JP2021017545A - Fluidity improver, thermoplastic resin composition and molding thereof - Google Patents

Abstract

To provide a fluidity improver capable of improving melt fluidity and drug resistance without damaging transparency and mechanical strength that are characteristic intrinsic to engineering plastic, and a thermoplastic resin composition and a molding that contains the fluidity improver and have excellent fluidity.SOLUTION: Provided are a fluidity improver, a resin composition containing the same and a molding, the fluidity improver including a polymer (A) which contains 60.0 mass% or larger and 99.4 mass% or smaller of an aromatic vinyl monomer unit (a1), 0.1 mass% or larger and 39.5 mass% or smaller of the following (meth)acrylic acid ester monomer unit (a2), 0.5 mass% or larger and 39.9 mass% or smaller of alkyl (meth)acrylate monomer unit (a3), and also contains 60 mass% or larger of styrene monomer unit as the aromatic vinyl monomer unit (a1). The (meth)acrylic acid ester monomer unit (a2):a monomer unit constituted from monomers selected from phenyl (meth)acrylate, 4-t-butyl phenyl (meth)acrylate, bromophenyl (meth)acrylate, dibromophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, monochlorphenyl (meth)acrylate, dichlorophenyl (meth)acrylate, and trichlorophenyl(meth)acrylate.SELECTED DRAWING: None

Description

The present invention is a fluidity improver capable of improving its melt fluidity and chemical resistance without impairing the transparency and mechanical strength inherent in engineering plastics, and a flow containing the fluidity improver. The present invention relates to a resin composition having excellent properties and a molded product.

Among engineering plastics, polycarbonate resin is used in many applications such as mechanical parts, automobile parts, and electrical / electronic parts due to its excellent properties such as mechanical strength and transparency. However, since the polycarbonate resin has a high melt viscosity, it has a drawback of poor fluidity and poor moldability. On the other hand, the characteristics of the polycarbonate resin change depending on the molecular weight, the molecular weight distribution, the amount of the branched component, the structure at the end of the molecular chain, the copolymerization with another monomer having no carbonate group, and the like. A resin more suitable for various uses is used by utilizing such a change in characteristics.

For example, by containing a polycarbonate resin component having an extremely high molecular weight (for example, a component having a viscosity average molecular weight of about 100,000), the melt viscosity and the extensional viscosity in a low shear rate range are increased, and blow molding is performed by utilizing such characteristics. Resin compositions having improved properties and drip prevention properties (flame retardancy based on the properties) have already been proposed.

Almost the same effect can be obtained by introducing a branched structure into the polycarbonate resin, and improvements in blow moldability and flame retardancy have been proposed and used.

Further, in the aromatic polycarbonate resin, the polycarbonate resin in which the aromatic dihydroxy component is a 2,2-bis (4-hydroxy-3-methylphenyl) propane component (hereinafter referred to as “C-PC resin”), or 2 It has been reported that a polycarbonate resin obtained by copolymerizing a 2-bis (4-hydroxy-3-methylphenyl) propane component and a 2,2-bis (4-hydroxyphenyl) propane component has excellent surface hardness. There is.

Further, it is known that crystallization of the polycarbonate resin improves solvent resistance and mechanical strength.

However, such a polycarbonate resin has a drawback that it has a high melt viscosity and its fluidity is insufficient, for example, in injection molding. Such viscosity characteristics constrain the shape of the molded product, processing conditions, hue of the molded product, and the like in extrusion molding and injection molding.

As a method for improving melt fluidity during molding without impairing the excellent properties of the polycarbonate resin, a copolymer obtained by polymerizing an aromatic vinyl monomer and a phenyl (meth) acrylate monomer is used. , A method of blending with a polycarbonate resin has been proposed (Patent Document 1).
In this method, although the melt fluidity during molding is improved, the mechanical strength such as impact resistance, which is a characteristic of the polycarbonate resin, is impaired. Further, the transparency and chemical resistance of the obtained molded product are not sufficient, and further improvement is required. In addition, it is transparent to 2,2-bis (4-hydroxyphenyl) propane, that is, a polycarbonate resin using bisphenol A (hereinafter referred to as "A-PC resin"), which is widely used at present. Although it is secured, a polycarbonate resin other than the A-PC resin, such as the above-mentioned C-PC resin, a polycarbonate resin having a branched structure, or a polycarbonate resin having another copolymerization component, or an A-PC resin and another type of polycarbonate resin When blended in the alloy of, the transparency of the molded product may be impaired.

International Publication No. 2005/03819

In the above-mentioned conventional method, the balance between the transparency of the molded product, the mechanical strength, the chemical resistance and the melt fluidity of the engineering plastic is still insufficient.

An object of the present invention is to include a fluidity improver capable of improving the melt fluidity and chemical resistance thereof without impairing the transparency and mechanical strength inherent in engineering plastics, and the fluidity improver. It is an object of the present invention to provide a thermoplastic resin composition and a molded product having excellent fluidity.

As a result of diligent studies, the present inventors have made a weight containing an aromatic vinyl monomer unit (a1), a (meth) acrylic acid ester monomer unit (a2) and an alkyl (meth) acrylate monomer unit (a3). A polymer (A) which is a coalescence (A) and contains 60% by mass or more of a styrene monomer unit as an aromatic vinyl monomer unit (a1) is used as a fluidity improver, and the fluidity improver is used. It has been found that by melt-kneading with an engineering plastic, it is possible to improve the fluidity and chemical resistance during the molding process without impairing the characteristics of the engineering plastic.

That is, the above object is achieved by the following inventions [1] to [20].
[1] Aromatic vinyl monomer unit (a1) 60.0% by mass or more and 99.4% by mass or less,
The following (meth) acrylic acid ester monomer unit (a2) 0.1% by mass or more and 39.5% by mass or less,
A polymer (A) containing 0.5% by mass or more and 39.9% by mass or less of an alkyl (meth) acrylate monomer unit (a3).
A fluidity improver containing a polymer (A) containing 60% by mass or more of a styrene monomer unit as the aromatic vinyl monomer unit (a1).
(Meta) acrylic acid ester monomer unit (a2): phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6 -A monomer unit composed of a monomer selected from tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, and trichlorophenyl (meth) acrylate.
[2] The fluidity improver according to [1], wherein the polymer (A) has a weight average molecular weight of 5,000 or more and 150,000 or less.
[3] The alkyl (meth) acrylate monomer unit (a3) is a monomer unit having a structure in which (meth) acrylic acid and a linear saturated fatty acid are ester-bonded, according to [1] or [2]. The fluidity improver according to any one.
[4] The fluidity improver according to any one of [1] to [3], wherein the alkyl (meth) acrylate monomer unit (a3) is methyl methacrylate.
[5] The fluidity improver according to any one of [1] to [4], wherein the polymer (A) has a refractive index of 1.550 or more and 1.585 or less.
[6] A resin composition obtained by blending 90 parts by mass of a fluidity improver with 90 parts by mass of a polycarbonate resin having a refractive index of 1.560 or more and 1.585 or less is injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. A flat plate having a thickness of 2 mm and a thickness of 5 cm × 10 cm was injected at a haze of 7.0% or less, a brittle fracture rate of 33% or less, a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure of 50 MPa. A fluidity improver in which the spiral flow length of a molded product having a thickness of 2 mm and a width of 15 mm satisfies the relationship of the following formula (1-1).
SPL ≧ 1.80 × Lpc ・ ・ ・ (1-1)
(In the formula, SPL is the spiral flow length of the polycarbonate resin-based composition, and Lpc is the spiral flow length of the polycarbonate resin. A resin composition obtained by blending 90 parts by mass of the polycarbonate resin with 10 parts by mass of the fluidity improver was used. The SPL was measured.)
[7] A thermoplastic resin composition obtained by blending the engineering plastic (B) with the fluidity improver according to any one of [1] to [6].
[8] The thermoplastic resin composition according to [8], wherein 100 parts by mass of the engineering plastic (B) is mixed with 0.1 part by mass or more and 30 parts by mass or less of the fluidity improver.
[9] The thermoplastic resin composition according to [7] or [8], wherein the engineering plastic (B) is a polyester polymer.
[10] The thermoplastic resin composition according to [9], wherein the polyester polymer has a refractive index of 1.540 or more and 1.595 or less.
[11] The thermoplastic resin composition according to any one of [9] and [10], wherein the polyester-based polymer is a polycarbonate resin.
[12] Light diffusion with 40.0 parts by mass or more and 99.8% by mass or less of the polycarbonate resin and 0.1 parts by mass or more and 30% by mass or less of the fluidity improver according to any one of [1] to [6]. A thermoplastic resin composition containing 0.1 part by mass or more and 30% by mass or less of the agent.
[13] A molded product obtained by injection molding the thermoplastic resin composition according to any one of [7] to [12].
[14] An automobile member obtained by injection molding the thermoplastic resin composition according to any one of [7] to [12].
[15] A hard-coated product in which a hard-coat layer is provided on the surface of the molded product according to [13].
[16] A display front plate using the molded product according to [13].
[17] A glazing material using the molded product according to [13].
[18] A light diffusing plate obtained by molding the thermoplastic resin composition according to any one of [7] to [12].
[19] An optical disk substrate obtained by molding the thermoplastic resin composition according to any one of [7] to [12].
[20] A light guide plate obtained by molding the thermoplastic resin composition according to any one of [7] to [12].

When the fluidity improver of the present invention is melt-molded in an engineering plastic, the fluidity improver causes phase separation in the engineering plastic, and the dispersed phase is greatly stretched in the flow direction to form a layered structure. As a result, the fluidity during melt molding can be significantly improved. On the other hand, the fluidity improver of the present invention copolymerizes two or more (meth) acrylic acid esters having different compatibility with a monomer that is incompatible with the engineering plastic, and is a fluidity improver of the engineering plastic. Since the compatibility is controlled, it is easily dispersed in the engineering plastic during melt molding, and is easily stretched in the flow direction. Further, in the operating temperature range of the molded product, the transition is in the direction of free energy compatibility, so that the impact resistance is not significantly reduced. For these reasons, the fluidity improver of the present invention can impart unprecedented remarkable melt fluidity and chemical resistance without impairing mechanical strength such as transparency and impact resistance of engineering plastics. ..

It is a schematic diagram which shows the part of the molded article which gives an impact when the surface impact test is performed on the molded article of this invention. It is a figure which shows the crack which occurs when the surface impact test is performed on the molded article of this invention. It is a figure which shows the example which does not generate the crack when the surface impact test is performed on the molded article of this invention.

The polymer (A) of the present invention contains an aromatic vinyl monomer unit (a1), a (meth) acrylic acid ester monomer unit (a2), and an alkyl (meth) acrylate monomer unit (a3). It can be obtained by polymerizing the monomer mixture (a).

The polymer (A) of the present invention is a fluidity improver that exhibits excellent fluidity and chemical resistance improving effect by containing a predetermined amount of the aromatic vinyl monomer unit (a1).
Examples of the aromatic vinyl monomer unit (a1) that can be used in the present invention include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-methoxystyrene, o-methoxystyrene, and the like. Examples thereof include 2,4-dimethylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinylnaphthalene, vinylanthracene and the like, and these can be used alone or in combination of two or more. Among these, styrene, α-methylstyrene, and pt-butylstyrene are preferable, and the fluidity is remarkably increased, because the glass transition temperature of the polymer (A) becomes high and the transparency at a high temperature becomes good. Styrene is particularly preferable in terms of improvement.
The content of the aromatic vinyl monomer unit (a1) in the monomer mixture (a) is 60.0% by mass or more and 99.4% by mass or less. When the content of the aromatic vinyl monomer unit (a1) is 60.0% by mass or more, it becomes incompatible with the engineering plastic, and the fluidity during the molding process can be improved. When it is 99.4% by mass or less, the compatibility with the engineering plastic is not insufficient, the phase separation size is not too large, and the resin composition is a mixture of the fluidity improver and the engineering plastic. It is preferable because the impact resistance of the molded product obtained by molding the product is not impaired.
Considering these balances, the content of the aromatic vinyl monomer unit (a1) in the monomer mixture (a) is preferably 98% by mass or less, more preferably 96% by mass or less, and further preferably. Is 94.9% by mass or less, and most preferably 90% by mass or less.
The content of the aromatic vinyl monomer unit (a1) is preferably 60.0% by mass or more, more preferably 65.0% by mass or more, still more preferably 74.0% by mass or more. Most preferably, it is 80.0% by mass or more.

The content of the styrene monomer unit as the aromatic vinyl monomer unit (a1) in the monomer mixture (a) is 60.0% by mass or more and 99.4% by mass or less. When the content of the styrene monomer is 60% by mass or more, a remarkable effect of improving fluidity during molding can be obtained. The content of the styrene monomer unit is preferably 65.0% by mass or more, more preferably 68.0% by mass or more, and most preferably 69.0% by mass or more.

The polymer (A) of the present invention contains the (meth) acrylic acid ester monomer unit (a2) exemplified below. When the polymer (A) contains a predetermined amount of the (meth) acrylic acid ester monomer unit (a2), it becomes a fluidity improver that exhibits an effect of improving compatibility.
Examples of the (meth) acrylic acid ester monomer unit (a2) include phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4. , 6-Tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate and the like, and these can be used alone or in combination of two or more. Of these, phenyl (meth) acrylate is particularly preferable.

The content of the (meth) acrylic acid ester monomer unit (a2) in the monomer mixture (a) needs to be 0.1% by mass or more and 39.5% by mass or less.
When the content of the (meth) acrylic acid ester monomer unit (a2) is 0.1% by mass or more, the compatibility with engineering plastics is sufficient and the phase separation size does not become too large. A molded product obtained by molding a resin composition containing a fluidity improver and an engineering plastic does not impair mechanical properties such as impact resistance.
Further, when the content of the (meth) acrylic acid ester monomer unit (a2) is 39.5% by mass or less, the compatibility with engineering plastics is appropriate, so that the phase separation behavior is sufficient. It can be formed, and the effect of improving fluidity can be easily obtained.
Considering these balances, the content of the (meth) acrylic acid ester monomer unit (a2) is preferably 35.0% by mass or less, more preferably 30.0% by mass or less, and further preferably 25. It is 0% by mass or less, most preferably 14.5% by mass or less.
The content is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.8% by mass or more.

The polymer (A) of the present invention contains an alkyl (meth) acrylate monomer unit (a3). When the polymer (A) contains a predetermined amount of the (meth) acrylic acid ester monomer unit (a3), the balance of compatibility with engineering plastics is excellent, and thus the effect of improving fluidity is impaired. It is a fluidity improver that has both excellent impact resistance and chemical resistance.
Examples of the alkyl (meth) aclate monomer unit (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, and ( N-Butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2 (meth) acrylate -Ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate and the like can be mentioned. One of these monomers may be used alone, or two or more of these monomers may be used in combination.
Among these, a monomer unit having a structure in which a linear saturated fatty acid is ester-bonded to (meth) acrylic acid is preferable. Further, among them, since the refractive index of the polymer (A) becomes close to that of the polycarbonate resin and the transparency is improved, it is preferable to use a monomer unit having a refractive index of 1.450 or more and 1.580 or less. Further, in order to make it difficult to reduce the heat resistance which is a characteristic of engineering plastics, a monomer having a glass transition temperature of 0 ° C. or higher is preferable. Among these, methyl methacrylate is particularly preferable because it has an excellent balance of compatibility with engineering plastics. In the present application, (meth) acrylic means acrylic or methacrylic.

The content of the alkyl (meth) acrylate monomer unit (a3) in the monomer mixture (a) is 0.5% by mass or more and 39.9% by mass or less. When the content of the alkyl (meth) acrylate monomer unit (a3) in the monomer mixture (a) is 0.5% by mass or more, the impact resistance and transparency of the molded product are not impaired. Further, chemical resistance is improved. It is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. When the content of the alkyl (meth) acrylate monomer unit (a3) in the monomer mixture (a) is 39.9% by mass or less, the polymer (A) is incompatible with the engineering plastic. Therefore, the fluidity during molding is improved and the chemical resistance is not lowered. It is preferably 34.9% by mass or less, more preferably 30.0% by mass or less, and further preferably 25.0% by mass or less. When these conditions are satisfied, the balance of compatibility with engineering plastics is excellent, and the fluidity and impact resistance of the molded product are improved.

The monomer mixture (a) is an aromatic vinyl monomer unit (a1), and the content of the styrene monomer unit is 60.0% by mass or more and 92.0% by mass or less, and the alkyl (meth) acrylate unit is simple. When the content of the body unit (a3) is 4% by mass or more and 20% by mass or less at the same time, the chemical resistance is improved. Further, the content of the styrene monomer unit is 70.0% by mass or more and 90.0% by mass or less, and the content of the alkyl (meth) acrylate monomer unit (a3) is 6% by mass or more and 18% by mass or less at the same time. It is preferable to satisfy, and the content of the styrene monomer unit is 80.0% by mass or more and 88.0% by mass or less, and the content of the alkyl (meth) acrylate monomer unit (a3) is 7% by mass or more and 15% by mass. It is particularly preferable to satisfy the following at the same time.

The monomer mixture (a) contains 0.5% by mass or more of the (meth) acrylic acid ester monomer unit (a2) and 4% by mass of the alkyl (meth) acrylate monomer unit (a3). Impact resistance is improved when% or more is satisfied at the same time. Further, the content of the (meth) acrylic acid ester monomer unit (a2) is 0.7% by mass or more, and the content of the alkyl (meth) acrylate monomer unit (a3) is 6% by mass or more at the same time. It is preferable that the content of the (meth) acrylic acid ester monomer unit (a2) is 3% by mass or more and the content of the alkyl (meth) acrylate monomer unit (a3) is 7% by mass or more at the same time. Especially preferable.

The monomer mixture (a) may contain other monomer units (a4) that can be copolymerized with the monomer units (a1) to (a3), if necessary.
Examples of the monomer unit (a4) include vinyl benzoate; vinyl acetate; maleic anhydride; maleimide compounds such as N-phenylmaleimide and cyclohexylmaleimide; and ethylenically unsaturated monomers having a piperidyl group. One of these may be used alone, or two or more thereof may be used in combination.

The content of the monomer (a4) in the monomer mixture (a) (100% by mass) is 0% by mass or more and 40% by mass or less. When the content of the mass monomer (a4) in the monomer mixture (a) (100% by mass) is 40% by mass or less, the fluidity during the molding process is improved and the impact resistance of the molded product is improved. Is not impaired.

Examples of the polymerization method for obtaining the polymer (A) of the present invention include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a massive polymerization method, but the recovery method is easy. The turbid polymerization method and the emulsion polymerization method are preferable. However, in the case of the emulsified polymerization method, the salts remaining in the polymer (A) may cause decomposition of the aromatic polycarbonate resin, so the polymer is recovered by acid coagulation or the like using a carboxylic acid emulsifier. Alternatively, it is preferable to use a nonionic anionic emulsifier such as a phosphoric acid ester for salt coagulation with calcium acetate or the like.
Examples of the polymerization initiator include organic peroxides, persulfates, organic peroxides or redox-based initiators composed of a combination of persulfates and a reducing agent, and azo compounds.

The weight average molecular weight of the polymer (A) of the present invention is 5,000 or more, preferably 10,000 or more, more preferably 15,000 or more, further preferably 30,000 or more, and particularly preferably 40,000 or more. .. The weight average molecular weight of the polymer (A) is 200,000 or less, preferably 170,000 or less, more preferably 150,000 or less, further preferably 120,000 or less, and particularly preferably 100,000 or less.

When the weight average molecular weight of the polymer (A) of the present invention is 5,000 or more, there are relatively few low molecular weight substances, and the heat resistance of the molded product is not impaired. In addition, the appearance of the molded product does not deteriorate due to smoke generated during melt-kneading. When a molded product having good transparency at high temperature (a molded product having a small temperature dependence of transparency) is required, the weight average molecular weight of the polymer should be high.
When the weight average molecular weight of the polymer (A) is 200,000 or less, the melt viscosity of the polycarbonate resin composition does not increase, and a sufficient effect of improving melt fluidity can be obtained.

The refractive index of the polymer (A) of the present invention is 1.550 or more and 1.585 or less. The refractive index is preferably 1.560 or more and 1.585 or less, and more preferably 1.570 or more and 1.580 or less.

The fluidity improver containing the polymer (A) of the present invention is incompatible with engineering plastics in order to significantly improve the fluidity, while the dispersed phase is sufficiently stretched in the flow direction. It is necessary to have compatibility as well.
That is, the domain of the polymer (A) dispersed in the matrix of the engineering plastic can be confirmed as a phase separation in the form of being stretched into fibers in the flow direction. The shape of the domain of the polymer (A) dispersed in the matrix of the engineering plastic is confirmed by observing the phase structure of the molded piece with a transmission electron microscope. Since a high shearing force is applied near the wall surface of the mold during injection molding, the domain of the polymer (A) tends to have a shape stretched in the flow direction near the surface layer of the molded piece.

[Engineering plastic]
The engineering plastic (B) used in the thermoplastic resin composition of the present invention is not particularly limited as long as it is a conventionally known various thermoplastic engineering plastics, such as polyphenylene ether, polycarbonate, polyethylene terephthalate, and polybutylene terephthalate. Nylon-based polymers such as polyester-based polymers, syndiotactic polystyrene, 6-nylon, 6,6-nylon, polyarylate, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, polyethersulfone, polyamideimide, Examples thereof include polyetherimide and polyacetal.
Further, special styrene resins such as heat-resistant ABS and heat-resistant acrylic resins, which are highly heat-resistant and require melt fluidity, can also be exemplified as engineering plastics in the present invention. Among these, polyphenylene ether, polycarbonate resin and the like are preferable, and aromatic polycarbonate resin is more preferable, in consideration of the effect of improving fluidity. In addition, these can be used alone or in combination of two or more.
Examples of the aromatic polycarbonate resin include those having a structural unit represented by the following general formula (I).

(In the general formula (I), R1 and R2 independently represent an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and a and b each independently represent an integer of 0 to 4. X is a single bond. An alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkoxylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, -CO-, or

R1 and R2 each independently represent a hydrogen atom or a methyl group, and Z may be bonded to a carbon atom (C) and have a substituent. An alicyclic type having 6 to 12 carbon atoms. Indicates a group that forms a hydrocarbon. )
The aromatic polycarbonate resin having a structural unit represented by the following general formula (I) includes an aromatic polycarbonate resin polycarbonate in which the aromatic dihydroxy component is a 2,2-bis (4-hydroxy-3-methylphenyl) propane component. Resin (A-PC resin), or polycarbonate resin (C-PC resin) in which the aromatic dihydroxy component is 2,2-bis (4-hydroxy-3-methylphenyl) propane component, or 2,2-bis (4) Examples thereof include a polycarbonate resin obtained by copolymerizing a −hydroxy-3-methylphenyl) propane component and a 2,2-bis (4-hydroxyphenyl) propane component. These can be used alone or in combination of two or more. It is also possible to mix the crystallized polycarbonate resin.

Further, the engineering plastic (B) may have a structural unit represented by the general formula (I) and another structural unit. For example, a polycarbonate-polyorganosiloxane copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) can be mentioned. Further, the polycarbonate-polyorganosiloxane copolymer may be used in combination with an aromatic polycarbonate resin.

(In the general formula (II), R3 to R6 independently form a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, respectively. Indicated, Y indicates an organic residue containing an aliphatic or aromatic, and n indicates an average number of repetitions.)

The refractive index of the engineering plastic (B) is preferably 1.540 or more and 1.595 or less for the purpose of reducing the difference in the refractive index from the polymer (A). It is more preferably 1.550 or more and 1.590 or less, and further preferably 1.570 or more and 1.590 or less.

The molecular weight of the engineering plastic (B) may be appropriately determined as desired, and is not particularly limited in the present invention.
The engineering plastic (B) can be produced by various conventionally known methods. For example, in the case of producing 4,4'-dihydroxydiphenyl-2,2-propane-based polycarbonate, 4,4'-dihydroxydiphenyl-2,2-propane is used as a raw material in the presence of an alkaline aqueous solution and a solvent. Examples include a method in which phosgene is blown into the reaction, and a method in which 4,4'-dihydroxydiphenyl-2,2-propane and a carbonate diester are transesterified in the presence of a catalyst.

Further, the engineering plastic (B) has a range that does not impair the excellent heat resistance, impact resistance, flame retardancy, etc. inherent in the engineering plastic, specifically, 50 parts by mass or less with respect to 100 parts by mass of the engineering plastic. It is also possible to use engineering plastic polymer alloys containing thermoplastic resins other than engineering plastics such as ABS, HIPS, PS, PAS and other styrene resins, acrylic resins, polyolefin resins and elastomers. is there.

[Liquidity improver + engineering plastic (B)]
The blending ratio of the fluidity improver and the engineering plastic (B) may be appropriately determined according to the desired physical properties and the like, and is not particularly limited in the present invention, but the performance (heat resistance, impact strength, etc.) of the engineering plastic can be determined. In order to obtain an effective fluidity improving effect without reducing the fluidity, it is preferable to add 0.1 parts by mass or more and 30 parts by mass or less of the fluidity improver to 100 parts by mass of the engineering plastic. When the blending amount of the fluidity improver is 0.1 parts by mass or more, a sufficient improvement effect can be obtained. Further, when the blending amount of the fluidity improver is 30 parts by mass or less, there is no risk of impairing the excellent mechanical properties of the engineering plastic. The amount of the fluidity improver to be blended is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 8 parts by mass or more. The blending amount is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and most preferably 15 parts by mass or less.

The difference in refractive index between the fluidity improver and the engineering plastic (B) is preferably 0.05 or less. When the difference in refractive index is small, the transparency of the molded product is maintained. The difference in refractive index between the fluidity improver and the engineering plastic (B) is more preferably 0.02 or less, and particularly preferably 0.01 or less.

Further, the thermoplastic resin composition of the present invention may be blended with additives such as known stabilizers, strengthening agents, inorganic fillers, impact resistance modifiers, flame retardants, and fluoroolefins, if necessary. Good. For example, talc, mica, calcium carbonate, glass fiber, carbon fiber, potassium titanate fiber and the like can be contained in order to improve the strength, rigidity and flame retardancy of the molded product. Further, another thermoplastic resin composition such as polyethylene terephthalate for improving chemical resistance and the like, and a rubber-like elastic body having a core-shell two-layer structure for improving impact resistance may be blended.

The compounding of the engineering plastic (B) and the fluidity improver may be a mixture of powders, or may be obtained by heating and kneading the engineering plastic (B) and the fluidity improver. ..
Examples of such a blending method include a method using a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, two rolls, a kneader, a lavender, and the like. Further, a master batch in which the fluidity improver and the engineering plastic (B) are mixed is prepared in advance so that the ratio of the fluidity improver becomes large, and then the master batch and the engineering plastic (B) are mixed again. The desired composition can also be obtained.

The molded product of the present invention can be obtained by injection molding the above-mentioned thermoplastic resin composition. In particular, since it is possible to improve the balance of fluidity / chemical resistance / mechanical strength that cannot be achieved by conventional fluidity improvers, automobile exteriors such as headlamps that require chemical resistance and mechanical strength. It is extremely effective for members, automobile interior members such as display front plates, large and thin injection molded products such as OA equipment and electrical / electronic equipment.
The method of injection molding is not particularly limited, and a known method can be used.

The thermoplastic resin composition of the present invention preferably contains a polycarbonate resin and a fluidity improver, and the content thereof may be appropriately determined according to desired physical properties and the like, and is not particularly limited in the present invention. However, in order to obtain an effective moldability improving effect and a chemical resistance improving effect without deteriorating the performance (heat resistance, impact strength, etc.) of the thermoplastic resin composition, the polycarbonate resin is 80% by mass or more 99. It is preferably 5% by mass or less, and the fluidity improver is preferably 0.5% by mass or more and 20% by mass or less. When the content of the fluidity improver is 0.5% by mass or more, a sufficient improvement effect can be obtained. Further, when the content of the fluidity improver is 20% by mass or less, there is no risk of impairing the excellent mechanical properties of the polycarbonate resin. The lower limit of the content of the fluidity improver is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. Further, the upper limit of the preferable content of the fluidity improver is 15% by mass or less, and more preferably 10% by mass or less.

Further, the fluidity improver of the present invention is a resin composition obtained by blending 10 parts by mass of a fluidity improver with 90 parts by mass of a polycarbonate resin having a refractive index of 1.560 or more and 1.585 or less, and has a haze of 7. It is 0% or less. The haze is preferably 5.0% or less, more preferably 3.0% or less, and particularly preferably 2.0% or less.

Further, in the fluidity improver of the present invention, a resin composition obtained by blending a fluidity improver with a polycarbonate resin having a refractive index of 1.560 or more and 1.585 or less satisfies the relationship of the following formula (1-1). To do.
SPL ≧ 1.80 × Lpc ・ ・ ・ (1-1)
(In the formula, SPL is the spiral flow length of the thermoplastic resin composition, and Lpc is the spiral flow length of the thermoplastic resin. A resin composition obtained by blending 90 parts by mass of a polycarbonate resin with 10 parts by mass of a fluidity improver. The SPL was measured using.)
The SPL preferably satisfies SPL ≧ 1.90 × Lpc, and more preferably SPL ≧ 2.00 × Lpc.

Further, in the present invention, the thermoplastic resin composition is, if necessary, for example, triphenylphosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, diphenylhydrodigenphosphite, irganox 1076. Stabilizers such as [stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-Hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2-hydroxy-4-octoxybenzophenone, etc. The above-mentioned weather resistant agent, antistatic agent, mold release agent, dyeing pigment and the like may be added as long as the transparency of the alloy and the effect of the present invention are not impaired.

The thermoplastic resin composition of the present invention may contain a light diffusing agent.
Examples of the light diffusing agent include inorganic fine particles such as glass filler, calcium carbonate, barium sulfate, silica, talc, mica, wallastonite, and titanium oxide; obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Examples thereof include amorphous heat-resistant polymer particles such as organic crosslinked particles, silicone-based crosslinked particles, and polyether sulfone particles, epoxy resin particles, urethane resin particles, melamine resin particles, benzoguanamine resin particles, and polymer fine particles such as phenol resin particles. ..

As the light diffusing agent, polymer fine particles are preferable to inorganic fine particles. By using the polymer fine particles, it is possible to achieve both light diffusivity and total light transmittance at a higher level.
The refractive index of the polymer fine particles is usually 1.33 or more and 1.7 or less. When the refractive index of the polymer fine particles is within this range, a sufficient light diffusing function is exhibited in the state of being blended with the resin composition.

The average particle size of the light diffusing agent is preferably 0.01 μm or more and 50 μm or less, more preferably 0.1 μm or more and 10 μm or less, and further preferably 0.1 μm or more and 8 μm or less. The average particle size is represented by 50% (D50) of the integrated distribution of the particle size obtained by the laser light scattering method.
The light diffusing agent preferably has a narrow particle size distribution, and more preferably has a distribution in which fine particles in the range of an average particle size of ± 2 μm account for 70% by mass or more of the whole.

The absolute value of the difference between the refractive index of the light diffusing agent and the refractive index of the thermoplastic resin is preferably 0.02 or more and 0.2 or less. When the difference in refractive index is within this range, it is possible to achieve both light diffusivity and total light transmittance at a high level.

When the light diffusing agent is contained, the polycarbonate resin is 40.0% by mass or more and 99.8% by mass or less, the fluidity improver of the present invention is 0.1% by mass or more and 30% by mass or less, and the light diffusing agent is 0.1% by mass. It is preferable to contain% or more and 30% by mass or less. When the content of the light diffusing agent in the thermoplastic resin composition (100% by mass) of the present invention is 0.1% by mass or more and 30% by mass or less, a sufficient light diffusing function is exhibited.

The thermoplastic resin composition of the present invention contains, if necessary, known stabilizers, coloring materials, antistatic agents, hydrolysis improvers, heat ray absorbers, mold release agents, strengthening agents, and impact resistance modifiers. , Additives such as flame retardants may be blended. As the stabilizer, for example, a phosphorus-based stabilizer, a hindered phenol-based stabilizer, an ultraviolet absorber, a light stabilizer and the like can be contained in order to stabilize the molecular weight and hue during molding. As the coloring material, for example, a bluing agent, a fluorescent dye, or the like can be contained. Examples of the antistatic agent include organic sulfates such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Sulfonic acid (earth) metal salts can be mentioned. Examples of the mold release agent include fatty acid esters, polyolefin waxes, silicone compounds, fluorine compounds, paraffin waxes, beeswax and the like, and by containing them, mold release defects can be prevented. In order to improve the strength, rigidity and flame retardancy of the molded product, glass fiber, carbon fiber, potassium titanate fiber and the like can be contained. Further, other engineering plastic compositions such as polyethylene terephthalate may be blended to improve chemical resistance, and a rubber-like elastic body or the like may be blended to improve impact resistance.

Further, various dyes and pigments, inorganic fillers, antibacterial agents, photocatalytic antifouling agents and the like can be blended in the thermoplastic resin composition of the present invention.

The thermoplastic resin composition of the present invention uses, for example, a Henschel mixer, a Banbury mixer, a simple screw extruder, a twin screw extruder, two rolls, a kneader, and a brabender, and uses a fluidity improver and an aromatic polycarbonate resin. , And if necessary, a light diffusing agent or the like is blended and kneaded, and the mixture is prepared by a known method.

The molded product of the present invention can be obtained by molding the thermoplastic resin composition of the present invention by a known method such as an injection molding method, an extrusion molding method, a compression molding method, a blow molding method, or a casting molding method. The thermoplastic resin composition of the present invention is particularly useful as a raw material for injection molded products.

The molded product of the present invention includes a hard coat product, a glazing material, a light diffusing plate, an optical disk substrate, a light guide plate, a building, a building material, an agricultural material, a marine material, an electric / electronic device, a machine, a medical material, a vehicle member, and miscellaneous goods. It can be used for a wide range of purposes such as.

Next, the hard-coated product of the present invention will be described.
The hard-coated product of the present invention is obtained by providing a hard-coated layer on the surface of a molded product obtained by molding the thermoplastic resin composition of the present application.
The hard coat layer is formed by applying a hard coat agent to the surface of a molded product obtained by molding a thermoplastic resin composition and curing it.
Examples of the hard coating agent include silicone resin-based hard coating agents and other organic resin-based hard coating agents.

The silicone resin-based hard coat agent forms a cured resin layer having a siloxane bond. Examples of the silicone resin-based hard coat agent include a partially hydrolyzed condensate of a compound containing a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound, etc.) as a main component, and a compound corresponding to a trifunctional siloxane unit and a tetrafunctional compound. Examples thereof include a partially hydrolyzed condensate of a compound containing a compound corresponding to a siloxane unit (tetraalkoxysilane compound, etc.), and a partially hydrolyzed condensate obtained by filling these partially hydrolyzed condensates with fine metal oxide particles such as colloidal silica. ..

Examples of other organic resin-based hard coating agents include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Among these, monofunctionals such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, organic-inorganic hybrid (meth) acrylate obtained by condensing colloidal silica and (meth) acryloyl alkoxysilane, etc. Meta) acrylates or polyfunctional (meth) acrylates; monomers or oligomers such as organic-inorganic hybrid vinyl compounds are preferred.

The hard coating agent can be applied to a molded product from known coating methods such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, and a roller coating method, depending on the shape of the molded product. The coating method can be appropriately selected. Of these, the dip coating method, the flow coating method, and the spray coating method are preferable in terms of easy handling of complicated shapes and easy film thickness control.
Curing of the hard coating agent can be performed by volatilizing the organic solvent when an organic solvent is used, and then irradiating and / or heating the organic solvent with active energy rays such as ultraviolet rays and electron beams.

The hard-coated product described above can improve its melt fluidity and chemical resistance without impairing the transparency and mechanical strength that are the original characteristics of engineering plastics.
Since the hard-coated product of the present invention is excellent in transparency, heat resistance, impact resistance, and appearance, various electronic / electrical equipment, OA equipment, vehicle parts, mechanical parts, agricultural materials, fishery materials, transport containers, and packaging containers. , Playing equipment, miscellaneous goods, etc. In addition, because it is possible to increase the size, reduce the weight and thickness, complicate the shape, and improve the performance, front door window (windshield), rear door window, quarter window, back window, back door window, sunroof, roof panel, etc. Suitable for glazing materials for construction and vehicles such as window materials.

Next, the light diffusing plate of the present invention will be described.
The light diffusing plate of the present invention is usually produced from the above-mentioned resin composition by a known injection molding method.
The thermoplastic resin composition of the present invention is particularly suitable for producing a large and thin light diffusing plate (particularly a light diffusing plate for an image display device). According to the polycarbonate resin composition of the present invention, the light diffusing plate obtained surface area of 500 cm ² or more 50,000 cm ² or less. The surface area of the light diffusing plate is preferably 1,000 cm ² or more and 25,000 cm ² or less, and the thickness is preferably 0.3 mm or more and 3 mm or less. As described above, according to the polycarbonate resin composition of the present invention, it is possible to produce a light diffusing plate which is large in size, has high dimensional stability, and is thin (lightweight).

The light diffusing plate may be a single-layer plate having a surface shape such as a Fresnel lens shape or a cylindrical lens shape, and another material having a surface shape such as a Fresnel lens shape or a cylindrical lens shape is laminated on the light diffusing plate. It may be a laminated plate.

The light diffusing plate described above has high melt fluidity without impairing the original characteristics (transparency heat resistance, impact resistance, and chemical resistance) of the aromatic polycarbonate resin.
Further, since the light diffusing plate of the present invention has excellent chemical resistance, it can be surface-modified, and as a result, other functions can be imparted. "Surface modification" is a new layer on the surface of a light-diffusing molded product by vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. It means to provide.

Next, the optical disk substrate of the present invention will be described.
The optical disk substrate of the present invention is usually produced from the above-mentioned resin composition by melt molding such as a known injection molding method (including an injection compression molding method), and in particular, the above-mentioned resin composition. Is suitable for an optical disc substrate of the present invention in which grooves and pits are transferred to one or both sides by an injection molding method using a stamper, because the optical disc substrate has high melt fluidity. It is possible to handle a wide range from to high recording densities.

The injection molding machine and stamper used may be general ones, but from the viewpoint of suppressing the generation of carbides derived from the resin composition in the cylinder and screw of the injection molding machine and improving the reliability of the optical disk substrate. , It is preferable to use a material having low adhesion to the resin composition and having corrosion resistance and abrasion resistance.
Further, the environment of the molding process is preferably as clean as possible from the viewpoint of the object of the present invention, and further, before molding, the resin composition is sufficiently dried to remove water and the resin composition. It is also important to take care so that the material does not stay in the molding machine and melt and decompose.

As long as the optical disk includes an optical disk substrate made of the above-mentioned resin composition, there is no limitation on the specific laminated structure thereof, and a reflective film, a recording layer, and a light transmitting layer are formed on one or both sides of the optical disk substrate. For example, a form in which such as is laminated as needed can be exemplified.

The optical disk substrate described above has high melt fluidity without impairing the original characteristics (transparency, heat resistance, impact resistance, and chemical resistance) of the aromatic polycarbonate resin, and therefore has good transferability and the like. Furthermore, the birefringence of the molded product is also improved. Therefore, such an optical disk substrate can be applied from an audio CD (recording density of about 650 MB per 12 cm diameter disc) to a high density disc.

Next, the light guide plate of the present invention will be described.
The light guide plate of the present invention is usually produced from the above-mentioned resin composition by a known injection molding method. The specific shape of the light guide plate is not particularly limited, but the above-mentioned resin composition has high melt fluidity and can satisfactorily transfer fine irregularities formed in the cavity of the injection molding die. Therefore, a light guide plate having a wedge-shaped cross section, in which one surface is an inclined surface having a uniform inclination and a continuous prism-shaped uneven pattern is applied to the inclined surface to form a diffused reflection portion, can be preferably exemplified. Such a light guide plate can be manufactured by injection molding while transferring the uneven portion using an injection molding mold having an uneven portion formed in the cavity. As a method of providing the uneven portion in the cavity of the injection molding die, a method of forming the uneven portion in the nest is convenient and preferable.

By providing at least such a light guide plate and a light source that emits light toward the light guide plate, a mobile phone, a mobile terminal, a camera, a clock, a laptop computer, a display, a lighting, a signal, a tail lamp of an automobile, and electromagnetic cooking are provided. It is possible to construct an edge type surface light source body used for displaying the thermal power of a vessel. As the light source, in addition to a fluorescent lamp, a self-luminous body such as a cold cathode tube, an LED, or an organic EL can be used.

Since the light guide plate described above is made of a polycarbonate resin composition having high melt fluidity without impairing the original characteristics (transparency, heat resistance, impact resistance, and chemical resistance) of the aromatic polycarbonate resin. It can be used for a wide range of purposes without limiting the usage environment, and fine irregularities formed in the cavity of the injection molding mold are sufficiently transferred, and the molding is performed well, and problems such as a decrease in brightness are suppressed. ing. Therefore, by using such a light guide plate, it is possible to provide a surface light source body having high performance and high industrial value.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
“Parts” and “%” in the examples represent “parts by mass” and “% by mass”, respectively.

(Measurement of polymerization rate)
The polymerization rate of the polymer was measured by the following procedure.
1) Measure the mass of the aluminum dish to the unit of 0.1 mg. (A)
2) Take 1 g of the polymer in an aluminum dish and measure the mass to the unit of 0.1 mg. (B)
3) Place the aluminum dish containing the polymer in a dryer at 180 ° C and heat it for 45 minutes.
4) The aluminum dish containing the polymer is taken out from the dryer, cooled to 24 ° C. in a desiccator, and then the mass is measured to the unit of 0.1 mg. (C)
5) The solid content of the polymer is calculated by the following formula.
(CA) / (BA) x 100 [%]
6) The calculated solid content is divided by the solid content at the time of preparation to calculate the polymerization rate of the polymer.

(Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn))
The (Mw) and (Mn) of the polymer were measured by the following procedure.
It was determined from a calibration curve with standard polystyrene using gel permeation chromatography. The measurement conditions are as follows.
Column: TSK-GEL SUPER HM-H (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C
Eluent: Tetrahydrofuran Eluent rate: 0.6 ml / min Detector: RI

[Production example of fluidity improver]
<Manufacturing example 1>
Production of Polymer (A-1) The following emulsifier mixture is placed in a separable flask equipped with a thermometer, nitrogen introduction tube, cooling tube and stirring device and stirred, and the internal temperature is raised to 60 ° C. in a nitrogen atmosphere. It was heated.
Emulsifier mixture:
Perex SS-L 0.6 part (manufactured by Kao Corporation, sulfonic acid emulsifier)
285 parts of deionized water

Then, the following reducing agent mixture was put into a separable flask.
Reducing agent mixture:
Ferrous sulfate 0.0001 part Ethylenediaminetetraacetic acid disodium salt 0.0003 part Longarit 0.3 part Deionized water 3 parts

A mixture of the monomeric mixture "Component 1" shown in Table 1, 0.5 part of n-octyl mercaptan and 0.2 part of t-butyl hydroperoxide was added dropwise to a separable flask over 360 minutes, and then at 80 ° C. After the temperature was raised to the above, the mixture was stirred for 60 minutes and polymerized to obtain a polymer (A-1) latex.

0.7 parts of Perex SS-L (manufactured by Kao Co., Ltd.) and Irg1076 (n-octadecyl-3- (3', 5'), a phenolic antioxidant, are added to the obtained polymer (A-1) latex. Di-t-butyl-4'-hydroxyphenyl) propionate) 0.25 parts by mass and AO-412S (bis [3- (dodecylthio) propionic acid] 2,2-bis [[3), which is a thioether-based antioxidant. -(Dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl) was added in an amount of 0.75 parts by mass to prepare a polymer (A-1) latex mixture. 273 parts of an aqueous solution prepared by dissolving 5 parts of calcium acetate in the obtained polymer (A-1) latex mixture was heated to 90 ° C. and stirred. The obtained polymer (A-1) latex was gradually added dropwise thereto. Then, the temperature was raised to 94 ° C. and held for 5 minutes to solidify the latex. The coagulated product was separated and washed, and then dried at 80 ° C. for 24 hours to obtain a polymer (A-1).
The polymerization rate of the polymer (A-1) was 99%.

<Manufacturing Examples 2 to 13>
Polymers (A-2) to (A-9), (B-1) and (B-4) to (B-5) were prepared in the same manner as in Production Example 1 except that each component shown in Table 1 was changed. Obtained. Regarding the polymer (B-2), the polymer (B-2) was the same as in Production Example 1 except that each component shown in Table 1 was changed and the amount of n-octyl mercaptan was changed to 0.55 part. -2) was obtained. The polymerization rates of the polymers (A-2) to (A-9), (B-1) to (B-2) and (B-4) to (B-5) were all 97% or more.

The polymerization rates and weight average molecular weights (Mw) of the produced polymers (A-2) to (A-9), (B-1) to (B-2) and (B-4) to (B-5) are determined. It was measured. The measurement results are shown in Table 2.

The abbreviations in the table are as follows.
St: Styrene, α-MeSt: α-methylstyrene, PhMA: Phenylmethacrylate, MMA: Methylmethacrylate

<Manufacturing example 14>
Production of (meth) Acrylate Copolymer (B-3) 200 parts of deionized water, the following dispersant, in a warmable reaction vessel equipped with a thermometer, nitrogen introduction tube, reflux cooling tube, and stirrer. 0.3 parts, sodium sulfate 0.5 parts, 2,2'-azobisisobutyronitrile 0.3 parts, phenyl methacrylate 20 parts, methyl methacrylate 78.5 parts, methyl acrylate 1.5 parts, n-octyl Two parts of mercaptan were charged, the inside of the reaction vessel was replaced with nitrogen, and the temperature was raised to 80 ° C. After stirring for 4 hours, the obtained bead-shaped polymer was washed with water and dried to obtain a (meth) acrylate copolymer (B-3). The weight average molecular weight of this (meth) acrylate copolymer (B-3) was 14,000.

[Manufacturing example of polycarbonate resin]
As the polycarbonate resin (PC1), the aromatic polycarbonate resin of Production Example 15 below was used.

<Manufacturing example 15>
A method for producing an aromatic polycarbonate resin will be described. The DPC (diphenyl carbonate) melt prepared at 140 ° C. under a nitrogen gas atmosphere and 2,2-bis (4-hydroxy-3-methylphenyl) propane were mixed in a molar ratio ratio (DPC / 2,2-bis (DPC / 2,2-bis). 4-Hydroxy-3-methylphenyl) propane) is continuously supplied to the mixing tanks adjusted at 140 ° C. under a nitrogen atmosphere so as to be 1.010, and then continuously supplied to the first polymerization tank. did. On the other hand, at the same time as the supply of the above mixture was started, a 2 mass% cesium carbonate aqueous solution was continuously supplied as a catalyst in an amount of 3.5 μmol with respect to 1 mol of 2,2-bis (4-hydroxy-3-methylphenyl) propane.
The first polymerization tank was kept at a temperature of 215 ° C. and a pressure (gauge pressure) of 11 kPa, and the discharged polymerization liquid was continuously continuously supplied to the second and third polymerization tanks and the fourth polymerization tank. .. The temperature of the second polymerization tank is 250 ° C. and the pressure (gauge pressure) is 3 kPa, the temperature of the third polymerization tank is 268 ° C. and the pressure (gauge pressure) is 100 Pa, the temperature of the fourth polymerization tank is 280 ° C. and the pressure (gauge pressure) is. The reaction was carried out under reaction conditions of 50 to 200 Pa. During the reaction, by-produced phenol was removed. Further, the aromatic polycarbonate resin extracted from the bottom of the fourth polymerization tank is introduced into a twin-screw extruder equipped with a three-stage vent port in a molten state, and p-toluenesulfonebutyl is theoretically neutralized by the catalyst. It was added in a molar amount four times the amount, devolatile, and then pelletized to obtain an aromatic polycarbonate resin (PC1). The viscosity average molecular weight (Mv) of the obtained aromatic polycarbonate resin was 26100.

<Examples 1 to 7, Comparative Examples 1 to 2>
The fluidity improvers obtained in Production Examples 1 to 13 and the polycarbonate resin obtained in Production Example 15 were mixed at the mass ratios shown in Table 3 to create a devolatilization twin-screw extruder (manufactured by Ikegai Iron Works, PCM). -30) was supplied and melt-kneaded at 280 ° C. to obtain an engineering plastic composition.
The obtained thermoplastic resin composition was evaluated in (1) to (3) described later. The results are shown in Table 3.

(Performance evaluation method)
(1) Melt fluidity The spiral fluidity length SPL of the obtained engineering plastic composition was evaluated using a Sumitomo injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.). The molding temperature was a cylinder temperature of 280 ° C., the mold temperature was 80 ° C., the injection pressure was 50 MPa, and 15 shots were continuously injected to obtain 15 molded products having a thickness of 2 mm and a width of 15 mm. The length from the gate of the molded product to the tip in the injection direction was measured with a caliper, and the average value of the 15 lengths was taken as the spiral flow length (SPL).
(2) Transparency Using the obtained engineering plastic composition, an injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.) was used at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C., thickness 2 mm, 5 cm × A 10 cm flat plate molded product was molded. The total light transmittance and haze of the molded product were measured at 23 ° C. according to ASTM D1003. The haze (%) needs to be 7.0 or less, preferably 4.0 or less, and even more preferably 3.0 or less.
(3) Chemical resistance Using the obtained engineering plastic composition, a Sumitomo injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.) was used to obtain a thickness of 2 mm at a cylinder temperature of 300 ° C and a mold temperature of 80 ° C. A 15 cm square flat plate was prepared and cut to obtain a molded product having a thickness of 2 mm and a thickness of 15 cm × 2.5 cm. The test piece was annealed at 120 ° C. for 2 hours and then attached to a quarter elliptical jig having a major axis of 120 mm and a minor axis of 40 mm. The chemical was applied to the surface of the specimen and then allowed to stand for 5 minutes, and the chemical was applied to the surface of the specimen again and then allowed to stand for 3 minutes. The maximum stress strain value ε (%) at which no cracks occurred was calculated from the crack occurrence position of the sample after chemical application, and used as an index of chemical resistance. The measurement conditions were a test temperature of 23 ° C., and the chemical used was acetone / ethanol = 1/1 (mass ratio). The maximum stress strain value ε (%) is preferably 0.35 or more, more preferably 0.45 or more, and most preferably 0.55 or more.

As is clear from the results in Table 3, the engineering plastic compositions obtained in Examples 1 to 7 showed a significant improvement in fluidity and chemical resistance as compared with Comparative Example 2 without impairing transparency. , The balance of physical properties was very good.
On the other hand, the fluidity improver (B-1) blended in the engineering plastic resin composition obtained in Comparative Example 1 does not contain an alkyl (meth) acrylate monomer unit (a3), and therefore is compatible. The balance of (compatibility) was not good, and sufficient transparency and chemical resistance could not be obtained. Further, in Comparative Example 2 which did not contain the fluidity improver of the present invention, sufficient fluidity and chemical resistance could not be obtained.

<Examples 8 to 12, Comparative Example 3>
The fluidity improvers obtained in Production Examples 1 to 13 and the polycarbonate resin obtained in Production Example 15 were mixed at the mass ratios shown in Table 4, and a devolatilization type twin-screw extruder (manufactured by Ikegai Iron Works, PCM) was mixed. -30) was supplied and melt-kneaded at 280 ° C. to obtain an engineering plastic composition.
The obtained thermoplastic resin composition was evaluated for (1) melt fluidity described above and (4) to (5) described later. The results are shown in Table 4.

(Performance evaluation method)
(4) Transparency Using the obtained engineering plastic composition, an injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.) was used at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C, and a thickness of 2 mm, 5 cm ×. A 10 cm flat plate molded product was molded. The total light transmittance and haze of the molded product were measured at 23 ° C. according to ASTM D1003. The haze (%) needs to be 7.0 or less, preferably 4.0 or less, and even more preferably 3.0 or less.
(5) Tensile properties Using the obtained engineering plastic composition, the tension specified by JIS-7139 was used by an injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C. A test piece was obtained. The tensile test was carried out at a tensile speed of 5 mm / min in accordance with ISO-527, and the yield point strength (MPa) was measured. The yield point strength (MPa) is preferably 68.5 or more, and more preferably 69.0 or more.
(6) Impact resistance Using the obtained engineering plastic composition, the thickness is 2 mm and 5 cm at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C by an injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.). A molded product of a flat plate of × 10 cm was molded. Using the molded product, a surface impact test was performed with a DuPont impact tester (load: 200 g, height: 150 mm, punch diameter: 0.5 inch, pedestal diameter: 30 mm, n = 3). If an impact is applied to the part shown in FIG. 1 of the molded product and cracks are visually confirmed in the test part as shown in FIG. 2a, it is judged to be brittle fracture, and the brittle fracture rate is calculated using the following formula [1]. However, it was used as an index of impact resistance. The lower the brittle fracture rate, the better the impact resistance.
Brittle fracture rate (%) = (number of brittle fractures) / (total number of test pieces) x 100 ... [1]
The brittle fracture rate is preferably 33% or less, most preferably 0%.

As is clear from the results in Table 4, the engineering plastic compositions obtained in Examples 8 to 12 had improved tensile strength and impact resistance as compared with Comparative Example 3. Since the fluidity improver of the present invention contains the (meth) acrylic acid ester monomer unit (a2) and the alkyl (meth) acrylate monomer unit (a3), the compatibility becomes good. , It is considered that the mechanical strength has improved.

<Examples 13 to 17, Comparative Examples 4 to 9>
The fluidity improvers obtained in Production Examples 1 to 13 and the polycarbonate resin (PC1) and PC2 obtained in Production Example 15 were mixed at the mass ratios shown in Table 5, and a devolatilization type twin-screw extruder (Ikegai) was mixed. It was supplied to PCM-30) manufactured by Iron Works Co., Ltd. and melt-kneaded at 280 ° C. to obtain an engineering plastic composition.
The obtained thermoplastic resin composition was evaluated for (1) melt fluidity, (4) transparency, and (6) impact resistance described above. The results are shown in Table 5.

PC2: Aromatic polycarbonate resin "Iupilon S-2000F" (trade name, manufactured by Mitsubishi Engineering Plastics Co., Ltd., nominal aromatic polycarbonate resin Mv: 22000)

From the evaluation results of the engineering plastic compositions obtained in Examples 13 to 17 of Table 5, the fluidity improver of the present invention has impact resistance, which is an original characteristic of the polycarbonate resin, even in a system in which two types of PCs are mixed. It was confirmed that the fluidity during the molding process was remarkably improved while maintaining sufficient transparency without impairing the properties.
On the other hand, the fluidity improver (B-1) blended in the engineering plastic resin composition obtained in Comparative Example 4 does not contain an alkyl (meth) acrylate monomer unit (a3), and therefore is compatible. The balance of (compatibility) was not good, and transparency and impact resistance were reduced. Further, the fluidity improver (B-2) blended in the engineering plastic resin composition obtained in Comparative Example 5 contains a large amount of the aromatic vinyl monomer unit (a1), but is a styrene monomer unit. Since the content was not sufficient, the melt fluidity was low. The engineering plastic resin composition obtained in Comparative Example 6 did not have sufficient fluidity as compared with Examples 13 to 17. Since the fluidity improver (B-3) blended in the engineering plastic resin composition obtained in Comparative Example 6 is a low molecular weight acrylic copolymer, the polycarbonate resin (PC1) and PC2 obtained in Production Example 15 Is completely compatible with. Therefore, a remarkable fluidity improving effect as in the fluidity improving agent of the present invention could not be obtained. The fluidity improver (A-3) and the fluidity improver (B-4) have the same amount of aromatic vinyl monomer unit (a1), phenylmethacrylate and methylmethacrylate, but the fluidity improver (B-). Since the content of the styrene monomer unit in 4) was not sufficient, the melt fluidity of the engineering plastic resin composition obtained in Comparative Example 7 was poor. The fluidity improver (B-5) blended in the engineering plastic resin composition obtained in Comparative Example 8 was a (meth) acrylic acid ester monomer unit (a2): phenyl (meth) acrylate, 4-. t-Butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) Since it does not contain a monomer unit composed of a monomer selected from acrylate and trichlorophenyl (meth) acrylate, the compatibility is not sufficient and the impact resistance is lowered.

<Examples 18 to 23, Comparative Examples 10 to 12>
The fluidity improvers obtained in Production Examples 1 to 13 and the polycarbonate resin (PC1) and PC2 obtained in Production Example 15 were mixed at the mass ratios shown in Table 6 to create a devolatilization twin-screw extruder (Ikegai). It was supplied to PCM-30) manufactured by Iron Works Co., Ltd. and melt-kneaded at 280 ° C. to obtain an engineering plastic composition.
The obtained thermoplastic resin composition was evaluated in (8) described later. The results are shown in Table 6.

PC2: Aromatic polycarbonate resin "Iupilon S-2000F" (trade name, manufactured by Mitsubishi Engineering Plastics Co., Ltd., nominal aromatic polycarbonate resin Mv: 22000)

(Performance evaluation method)
(8) Chemical resistance Using the obtained engineering plastic composition, an injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries, Ltd.) was used at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C to a thickness of 2 mm and 5 cm. A molded product of a flat plate of × 10 cm was molded. This was cut to obtain a molded product having a thickness of 2 mm and a thickness of 10 cm × 2.5 cm. After annealing the test piece at 100 ° C. for 3 hours, a cantilever test was performed, and the time until cracks were visually observed in the test piece by applying chemicals was measured. The measurement conditions were carried out at a test temperature of 23 ° C. and a load of 6 MPa. After applying 0.01 mL of toluene / isooctane = 1/1 (mass ratio) as a chemical, the test site was covered with a 2 cm × 1 cm PET film.
The crack generation time is preferably 60 seconds or longer, more preferably 80 seconds or longer, and most preferably 100 seconds or longer.

As is clear from the results in Table 6, the engineering plastic compositions obtained in Examples 18 to 23 had improved chemical resistance as compared with Comparative Examples 10 to 12.

Claims (20)

Aromatic vinyl monomer unit (a1) 60.0% by mass or more and 99.4% by mass or less,
The following (meth) acrylic acid ester monomer unit (a2) 0.1% by mass or more and 39.5% by mass or less Alkyl (meth) acrylate monomer unit (a3) 0.5% by mass or more and 39.9% by mass or less It is a polymer (A) containing
A fluidity improver containing a polymer (A) containing 60% by mass or more of a styrene monomer unit as the aromatic vinyl monomer unit (a1).
(Meta) acrylic acid ester monomer unit (a2): phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6 -A monomer unit composed of a monomer selected from tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, and trichlorophenyl (meth) acrylate. The fluidity improver according to claim 1, wherein the polymer (A) has a weight average molecular weight of 5,000 or more and 150,000 or less. According to any one of claims 1 or 2, the alkyl (meth) acrylate monomer unit (a3) is a monomer unit having a structure in which (meth) acrylic acid and a linear saturated fatty acid are ester-bonded. The fluidity improver described. The fluidity improver according to any one of claims 1 to 3, wherein the alkyl (meth) acrylate monomer unit (a3) is methyl methacrylate. The fluidity improver according to any one of claims 1 to 4, wherein the polymer (A) has a refractive index of 1.550 or more and 1.585 or less. A resin composition containing 90 parts by mass of a polycarbonate resin having a refractive index of 1.560 or more and 1.585 or less and 10 parts by mass of a fluidity improver was injection-molded at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C. The haze of a 2 mm, 5 cm × 10 cm flat plate is 7.0% or less, and the brittle fracture rate is 33% or less.
A fluidity improver in which the spiral flow length of a molded product having a thickness of 2 mm and a width of 15 mm, which is injected at a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure of 50 MPa, satisfies the relationship of the following formula (1-1). ..
SPL ≧ 1.80 × Lpc ・ ・ ・ (1-1)
(In the formula, SPL is the spiral flow length of the polycarbonate resin-based composition, and Lpc is the spiral flow length of the polycarbonate resin.) A thermoplastic resin composition obtained by blending the engineering plastic (B) with the fluidity improver according to any one of claims 1 to 6. The thermoplastic resin composition according to claim 7, wherein 100 parts by mass of the engineering plastic (B) is mixed with 0.1 part by mass or more and 30 parts by mass or less of the fluidity improver. The thermoplastic resin composition according to claim 7 or 8, wherein the engineering plastic (B) is a polyester-based polymer. The thermoplastic resin composition according to claim 9, wherein the polyester polymer has a refractive index of 1.540 or more and 1.595 or less. The thermoplastic resin composition according to claim 9 or 10, wherein the polyester-based polymer is a polycarbonate resin. Polycarbonate resin 40.0% by mass or more and 99.8% by mass or less, the fluidity improver 0.1% by mass or more and 30% by mass or less according to any one of claims 1 to 6, and the light diffusing agent 0. A thermoplastic resin composition containing 1% by mass or more and 30% by mass or less. A molded product obtained by injection molding the thermoplastic resin composition according to any one of claims 7 to 12. An automobile member obtained by injection molding the thermoplastic resin composition according to any one of claims 7 to 12. A hard-coated product in which a hard coat layer is provided on the surface of the molded product according to claim 13. A display front plate using the molded product according to claim 13. A glazing material using the molded product according to claim 13. A light diffusing plate obtained by molding the thermoplastic resin composition according to any one of claims 7 to 12. An optical disc substrate obtained by molding the thermoplastic resin composition according to any one of claims 7 to 12. A light guide plate obtained by molding the thermoplastic resin composition according to any one of claims 7 to 12.