOF Corporation, 1 minute half-life temperature = 175 ° C.]

  From Examples 1-8 and Comparative Examples 1-8, a thermoplastic resin composition comprising a polycarbonate resin, a polymerizable monomer, a polyolefin resin, and a curing agent has excellent moldability, ductility, heat resistance, solvent resistance, and peelability. It is clear that it is excellent.

Claims (4)

(A) Polycarbonate resin (component A) 95-5 parts by weight and (B) polyolefin resin (component B) 5 parts by weight to 100 parts by weight of resin component (C) Two or more allyl groups polymerizable monomer (C component) 8-95 parts by weight containing, as well as the polymerizable monomer 100 parts by weight of a thermoplastic resin obtained by melt-kneading a 0.5 to 10 parts by weight (D) a curing agent component (D) a method of manufacturing a composition, the polymerizable monomer is compatible with the polycarbonate resin before melting and kneading method for producing a thermoplastic resin composition characterized by polymerizing in the melt-kneading. The content of the polymerizable monomer is 100 parts by weight of polycarbonate resin to process according to claim 1 Symbol placement of the thermoplastic resin composition, characterized in that 10 to 100 parts by weight. The method for producing a thermoplastic resin composition according to claim 1 or 2 viscosity-average molecular weight of the polycarbonate resin is characterized in that it is a ^{1.4 × 10 4 ~3 × 10 4} . The method for producing a thermoplastic resin composition according to any one of claims 1 to 3 , wherein the curing agent is an organic peroxide.