JP6489944B2 - Resin composition and method for producing the same - Google Patents

Description

  The present invention relates to a resin composition, particularly a flame retardant resin composition having an aromatic polycarbonate resin, and a method for producing the same.

  Aromatic polycarbonate resins are not only excellent in heat resistance but also excellent in impact resistance, and thus have been used in various fields including automobile parts, home appliance parts, and OA equipment parts. However, in recent years, fire safety requirements have been particularly highlighted, and regulations on household electrical appliances and OA equipment have become stricter year by year, and there is a strong desire to develop technology that improves flame retardancy while maintaining heat resistance and impact resistance. It is rare.

  Also, from the viewpoint of ensuring moldability, aromatic polycarbonate resins are usually used industrially in alloys with other resins. Examples of the resin used as an alloy with the aromatic polycarbonate resin include styrene resins (acrylonitrile styrene (AS), acrylonitrile-butadiene-styrene (ABS), high impact polystyrene (HIPS)) and the like. For this reason, it is desired to develop a technology that brings the above physical properties (heat resistance, impact resistance, flame retardancy) in parallel by controlling the blending of an aromatic polycarbonate resin, a styrene resin, and a flame retardant.

  For example, Patent Document 1 discloses an aromatic polycarbonate resin composition containing a phosphoric acid ester that is a flame retardant.

JP 2001-220504 A

Hansen Solubility Parameters: A User's Handbook second edition, Charles M. Hamsen, CRC Press, 2007

  However, when phosphoric acid ester is used as a flame retardant as in Patent Document 1, although the flame retardancy is improved, the hydrolysis reaction of the aromatic polycarbonate resin resulting from the phosphoric acid ester proceeds, and the polycarbonate resin The molecular weight is reduced. Therefore, there is a problem that the mechanical strength is remarkably deteriorated with time. This problem also occurs in a resin composition that is an alloy of an aromatic polycarbonate resin and another resin. The resin composition has a phase separation structure composed of an aromatic polycarbonate resin phase and another resin phase, and the phosphate ester has high compatibility with the aromatic polycarbonate resin phase. It has been known. From this, the hydrolysis reaction resulting from the phosphoric acid ester is further promoted in the phase of the aromatic polycarbonate resin, and it cannot be said that both the flame retardancy and the mechanical strength are sufficient in the entire resin composition.

  This invention is made | formed in order to solve the subject mentioned above, The objective is to provide the resin composition which made the flame retardance and mechanical strength compatible, and its manufacturing method.

The resin composition of the present invention is a resin composition having at least an aromatic polycarbonate resin that is an A component, a styrene resin that is a B component, and a phosphate ester that is a C component,
The following general formula (1)
P _B / P _A > 0.70 (1)
(In the formula (1), P _A represents a peak intensity of phosphorus atoms contained in the phase of the A component in the EDX measurement, the P _B, represents a peak intensity of phosphorus atoms contained in the phase of the B component in the EDX measurement .)
And (2a) or (2b) below
(2a) | ΔSP _AC |> | ΔSP _BC | and | ΔSP _AC | − | ΔSP _BC | <0.1 [J / cm ³ ] ^0.5
(2b) | ΔSP _AC | <| ΔSP _BC | and | ΔSP _BC | − | ΔSP _AC | <2.0 [J / cm ³ ] ^0.5
(ΔSP _AC represents the difference in solubility parameter between the A component and the C component, and ΔSP _BC represents the difference in solubility parameter between the B component and the C component.)
It is characterized by satisfying.

  According to the present invention, it is possible to provide a resin composition having both flame retardancy and mechanical strength and a method for producing the same.

It is a mapping figure of the section of the resin composition of Example 1 by EDX measurement. It is a mapping figure of the section of the resin composition of comparative example 1 by EDX measurement.

  The present invention relates to a resin composition having at least an aromatic polycarbonate resin as component A, a styrene resin as component B, and a phosphate ester as component C.

In the present invention, the following general formula (1) is satisfied, and the following (2a) or (2b) is satisfied.
P _B / P _A > 0.70 (1)
(2a) | ΔSP _AC |> | ΔSP _BC | and | ΔSP _AC | − | ΔSP _BC | <0.1 [J / cm ³ ] ^0.5
(2b) | ΔSP _AC | <| ΔSP _BC | and | ΔSP _BC | − | ΔSP _AC | <2.0 [J / cm ³ ] ^0.5

  Details of the formula (1) and (2a) and (2b) will be described later.

  The resin composition of the present invention is a resin composition having at least an aromatic polycarbonate resin, a styrene resin, and a flame retardant phosphate ester. In the resin composition of the present invention, a phase separation structure is formed by an aromatic polycarbonate resin and a styrene resin. In the present invention, the phosphate ester is contained in the phase of the aromatic polycarbonate resin and the phase of the styrene resin, and is not segregated in the phase of the aromatic polycarbonate resin.

Here, segregation means that when a functional substance is contained in a resin composition having a phase separation structure, the concentration of the functional substance in a specific phase is higher than that of other phases. In the present invention, a uniformity ratio represented by the following formula is used as an index indicating whether or not the specific functional substance is segregated in a specific one phase. That is, if the uniformity rate is large, it indicates that the specific functional substance is not segregated into a specific one phase.
[Uniformity ratio] = [Concentration of functional substance in other phase] / [Concentration of functional substance in one specific phase]

  In the present invention, the uniformity ratio is defined on the basis of the concentration of the phosphate ester contained in each of the aromatic polycarbonate resin phase and the styrene resin phase contained in the resin composition. Here, the concentration of the phosphate ester in each phase can be determined by measuring the peak intensity of the phosphorus atom P using EDX (energy dispersive X-ray spectroscopy).

  Here, EDX is a technique for performing elemental analysis and composition analysis by detecting characteristic X-rays generated by electron beam irradiation and performing spectral analysis with energy. In many cases, measurement can be performed by attaching to a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Since X-rays corresponding to the element concentration of the sample are generated in proportion to the amount of irradiated electron beams, quantitative analysis can be performed from the count number and peak intensity where X-rays are generated. In the present invention, the abundance ratio of the phosphate ester contained in each of the A component and the B component in the same sample is quantitatively determined from the peak intensity of the phosphorus atom obtained by the measurement in the spectral mode of the phosphorus atom. Can do. That is, in the present invention, the abundance ratio of the phosphate ester corresponds to the uniformity rate.

  In the present invention, EDX measurement is performed on the cross-sectional phase separation structure in a minute region in the resin composition. And what becomes a measurement parameter | index of this EDX measurement is a phosphorus atom. The intensity of the characteristic X-ray generated when the electron beam irradiated during the measurement hits the phosphorus atom appears in the measurement result as the peak intensity of the phosphorus atom P.

  Here, when measuring and evaluating the phosphate ester (C component) content in each of the phase of the aromatic polycarbonate resin (component A) and the phase of the styrene resin (component B), the component A or B Target a continuous phase of ingredients. Here, the continuous phase means that the phase that can be confirmed in the target region is composed of only the A component or the B component and does not contain other components.

  In addition, since the peak intensity of phosphorus atoms depends on the area of the measurement region and the measurement time, when performing EDX measurement on the A component or the B component, the measurement region is set to a region having the same area and the same measurement. Do it in time. Here, the measurement area | region of EDX measurement can be suitably selected according to the domain size of the phase structure which a resin composition has. For example, an arbitrary planar region with a limited area such as 100 μm × 100 μm, 10 μm × 10 μm, or the like can be selected as the measurement region.

By the way, phosphoric acid ester (C component) is contained in the A component phase and the B component phase at a certain ratio. In this invention, the following general formula (1) is satisfy | filled about the phosphate ester contained in the phase of A component and the phase of B component, respectively.
P _B / P _A > 0.70 (1)

In the formula (1), P _A represents a peak intensity of phosphorus atoms contained in the phase of the A component in the EDX measurement, the P _B, represents a peak intensity of phosphorus atoms contained in the phase of the B component in the EDX measurement.

Here, P _B / P _A is a uniformity ratio. Incidentally, if, equal to the content of the phosphoric acid ester content of the phosphoric acid ester contained in the phase of the A component contained in the phase of the B component, since the P _B = P _A, uniform rate becomes 1 .

In the present invention, the uniformity ratio (P _B / P _A ) exceeds 0.7. Preferably, the uniformity rate is greater than 0.8. That is, it is preferable that the following general formula (1 ′) is satisfied.
P _B / P _A > 0.80 (1 ′)

  In the present invention, the resin composition satisfying the formula (1 ') is particularly excellent in terms of mechanical strength.

  By the way, as a result of intensive studies by the inventors, when a resin composition is prepared by kneading an aromatic polycarbonate resin, a styrene resin, and a phosphate ester by a normal method, the phosphate ester is segregated into the phase of the aromatic polycarbonate resin. I found out that For this reason, the molecular weight of the aromatic polycarbonate is likely to be lowered by hydrolysis of the carbonate group of the aromatic polycarbonate resin by phosphoric acid ester or phosphoric acid generated from the phosphoric acid ester. Moreover, since phosphate ester has a high plastic effect, especially the mechanical strength of the phase of an aromatic polycarbonate resin will be impaired from the initial stage. Thus, it has been found that the mechanical strength of the resin composition itself tends to deteriorate due to segregation of the phosphate ester in the phase of the aromatic polycarbonate resin over the initial period and over time.

Here, when the reason why the phosphoric acid ester segregates in the phase of the aromatic polycarbonate resin was examined, it was found that the reason could be explained by focusing on the relationship between the solubility parameters of each substance. That is, when the difference in solubility parameter between the phosphate ester and the aromatic polycarbonate resin (ΔSP _AC ) is compared with the difference in solubility parameter between the phosphate ester and the styrene resin (ΔSP _BC ), the former is generally Was found to be small. It was also found that the phosphate ester segregates in the aromatic polycarbonate resin phase due to the difference in solubility parameter.

Here, the solubility parameter is a measure of the affinity of two or more substances and is a value expressed by the square root of the molecular agglomeration energy, and is also a parameter called SP value. In the present invention, the SP value is derived using Hansen's method. Here, Hansen's method expresses the energy of one substance as three components of a dispersion energy term (δ _D ), a polarization energy term (δ _P ), and a hydrogen bond energy term (δ _H ). Is expressed as If the difference in SP value between the two types of substances is small (the distance between the two types of substances is short), it indicates that the two types of substances are highly soluble, that is, easy to mix. On the other hand, when the difference in SP value between the two types of substances is large (the distance between the two types of substances is long), the two types of substances have low solubility, that is, they are difficult to mix.

Δ _D , δ _P , δ _{H of} each component (A component, B component, C component) contained in the resin composition of the present invention, and the parameters for each substituent used when calculating by the group contribution method are This is disclosed in Patent Document 1. In addition, “Molecular Modeling Pro” of Chemistry-Software, Dynacomp, Inc. It can also be calculated using commercially available software such as “SLOPE”. In the present invention, the solubility parameter is calculated by using 3rd Edition 3.1.14 of calculation software “HSPiP” with database developed and sold by Hansen Group. At this time, the SP value of each component is calculated based on the following formula (a) [SP value] = (δ _D ² + δ _P ² + δ _H ² ) ^1/2 (a)

The difference in solubility parameter (ΔSP) between the two types of components is defined by the distance in the three-dimensional space, and the value is calculated by the following equation.
ΔSP = {4 (δ _D1 −δ _D2 ) ² + (δ _P1 −δ _P2 ) ² + (δ _H1 −δ _H2 ) ² } ^0.5

In view of the calculation result of the solubility parameter, the inventors decided to study a resin composition in which the phosphate ester is not segregated in the phase of the aromatic polycarbonate resin. Under the present circumstances, in this invention, it examined paying attention to the following points.
(I) To reduce the difference between the SP value difference between the phosphate ester and the aromatic polycarbonate resin (ΔSP _AC ) and the SP value difference between the phosphate ester and the styrene resin (ΔSP _BC ), specifically Specifically, the following (2a) or (2b) is satisfied.
(2a) | ΔSP _AC |> | ΔSP _BC | and | ΔSP _AC | − | ΔSP _BC | <0.1 [J / cm ³ ] ^0.5
(2b) | ΔSP _AC | <| ΔSP _BC | and | ΔSP _BC | − | ΔSP _AC | <2.0 [J / cm ³ ] ^0.5
(ΔSP _AC represents the difference in solubility parameter between the A component and the C component, and ΔSP _BC represents the difference in solubility parameter between the B component and the C component.)
(II) When kneading the components (component A, component B, component C) contained in the resin composition, divide into the following two steps.
(II-1) A step of preparing a kneaded product by kneading the styrene resin as the B component and the phosphate ester as the C component (first kneading step)
(II-2) Step of kneading the kneaded product and the aromatic polycarbonate resin as component A (second kneading step)

  As a result of investigations by the inventors, a resin composition produced under the condition that only at least one of the above (I) and (II) is satisfied in at least a normal kneading method is a phosphate ester into the phase of an aromatic polycarbonate resin. Segregated and the desired effect was not obtained. Therefore, the resin composition of this invention is produced on the conditions which satisfy | fill both said (I) and (II).

The uniformity ratio (P _A / P _B ) of the resin composition produced under the conditions satisfying both of the above (I) and (II) exceeds 0.7. For this reason, in the resin composition of the present invention, segregation of the phosphate ester into the phase of the aromatic polycarbonate resin is reduced. Thereby, since progress of the hydrolysis reaction of aromatic polycarbonate resin can be reduced, deterioration of mechanical strength can be prevented in the whole resin composition. Moreover, the resin composition of this invention contains more phosphoric acid ester which is a flame retardant in the other resin component (styrene resin) whose flame retardance is lower than aromatic polycarbonate resin than before. As a result, the resin composition of the present invention can more effectively improve flame retardancy.

  Next, the kneading method used when producing the resin composition of the present invention will be described. The kneading method used in the present invention is not particularly limited as long as the order of kneading is the above condition (II). For example, the kneading method using mixers, such as a tumbler, a V-type blender, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder, is mentioned. Preferably, it is melt kneading by a twin screw extruder.

  The resin composition obtained by the production method of the present invention and the kneaded product of a styrene resin and a phosphate ester obtained in the production process can be used in the form of a lump, but in the form of pellets from the viewpoint of ease of handling. May be used. When the resin composition or the kneaded product is formed into a pellet, the lump is directly cut into pellets, or after forming a strand, the strand is cut with a pelletizer into pellets. When it is necessary to reduce the influence of external dust or the like when the resin composition or the kneaded product is formed into pellets, it is preferable to clean the atmosphere around the extruder. The shape of the pellets to be produced may be a general shape such as a columnar shape, a prismatic shape, or a spherical shape, but is preferably a columnar shape.

  With the resin composition of the present invention, a molded product can be easily obtained by a known method such as injection molding, extrusion molding, compression molding or rotational molding. In the present invention, it is particularly preferable to form by injection molding.

  When producing a molded product by injection molding, in order to satisfy the characteristics required for the product, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (injecting supercritical fluid) Including molding methods), insert molding, in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, ultra-high speed injection molding, and the like can be used in combination. In molding, either a cold runner method or a hot runner method can be selected.

  Next, the material contained in the resin composition of this invention is demonstrated.

  The aromatic polycarbonate resin (component A) contained in the resin composition of the present invention is a synthetic resin obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the method of reacting the dihydric phenol and the carbonate precursor 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.

  Examples of the dihydric phenol used for the synthesis of the aromatic polycarbonate resin include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxy). Phenyl) propane (common name: 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-hydroxy) Phenyl) pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4′- m-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy) Phenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis ( 4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Of these dihydric phenols, bis (4-hydroxyphenyl) alkanes are preferred, and bisphenol A is particularly preferably used from the viewpoint of impact resistance. These dihydric phenols may be used alone or in a combination of two or more.

  Examples of the styrene resin (component B) contained in the resin composition of the present invention include, for example, a styrene monomer (for example, styrene, vinyltoluene, etc.) or a copolymer; a styrene monomer and a vinyl monomer. Mer [for example, α, β-monoolefinic unsaturation such as (meth) acrylic monomer (for example, (meth) acrylonitrile, (meth) acrylic acid ester, (meth) acrylic acid, etc.), maleic anhydride, etc. A carboxylic acid or an acid anhydride or an ester thereof; and the like; a styrene-based graft copolymer, a styrene-based block copolymer, and the like.

  As the styrene resin, preferably, polystyrene (GPPS), styrene-methyl methacrylate copolymer, styrene- (meth) acrylic acid copolymer, styrene-acrylonitrile copolymer (AS resin), rubber component (polybutadiene, acrylic) Rubber, styrene-butadiene copolymer rubber, EPDM, EVA, etc.) and a graft copolymer obtained by polymerizing a styrene monomer and, if necessary, a copolymerizable monomer (acrylonitrile, methyl methacrylate, etc.) [impact polystyrene (HIPS), ABS resin, MBS resin, etc.], copolymers composed of polystyrene blocks and diene or olefin blocks [for example, styrene-butadiene-styrene (SBS) block copolymers, styrene-isoprene block copolymers Styrene-isoprene-styrene (S S) block copolymer, hydrogenated styrene-butadiene-styrene (SEBS) block copolymer, hydrogenated styrene-isoprene-styrene (SEPS) block copolymer, epoxidized SBS, epoxidized SIS and the like. . One of these styrenic resins may be used alone, or two or more thereof may be mixed and used.

In the present invention, the phosphate ester (C component) contained in the resin composition is not particularly limited, but from the viewpoint of the difference in solubility parameter (ΔSP _AC , ΔSP _BC ) from the aromatic polycarbonate resin or styrene resin, the following formula The compound shown in (3) is preferred.

In the formula (3), R _{11 to} R ₁₄ each represent a phenyl group. The phenyl group may further have a substituent selected from a halogen atom, an alkyl group, and an aralkyl group. R _{11 to} R ₁₄ are preferably a phenyl group which may have a methyl group.

  In Formula (3), n is an integer of 0 to 5. Preferably, it is 1 to 3. Particularly preferred is 1.

  In Formula (3), X is a divalent substituent selected from the substituents shown below.

  Of these divalent substituents, a divalent substituent selected from the substituents shown below is preferable.

  When n is 2 or more, a plurality of Xs may be the same or different.

  In the present invention, the content of the phosphate ester is preferably 1% by weight to 25% by weight, preferably 2% by weight with respect to 100% by weight of the total of A component, B component and C component contained in the resin composition of the present invention. % To 20% by weight is more preferable, and 3% to 15% by weight is particularly preferable.

  Moreover, in the range which exhibits the effect of this invention, a heat stabilizer, antioxidant, a ultraviolet absorber, an antistatic agent, etc. can also be mix | blended with the resin composition of this invention.

  Examples of the heat stabilizer include phosphorus-based heat stabilizers such as phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples thereof include triphenyl phosphite, trisnonylphenyl phosphite. , Tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite , Monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis (4 6-di-t Phosphite compounds such as rt-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tributyl phosphate, trimethyl Phosphate compounds such as phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, Furthermore, tetrakis (2,4-di-tert-butylphenyl) -4,4 ′ is used as another phosphorus heat stabilizer. Biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenedi Examples thereof include phosphonite compounds such as phosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenephosphonite. Among these, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) Phosphite, triphenyl phosphate, trimethyl phosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4- Biphenylene phosphonite is preferred. These heat stabilizers may be used alone or in admixture of two or more. The blending amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, preferably 0.002 parts by weight based on 100 parts by weight of the total of the A component, the B component and the C component contained in the resin composition of the present invention. Part to 0.3 part by weight is more preferable.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-t- Til-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy- Benzylphosphonate-diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-t-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) Undecane etc. are mentioned. Such antioxidant may be used individually by 1 type, and 2 or more types may be mixed and used for it. Further, the blending amount of the antioxidant is preferably 0.0001 to 1 part by weight with respect to 100 parts by weight of the total of A component, B component and C component contained in the resin composition of the present invention, and 0.002 More preferred are parts by weight to 0.3 parts by weight.

  Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers represented by 2,2′-dihydroxy-4-methoxybenzophenone, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5- Chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl ) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and 2- (3 Examples thereof include benzotriazole-based ultraviolet absorbers represented by 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole. It is. Further, hindered amine light stabilizers typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like Can also be used. Such ultraviolet absorbers and light stabilizers may be used alone or in combination of two or more. The blending amount of the ultraviolet absorber and the light stabilizer is preferably 0.0001 to 1 part by weight with respect to 100 parts by weight of the total of A component, B component and C component contained in the resin composition of the present invention, 0.002 to 0.3 parts by weight is more preferable.

  Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like. Such antistatic agents may be used alone or in combination of two or more. The blending amount of the antistatic agent is preferably 0.0001 to 1 part by weight, preferably 0.002 parts by weight with respect to 100 parts by weight of the total of A component, B component and C component contained in the resin composition of the present invention. Part to 0.3 part by weight is more preferable.

  By using the resin composition of this invention, the resin composition which has aromatic polycarbonate resin which made flame retardance and mechanical strength compatible can be provided. The resin composition of the present invention can be used in various applications, for example, vehicle parts such as vehicle interiors, vehicle exteriors, precision equipment (eg, digital cameras, portable information terminals, etc.), office automation OA equipment (eg, personal computers). It can be applied to housing parts of electric / electronic devices such as computers, printers, copiers, facsimiles, etc.).

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. First, evaluation methods for resin compositions prepared in Examples and Comparative Examples will be described.

(1) Uniform rate of phosphate ester The phase separation structure in the micro area | region of the produced resin composition is SEM (S-4800, Hitachi High-Technology Co., Ltd. product) and attached EDX detector (PV7747 / 23ME, EDAX Inc.). ). Moreover, the peak intensity | strength of the phosphorus atom in the phase of aromatic polycarbonate resin (A component) and the phase of a styrene-type resin (B component) was each measured using attached software (Genesis). In the measurement, a continuous phase consisting only of the A component or the B component was targeted, and the area and measurement time of the arbitrarily selected measurement region were the same.

The peak intensity of the phosphorus atom in the phase of the A component was P _A , and the peak intensity of the phosphorus atom in the phase of the B component was P _B.
Uniformity (%) = P _B / P _A

  Incidentally, when calculating the peak intensity of phosphorus atoms, a value corrected by ZAF was adopted. In the measurement, the conductive treatment on the sample surface was performed by carbon coating (SC-701CT, Sanyu Electronics Co., Ltd.). Note that it is not appropriate to perform deposition using platinum instead of carbon coating because the peak derived from phosphorus atoms and the peak derived from platinum overlap.

(2) Impact strength (Charpy impact strength, kJ / m ² )
According to ISO179, using a test piece with a thickness of 4 mm, the impact strength was measured after setting the temperature condition to 23 ° C. Moreover, the acceleration test was done by leaving this test piece to stand for 100 hours under high-humidity conditions (65 ° C., 85% RH). The impact strength was also measured after the acceleration test. And the hydrolysis resistance was evaluated based on the following evaluation criteria from the change in impact strength before and after the acceleration test.
◎: Impact strength decrease rate after acceleration test is less than 8% ○: Impact strength decrease rate after acceleration test is 8% or more and less than 15% △: Impact strength decrease rate after acceleration test is 15% or more and 25% Less than x: The rate of decrease in impact strength after the acceleration test is 25% or more

(3) Flame retardance Based on UL standard 94V, the vertical combustion test was done about the test piece of thickness 1.5mm, and the combustibility rank was evaluated.

[Example 1]
(1) Used material In the present Example, the material shown below was used.
Component A: Polycarbonate A (LEXAN131, manufactured by SABIC Corporation, SP value = 20.3: δ _D = 18.2, δ _P = 5.9, δ _H = 6.9)
B component: polystyrene (polystyrene resin, 680, manufactured by PS Japan, SP value = 19.3: δ _D = 18.5, δ _P = 4.5, δ _H = 2.9)
Component C: condensed phosphate ester (CR-741, manufactured by Daihachi Chemical Co., Ltd., SP value = 22.8: δ _D = 21.5, δ _P = 4.7, δ _H = 6.0)

(2) First kneading step When kneading the materials, a kneading apparatus having the following equipment was used.
Extruder: Co-rotating twin screw extruder HK25D (φ25, L / D = 41) (manufactured by Parker Corporation)
Feeder: Weighing type single-axis feeder KS60 (manufactured by K-Tron)
Nozzle: φ5 × 1 hole Strand cooling: Water cooling

  First, 4090 parts by weight of B component and 910 parts by weight of C component were put into an extruder and kneaded at a preset temperature of 200 ° C. to obtain a strand.

  Subsequently, the obtained strand was cut with a pelletizer to obtain a kneaded product.

(3) Second kneading step Subsequently, 3000 parts by weight of the kneaded product obtained in the first kneading step and 2460 parts by weight of the component A are charged into the extruder and kneaded at a set temperature of 230 ° C. Thus, a resin composition was obtained.

  FIG. 1 is a mapping diagram of a cross section of the resin composition of Example 1 by EDX measurement. The mapping diagram shown in FIG. 1 is based on the phosphorus atom peak. Moreover, the white line segment shown by FIG. 1 is a scale which shows 50 micrometers. Although it was confirmed that the resin composition prepared in this example had a phase separation structure composed of the phase of the A component and the phase of the B component, in the mapping diagram of FIG. In each of the component phases, the brightness of the color was almost the same. This means that the phosphate ester as the C component is contained almost uniformly in the phase of the A component and the phase of the B component.

  It was 0.89 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Example 2]
In Example 1 (2), 3210 parts by weight of B component and 1790 parts by weight of C component were charged into the extruder, and in Example 1 (3), 7710 parts by weight of A component were charged into the extruder. A resin composition was obtained in the same manner as in Example 1. It was 0.84 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Example 3]
In Example 1 (2), 2250 parts by weight of B component and 2750 parts by weight of C component were charged into the extruder, and in Example 1 (3), 13500 parts by weight of A component were charged into the extruder. A resin composition was obtained in the same manner as in Example 1. It was 0.81 when the segregation rate was measured from cross-sectional observation of the obtained resin composition.

[Example 4]
In Example 1 (1), instead of CR-741 as the C component, condensed phosphate ester (TPP, manufactured by Daihachi Chemical Co., Ltd., SP value = 22.4: δ _D = 20.5, δ _P = 6.4, δ _H = 6.3) was used, and a resin composition was obtained in the same manner as in Example 1. It was 0.78 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Example 5]
In Example 1 (1), as a C component, instead of CR-741, condensed phosphate ester (CR-733S, manufactured by Daihachi Chemical Co., Ltd., SP value = 22.5: δ _D = 20.7, A resin composition was obtained in the same manner as in Example 1 except that δ _P = 5.4 and δ _H = 7.0) were used. It was 0.75 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Example 6]
In Example 1 (1), as a C component, instead of CR-741, condensed phosphate ester (PX200, manufactured by Daihachi Chemical Co., Ltd., SP value = 18.8: δ _D = 16.4, δ _P = 6.8, δ _H = 6.1), a resin composition was obtained in the same manner as in Example 1. It was 0.71 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Comparative Example 1]
(1) Used material In this comparative example, the material shown below was used.
Component A: Polycarbonate A (LEXAN131, manufactured by SABIC Corporation, SP value = 20.3: δ _D = 18.2, δ _P = 5.9, δ _H = 6.9, weight average molecular weight 51,000)
B component: Polystyrene (polystyrene resin, 680, manufactured by PS Japan, SP value = 19.3: δ _D = 18.5, δ _P = 4.5, δ _H = 2.9, weight average molecular weight 22, 8000)
Component C: condensed phosphate ester (CR-741, manufactured by Daihachi Chemical Co., Ltd., SP value = 22.8: δ _D = 21.5, δ _P = 4.7, δ _H = 6.0)

(2) Kneading step 2200 parts by weight of component A, 2200 parts by weight of component B, and 490 parts by weight of component C are charged at a time into the extruder provided in the kneading apparatus used in Example 1, and the set temperature is 230. A resin composition was obtained by kneading at 0 ° C.

  FIG. 2 is a mapping diagram of a cross section of the resin composition of Comparative Example 1 by EDX measurement. The mapping diagram shown in FIG. 2 is based on the phosphorus atom peak. Moreover, the white line segment shown by FIG. 2 is a scale which shows 50 micrometers. It was confirmed that the resin composition produced in this comparative example had a phase separation structure composed of the A component phase and the B component phase. Further, in the mapping diagram of FIG. 2, the portion corresponding to the phase of the A component appears as a bright color, and the portion corresponding to the phase of the B component appears as a dark color. This means that the phosphate ester which is the C component is included in the phase of the A component.

  It was 0.67 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Comparative Example 2]
In Comparative Example 1 (1), instead of CR-741 as the C component, condensed phosphate ester (CR-733S, manufactured by Daihachi Chemical Co., Ltd., SP value = 22.5: δ _D = 20.7, A resin composition was obtained in the same manner as in Comparative Example 1 except that δ _P = 5.4, δ _H = 7.0) was used.

  It was 0.62 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Comparative Example 3]
In Comparative Example 1 (1), instead of CR-741 as the C component, condensed phosphate ester (PX-200, manufactured by Daihachi Chemical Co., Ltd., SP value = 18.8: δ _D = 16.4, A resin composition was obtained in the same manner as in Comparative Example 1 except that δ _P = 6.8 and δ _H = 6.1) were used.

  It was 0.59 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Comparative Example 4]
In Comparative Example 1 (1), instead of CR-741 as the C component, condensed phosphate ester (PX-201, manufactured by Daihachi Chemical Co., Ltd., SP value = 19.5: δ _D = 16.4, A resin composition was obtained in the same manner as in Comparative Example 1 except that δ _P = 8.5 and δ _H = 6.1).

  It was 0.57 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

[Comparative Example 5]
In Example 1 (1), as a C component, instead of CR-741, condensed phosphate ester (PX-201, manufactured by Daihachi Chemical Co., Ltd., SP value = 19.5: δ _D = 16.4, A resin composition was obtained in the same manner as in Example 1 except that δ _P = 8.5 and δ _H = 6.1) were used.

  It was 0.61 when the uniformity rate was measured from cross-sectional observation of the obtained resin composition.

  Table 1 below shows physical property data relating to the resin composition, and Table 2 below shows the evaluation results of the resin composition.

  From Tables 1 and 2, the following was found. That is, a step of preparing a kneaded product obtained by kneading the B component (styrene resin) and the C component (phosphate ester) first, and a step of kneading the kneaded product and the A component (aromatic polycarbonate resin) Was found to be necessary. Moreover, it turned out that it is necessary to select A component, B component, and C component so that the difference of SP value may satisfy | fill the relationship of (2a) or (2b). Thereby, since the uniformity rate of the phosphate ester in the resin composition is improved, it is considered that the resin composition of the present invention can achieve both flame retardancy and mechanical strength.

Claims (10)

A resin composition comprising at least an aromatic polycarbonate resin that is an A component, a styrene resin that is a B component, and a phosphate ester that is a C component,
The following general formula (1)
P _B / P _A > 0.70 (1)
(In the formula (1), P _A represents a peak intensity of phosphorus atoms contained in the phase of the A component in the EDX measurement, the P _B, represents a peak intensity of phosphorus atoms contained in the phase of the B component in the EDX measurement .)
And (2a) or (2b) below
(2a) | ΔSP _AC |> | ΔSP _BC | and | ΔSP _AC | − | ΔSP _BC | <0.1 [J / cm ³ ] ^0.5
(2b) | ΔSP _AC | <| ΔSP _BC | and | ΔSP _BC | − | ΔSP _AC | <2.0 [J / cm ³ ] ^0.5
(ΔSP _AC represents the difference in solubility parameter between the A component and the C component, and ΔSP _BC represents the difference in solubility parameter between the B component and the C component.)
The resin composition characterized by satisfy | filling.   2. The resin composition according to claim 1, wherein the resin composition is a kneaded product of the aromatic polycarbonate resin and a kneaded product of the styrene resin and the phosphate ester. The resin composition according to claim 1, wherein the resin composition satisfies the following general formula (1 ′).
P _B / P _A > 0.80 (1 ′) The resin composition according to any one of claims 1 to 3, wherein the phosphate ester is a compound represented by the following general formula (3).

(In Formula (3), R _{11 to} R ₁₄ each represent a phenyl group. The phenyl group may further have a substituent selected from a halogen atom, an alkyl group, and an aralkyl group. Is an integer from 0 to 5. X is a divalent substituent selected from the substituents shown below: When n is 2 or more, a plurality of Xs may be the same. It may be good or different.

The resin composition according to claim 4, wherein n is 1 and R _{11 to} R ₁₄ are each a phenyl group which may have a methyl group.   A molded article obtained by molding the resin composition according to any one of claims 1 to 5.   The molded article according to claim 6, wherein the molded article is formed by injection molding.   A housing part for an electric / electronic device, wherein the resin composition according to any one of claims 1 to 5 is molded.   A vehicle part, which is obtained by molding the resin composition according to any one of claims 1 to 5. A method for producing a resin composition comprising at least an aromatic polycarbonate resin as an A component, a styrene resin as a B component, and a phosphate ester as a C component,
A step of preparing a kneaded product by kneading a styrene resin as the B component and a phosphate ester as the C component;
Kneading the kneaded material and the aromatic polycarbonate resin as component A, and the following (2a) or (2b)
(2a) | ΔSP _AC |> | ΔSP _BC | and | ΔSP _AC | − | ΔSP _BC | <0.1 [J / cm ³ ] ^0.5
(2b) | ΔSP _AC | <| ΔSP _BC | and | ΔSP _BC | − | ΔSP _AC | <2.0 [J / cm ³ ] ^0.5
(ΔSP _AC represents the difference in solubility parameter between the A component and the C component, and ΔSP _BC represents the difference in solubility parameter between the B component and the C component.)
The manufacturing method of the resin composition characterized by satisfy | filling.

Images