JP2023118157A - Resin composition and molded product thereof - Google Patents

Abstract

To provide a resin composition comprising a polycarbonate resin having excellent transparency, impact resistance and antistatic properties, an acrylic resin, an impact resistance improver and an antistatic agent.SOLUTION: There is provided a resin composition comprising 5 to 60 pts.wt. of an impact resistance improver (C) having a refractive index of 1.485 or more ad 1.495 or less and 22 to 100 pts.wt. of a block polymer (D) having a structure in which a block of a polyolefin and a block of a polyether are repeatedly and alternately bonded based on the total 100 pts.wt. of a polycarbonate resin (A) containing 5 to 85 mol% of a carbonate constituent unit (a) represented by the following formula (1) in 100 mol% of the total carbonate constituent units and an acrylic resin (B). (wherein, W represents an alkylene group having 1 to 20 carbon atoms or a cylcoalkylene group having 6 to 20 carbon atoms, R represents a branched or straight chain alkyl group having 1 to 20 carbon atoms or a cylcoalkylene group having 6 to 20 carbon atoms which may have a substituent, m represents an integer of 0 to 10.)SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a resin composition containing a specific polycarbonate resin, an acrylic resin, a specific impact modifier and a specific antistatic agent.

Conventionally, methacrylic resins, polycarbonate resins (hereinafter sometimes referred to as PC) and the like are known as transparent resins, and are used in the form of molded articles, films, sheets, and the like for electrical and electronic parts, optical parts, automobile parts, and mechanical parts. It is used in a wide range of fields such as

Methacrylic acid resins such as polymethyl methacrylate (hereinafter sometimes referred to as PMMA) have high transparency and hard surface hardness (pencil hardness H to 3H), and are widely used as optical materials such as lenses and optical fibers. . However, its glass transition temperature is as low as about 100° C. and its heat resistance is poor, so its use in fields requiring heat resistance is limited. Furthermore, there is a problem that impact resistance is low.

Polycarbonate resins composed of bisphenol A are widely used for vehicles and construction materials because of their excellent heat resistance, impact resistance, flame retardancy and transparency. Among these applications, high weather resistance is required especially for those used outdoors, but generally the weather resistance of polycarbonate resin is not superior to that of other transparent materials such as acrylic resin. Discoloration and devitrification occur. In addition, there is a problem that the surface is very soft (pencil hardness 4B to 2B) and easily scratched.

Blends of PC and PMMA are known to be essentially incompatible and yield opaque materials. For example, Patent Document 1 discloses that a blend of PC and PMMA is opaque and does not exhibit the physical properties of both polymers.

A resin composition using a polycarbonate resin having a special structure and an acrylic resin has been reported (Patent Document 2), and excellent transparency, weather resistance and surface hardness have been achieved. However, according to the studies of the present inventors, the resin composition described in Patent Document 2 has a problem in impact resistance.

Moreover, polycarbonate resins and acrylic resins are easily electrified, and there is a problem that dust tends to adhere to the surface of the molded product due to static electricity. As one of the countermeasures against static electricity, a method of adding a hydrophilic polyamide-based polymer such as polyetheresteramide or polyetheramide to impart antistatic performance is known (Patent Document 3). However, when these hydrophilic polyamide-based polymers are blended with polycarbonate resins or acrylic resins, there is a problem that the transparency is remarkably lowered.

Therefore, no composition of polycarbonate resin and acrylic resin having good transparency, impact resistance and antistatic properties has been reported so far.

U.S. Pat. No. 4,319,003 JP 2015-232091 A JP-A-2002-129026

An object of the present invention is to provide a resin composition containing a polycarbonate resin, an acrylic resin, an impact modifier and an antistatic agent, which have excellent properties of transparency, impact resistance and antistatic properties. be.

As a result of extensive research, the present inventors have found that a polycarbonate resin containing a specific spiro ring structure, an acrylic resin, an impact modifier having a specific range of refractive index, and a block polymer having a specific structure By containing, it was found that a resin composition having excellent properties in transparency, impact resistance and antistatic properties was obtained, and the present invention was completed.
That is, according to the present invention, the objects of the invention are achieved by the following.

1. Based on a total of 100 parts by weight of a polycarbonate resin (A) and an acrylic resin (B) containing 5 to 85 mol% of a carbonate structural unit (a) represented by the following formula (1) out of 100 mol% of all carbonate structural units , 5 to 60 parts by weight of an impact modifier (C) having a refractive index of 1.485 or more and 1.495 or less, and a block polymer (D ) containing 22 to 100 parts by weight.

(Wherein, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R is a branched or linear alkyl group having 1 to 20 carbon atoms, or having a substituent represents a cycloalkyl group having 6 to 20 carbon atoms, and m is an integer of 0 to 10.)

2. The polycarbonate resin (A) consists of a carbonate structural unit (a) represented by the formula (1) and another carbonate structural unit (b), and the carbonate structural unit (b) is an aliphatic diol compound, an alicyclic 2. The resin composition according to the preceding item 1, wherein the carbonate structural unit (b) is derived from at least one compound selected from the group consisting of diol compounds of the formula and aromatic dihydroxy compounds.
3. 3. The resin composition as described in 1 or 2 above, wherein the weight ratio of the polycarbonate resin (A) and the acrylic resin (B) is 30:70 to 99:1.
4. 4. The resin composition according to any one of 1 to 3 above, wherein the acrylic resin (B) contains 40 to 100 mol % of structural units derived from methyl methacrylate.
5. The resin composition according to any one of the preceding items 1 to 4, wherein a test piece having a thickness of 5.2 mm has a haze of 15 or less.
6. 6. The resin composition according to any one of the preceding items 1 to 5, which has a notched Charpy impact strength of 8 kJ/m ² or more measured according to ISO 179.
7. 7. The resin composition according to any one of the preceding items 1 to 6, wherein the molded article has a surface resistivity of 1×10 ¹⁰ (Ω/□) or less.
8. A molded article obtained by injection molding the resin composition according to any one of the preceding items 1 to 7.
9. A film or sheet formed from the resin composition according to any one of 1 to 7 above.

In the present invention, an impact modifier having a specific range of refractive index and a block polymer having a specific structure are contained in resin components of a polycarbonate resin containing a specific spiro ring structure and an acrylic resin. , transparency, impact resistance and antistatic properties. Therefore, its industrial effect is exceptional.

The present invention will be described in detail below.

(Polycarbonate resin (A))
The polycarbonate resin used in the resin composition of the present invention is a polycarbonate resin containing 5 to 85 mol % of carbonate structural units (a) represented by the following formula (1) in 100 mol % of all carbonate structural units.

(Wherein, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R is a branched or linear alkyl group having 1 to 20 carbon atoms, or having a substituent represents a cycloalkyl group having 6 to 20 carbon atoms, and m is an integer of 0 to 10.)

The carbonate structural unit (a) represented by formula (1) above is derived from a diol having a spiro ring structure. Examples of diol compounds having such a spiro ring structure include 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy- 1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8, 10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, etc. Alicyclic diol compounds are mentioned.

Preferably, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane is used.

The polycarbonate resin used in the resin composition of the present invention contains 5 to 85 mol% of the carbonate structural unit (a) represented by the above formula (1) in 100 mol% of the total carbonate structural units, and 10 to 80 mol. %, more preferably 15 to 75 mol %, even more preferably 20 to 70 mol %. When the carbonate structural unit (a) is within the above range, the resin composition does not become cloudy due to phase separation during extrusion or molding in the resin composition with the acrylic resin, and crystals are formed during polymerization of the polycarbonate resin. It is preferable because the polymerization is easy without the polymerization.

The polycarbonate resin used in the resin composition of the present invention contains a carbonate structural unit (a) represented by the above formula (1) and is used as a copolymer with another carbonate structural unit (b).

The carbonate structural unit (b) is preferably a carbonate structural unit (b) derived from at least one compound selected from the group consisting of aliphatic diol compounds, alicyclic diol compounds and aromatic dihydroxy compounds. The carbonate structural unit (b) is a carbonate structural unit (b) derived from at least one compound selected from the group consisting of aliphatic diol compounds and alicyclic diol compounds in terms of surface hardness and weather resistance. Preferably.

Aliphatic diol compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1.9-nonanediol, 1 , 10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1 ,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl- 1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc. 1,8-octanediol, 1.9-nonanediol, 1,10-decanediol and 1,12-dodecanediol are preferably used.

Alicyclic diol compounds include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and 1,2-cyclohexane cyclohexanedimethanols such as dimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol; norbornanedimethanols such as 2,3-norbornanedimethanol and 2,5-norbornanedimethanol; candimethanol, pentacyclopentadecanedimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalindimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide and the like. , cyclohexanedimethanols and isosorbide are preferably used.

Examples of aromatic dihydroxy compounds include α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (bisphenol M), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1- bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, bisphenol A, 2 , 2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (bisphenol AF ), and 1,1-bis(4-hydroxyphenyl)decane, and bisphenol A is preferably used.

The carbonate structural unit (b) contains 15 to 95 mol% in 100 mol% of the total carbonate structural units, preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and 30 to 80 mol%. is more preferred. When the carbonate structural unit (b) is within the above range, a resin composition having an excellent balance of transparency, impact resistance and antistatic properties can be obtained.

(Method for producing polycarbonate resin (A))
The polycarbonate resin used in the resin composition of the present invention is produced by a reaction means known per se for producing ordinary polycarbonate resins, for example, a method of reacting a diol component with a carbonate precursor such as a diester carbonate. Next, the basic means of these manufacturing methods will be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of the diol component and the carbonic acid diester are heated and stirred under an inert gas atmosphere to distill off the resulting alcohol or phenol. Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage while the alcohol or phenols produced are distilled off. Moreover, you may add a terminal terminator, an antioxidant, etc. as needed.

Carbonic acid diesters used in the transesterification reaction include esters such as optionally substituted aryl groups and aralkyl groups having 6 to 12 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate and m-cresyl carbonate. Among them, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate to be used is preferably 0.97-1.10 mol, more preferably 1.00-1.06 mol, per 1 mol of the total dihydroxy compound.

In the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate, and examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, etc. of alkali metals and alkaline earth metals are preferably used, and these compounds are They can be used singly or in combination.

Alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium Stearate, Potassium Stearate, Cesium Stearate, Lithium Stearate, Sodium Borohydride, Sodium Benzoate, Potassium Benzoate, Cesium Benzoate, Lithium Benzoate, Disodium Hydrogen Phosphate, Dipotassium Hydrogen Phosphate, Phosphorus Dilithium oxyhydrogen, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol and the like are exemplified.

Alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, diacetic acid. Barium, barium stearate and the like are exemplified.

Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having an alkyl or aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. mentioned. Also included are tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole. Bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate are also exemplified.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organic tin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. These compounds may be used alone or in combination of two or more.

The amount of these polymerization catalysts used is preferably 1×10 ⁻⁹ to 1×10 ⁻² equivalents, preferably 1×10 ⁻⁸ to 1×10 ⁻⁵ equivalents, more preferably 1×10 −9 equivalents, per 1 mol of the diol component. It is selected in the range of 10 ⁻⁷ to 1×10 ⁻³ equivalents.

Also, a catalyst deactivator can be added in the latter stage of the reaction. As the catalyst deactivator to be used, known catalyst deactivators are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acid are preferable. Further preferred are salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate and salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate.

Examples of sulfonic acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, Octyl p-toluenesulfonate, phenyl p-toluenesulfonate and the like are preferably used. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

When at least one polymerization catalyst selected from alkali metal compounds and/or alkaline earth metal compounds is used, the amount of these catalyst deactivators used is preferably 0.5 to 50 mol per 1 mol of the catalyst. It can be used in a proportion, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.

(Specific viscosity of polycarbonate resin (A): η _SP )
The specific viscosity (η _SP ) of the polycarbonate resin used in the resin composition of the present invention is preferably 0.2 to 1.5. When the specific viscosity is in the range of 0.2 to 1.5, the strength and moldability of the molded product are improved. It is more preferably 0.25 to 1.2, still more preferably 0.3 to 1.0, and particularly preferably 0.3 to 0.5.

The specific viscosity referred to in the present invention is obtained by using an Ostwald viscometer from a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
In addition, as a specific measurement of specific viscosity, for example, it can be performed in the following manner. First, the polycarbonate resin is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble matter is collected by celite filtration, then the solution is removed and sufficiently dried to obtain a methylene chloride soluble solid matter. The specific viscosity at 20° C. of a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride is determined using an Ostwald viscometer.

(Acrylic resin (B))
As the acrylic resin used in the resin composition of the present invention, an acrylic resin as a thermoplastic resin is used. Examples of monomers used in acrylic resins include the following compounds. For example, methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate ) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofluoro Furyl (meth)acrylate, acrylic (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)phthalate meth)acryloyloxyethyl, 2-(meth)acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate Acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, cyclododecyl acrylate and the like.

These may be used by polymerizing alone, or may be used by polymerizing two or more kinds. In particular, it preferably contains methyl methacrylate and/or methyl acrylate. In particular, it preferably contains 40 to 100 mol % of methyl methacrylate as a monomer component, more preferably 50 to 100 mol %, even more preferably 60 to 99 mol %. When the ratio of methyl methacrylate as a monomer component is within the above range, the heat decomposition resistance is excellent, molding defects such as silver are less likely to occur during molding, and the heat distortion temperature is favorable. Other monomers that can be polymerized with these acrylic monomers, such as polyolefin monomers and vinyl monomers, may also be used in combination.

The molecular weight of the acrylic resin is not particularly limited, but if the weight average molecular weight is in the range of 30,000 or more and 300,000 or less, appearance defects such as uneven flow may occur when the composition is molded. It is possible to provide a composition excellent in mechanical properties and heat resistance.

The acrylic resin used in the resin composition of the present invention preferably has a specific viscosity in the range of 0.12 to 0.55. If the specific viscosity is less than 0.12, the molded product may become brittle. When the specific viscosity is higher than 0.55, the melt viscosity of the resin becomes high and the moldability may deteriorate.

(Impact modifier (C))
The resin composition of the present invention contains an impact modifier (C). The impact modifier (C) is preferably a core-shell type polymer comprising a core of a rubber-like polymer and a shell obtained by graft polymerization to the rubber-like polymer. A core-shell type polymer tends to have good dispersibility in polycarbonate and high impact strength.

The average particle size of the impact modifier (C) is preferably 10 to 500 nm. It is more preferably 30 to 300 nm, still more preferably 50 to 200 nm, and most preferably 50 to 180 nm. If the average particle size is less than 10 nm, there is a tendency that sufficient impact strength cannot be obtained. On the other hand, when the average particle size exceeds 500 nm, the resulting resin composition tends to have reduced transparency. Incidentally, the average particle size is measured in the latex state of the rubber-like polymer and the graft copolymer. The volume average particle size was measured using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. as a measuring device.

The rubber-like polymer corresponding to the core of the impact modifier (C) is a vinyl-based monomer rubber-like polymer or a polymer of a diene-based monomer and a vinyl-based monomer, The fact that the vinyl-based monomer is at least one selected from (meth)acrylic acid monomers and (meth)acrylic acid alkyl ester monomers enhances the transparency and impact resistance of the resin composition of the present invention. It is preferable from the viewpoint of compatibility and also from the viewpoint of raw material costs.

A (meth)acrylic acid monomer means an acrylic acid monomer, a methacrylic acid monomer, or a mixture thereof. A (meth)acrylic acid alkyl ester monomer means an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, or a mixture thereof.

A specific example of the diene monomer is 1,3-butadiene. Specific examples of (meth)acrylic acid monomers and (meth)acrylic acid alkyl ester monomers include acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. , ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, and glycidyl methacrylate. Polymers obtained from such monomers include, for example, butadiene-acrylate copolymers.

The glass transition temperature (Tg) of the rubber-like polymer is preferably 0° C. or lower from the viewpoint of impact resistance improvement. It is more preferably -20°C or lower, still more preferably -40°C or lower.

The shell portion of the impact modifier (C) is at least one vinyl monomer. The shell portion can be formed by graft polymerization with at least one vinyl-based monomer.

Vinyl-based monomers include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acids and unsaturated carboxylic acid esters. Among aromatic vinyl compounds, styrene and α-methylstyrene are preferred. Among vinyl cyanide compounds, acrylonitrile and methacrylonitrile are preferred. Among unsaturated carboxylic acids and unsaturated carboxylic acid esters, acrylic Acids, methacrylic acid, acrylic acid esters and methacrylic acid esters having alkyl esters of 1 to 12 carbon atoms, and the like are preferred. Since the dispersibility in the polycarbonate resin is excellent and the transparency of the resulting resin composition is excellent, unsaturated carboxylic acid esters, or unsaturated carboxylic acid esters and aromatic vinyl monomers for use in graft polymerization are preferred. A mixture of compounds is preferred.

Furthermore, the impact modifier (C) contains one or more selected from an epoxy group, a hydroxy group, a carboxyl group, an alkoxy group, an isocyanate group, an acid anhydride group, and an acid chloride group in the graft portion. Reactive groups can be introduced. As a result, dispersibility and impact resistance may be improved as compared with the case of using a rubber graft copolymer containing no reactive group.

The impact modifier (C) used in the present invention has a refractive index of 1.485 or more and 1.495 or less, preferably 1.487 or more and 1.494 or less, and more preferably 1.490 or more and 1.495 or less. .493 or less. When the refractive index of the impact modifier (C) is within the above range, the resin composition is excellent in transparency and impact resistance.

As a method for producing the impact modifier (C), any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization may be employed, but emulsion polymerization, that is, emulsion graft polymerization is preferred. Specifically, latex is added to a reaction vessel equipped with a stirrer, a vinyl monomer, a polymerization initiator, and water are added. good.

There are no particular restrictions on the types of the polymerization initiator, chain transfer agent, and redox agent used here, and known ones can be used. Also, the method of adding each raw material to the reaction vessel is not particularly limited. In addition, the graft polymerization is carried out in one stage or two or more stages, and the monomer composition in each stage may be the same or different. or a combination of these.

When an emulsion polymerization method is employed, a known polymerization initiator, that is, a thermal decomposition type polymerization initiator such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate should be used. can be done. In addition, organic peroxides such as t-butylperoxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-hexyl peroxide, etc. oxides, or peroxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, and optionally sodium formaldehyde sulfoxylate, a reducing agent such as glucose, and optionally iron sulfate ( II), a chelating agent such as disodium ethylenediaminetetraacetate as necessary, and a phosphorus-based flame retardant such as sodium pyrophosphate as necessary as a redox polymerization initiator. can also

When a redox polymerization initiator system is used, the polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed. Among them, aromatic ring-containing peroxides such as cumene hydroperoxide and dicumyl peroxide are preferably used as redox polymerization initiators. The amount of the polymerization initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox polymerization initiator is used, can be used within a known range.

When synthesizing the impact modifier (C) by emulsion polymerization, the emulsifying agent may be an alkali metal salt of a higher fatty acid such as disproportionated rosin acid, oleic acid or stearic acid, or an alkali metal phosphate compound. Conventionally known polymerization emulsifiers such as salts, alkali metal salts of sulfonic acid and sulfuric acid compounds can be used.

When the impact modifier (C) is obtained by emulsion polymerization, for example, a latex of the impact modifier (C) and an acid such as hydrochloric acid, or calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride, or calcium acetate After coagulation by mixing a divalent or higher metal salt such as, the impact modifier can be separated from the aqueous medium by heat treatment, dehydration, washing and drying according to a known method (coagulation method also called). Alternatively, an alcohol such as methanol, ethanol, or propanol, or a water-soluble organic solvent such as acetone is added to the latex to precipitate the impact modifier, which is separated from the solvent by centrifugation or filtration, and then dried and isolated. You can also Alternatively, a slightly water-soluble organic solvent such as methyl ethyl ketone is added to the latex containing the impact modifier used in the present invention, and the impact modifier component in the latex is extracted into the organic solvent layer. A method of separating the solvent layer and then mixing it with water or the like to precipitate the impact resistance modifier component can be used. Alternatively, the latex can be directly pulverized by a spray drying method.

In the present invention, the resin composition may be a resin composition in which a polycarbonate resin contains an impact resistance modifier previously contained in an acrylic resin. Specific examples of acrylic resins containing impact modifiers are not particularly limited, but include the following.

For example, Mitsubishi Chemical Co., Ltd., trade names ACRYPET IRK304, IRL309, VRL40; Kuraray Co., Ltd., trade names Parapet GR00100, GR04970, GR-H60; Daicel-Evonik Co., trade names PLEXIGLAS AG100, zk6HF; namely Delpet SR8350, SR8500 and the like.

(Block polymer (D))
The resin composition of the present invention contains a block polymer (D) having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded.

The polyether chain functions as a hydrophilic segment, and having the polyether chain exhibits antistatic performance. The weight average molecular weight of such polyether chains is preferably 1,000 to 15,000 from the viewpoint of heat resistance and reactivity with polyolefin chains. Such a block polymer can be produced, for example, by acid-modifying polypropylene or polyethylene described in JP-A-2001-278985 and JP-A-2003-48990 and reacting it with polyalkylene glycol. .

Since the block polymer (D) used in the present invention exhibits antistatic performance by being dispersed in the polycarbonate resin and the acrylic resin, the surface resistance value of the block polymer (D) itself is generally preferably as low as possible. Such a block polymer usually has a surface resistance value of 1×10 ¹⁰ to 1×10 ⁴ Ω, whereas the block polymer (D) used in the present invention has a surface resistance value of 1×10 ⁹ to 1×10 ⁴ Ω. It is preferably 1×10 ⁸ to 1×10 ⁴ Ω.

For the purpose of further improving the antistatic properties, if necessary, other antistatic agents other than the above block polymers may be used in combination.

Other antistatic agents include surfactants [anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.], salts other than surfactant salts, and ionic liquids. can do.

(Method for producing resin composition containing polycarbonate resin, acrylic resin, impact modifier and block polymer)
The resin composition of the present invention is preferably a blend of polycarbonate resin, acrylic resin, impact modifier and antistatic agent containing block polymer in a molten state. As a method for blending in a molten state, an extruder is generally used, and kneading and pelletizing are carried out at a molten resin temperature of 200 to 320°C, preferably 220 to 300°C, more preferably 230 to 290°C. As a result, pellets of a resin composition in which both resins are uniformly blended are obtained. The structure of the extruder, the structure of the screw, etc. are not particularly limited. If the molten resin temperature in the extruder exceeds 320°C, the resin may be colored or thermally decomposed. On the other hand, if the resin temperature is lower than 200°C, the resin viscosity is too high and the extruder may be overloaded.

(weight ratio)
The weight ratio of polycarbonate resin (A) and acrylic resin (B) used in the present invention is preferably in the range of 30:70 to 99:1. It is more preferably in the range of 35:65 to 95:5, still more preferably in the range of 40:60 to 93:7, particularly preferably in the range of 45:55 to 92:8, most preferably 50: It ranges from 50 to 90:10. By setting it as the said range, the resin composition excellent in transparency and impact resistance can be obtained.

The impact modifier (C) used in the present invention is blended in the range of 5 to 60 parts by weight with respect to the total of 100 parts by weight of the polycarbonate resin and the acrylic resin. It is preferably in the range of 7 to 55 parts by weight, more preferably in the range of 8 to 50 parts by weight, still more preferably in the range of 9 to 48 parts by weight, and particularly preferably in the range of 10 to 45 parts by weight. . By setting it as the said range, the resin composition excellent in transparency and impact resistance can be obtained.

The block polymer (D) used in the present invention is blended in the range of 22 to 100 parts by weight with respect to a total of 100 parts by weight of the polycarbonate resin and the acrylic resin. It is preferably in the range of 24 to 95 parts by weight, more preferably in the range of 26 to 90 parts by weight, still more preferably in the range of 28 to 85 parts by weight, and particularly preferably in the range of 29 to 80 parts by weight. . A resin composition having excellent transparency, impact resistance, and antistatic properties can be obtained by setting the amount within the above range.

(Additive)
The resin composition used in the present invention contains a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, a surfactant, an antibacterial agent, and an ultraviolet absorber, depending on the application and need. Additives such as release agents, colorants, etc. can be added.

(Heat stabilizer)
The resin composition used in the present invention preferably contains a heat stabilizer in order to suppress molecular weight reduction and color deterioration during extrusion and molding. Examples of heat stabilizers include phosphorus-based heat stabilizers, phenol-based heat stabilizers, and sulfur-based heat stabilizers, and these may be used alone or in combination of two or more. A phosphite compound is preferably blended as the phosphorus stabilizer. Phosphite compounds include pentaerythritol-type phosphite compounds, phosphite compounds having a cyclic structure that have reacted with dihydric phenols, and phosphite compounds having other structures.

Specific examples of the pentaerythritol-type phosphite compound include, for example, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6 -di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like, preferably distearylpentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)penta Erythritol diphosphite may be mentioned.

Examples of the phosphite compound having a cyclic structure that reacts with the above dihydric phenols include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl ) phosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2′-methylenebis(4-methyl-6- tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2′-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) ) phosphite, 2,2′-methylene-bis-(4,6-di-t-butylphenyl)octyl phosphite, 6-tert-butyl-4-[3-[(2,4,8,10) -tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol and the like.

Examples of phosphite compounds having other structures above include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite and didecylmonophenylphosphite. , dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite phyte, tris(diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, and tris(2,6-di-tert-butylphenyl)phosphite.

Other than various phosphite compounds, for example, phosphate compounds, phosphonite compounds, and phosphonate compounds can be used.

Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate and the like can be mentioned, and triphenyl phosphate and trimethyl phosphate are preferred.

Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenedi Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite , tetrakis(2,6-di-tert-butylphenyl)-4,3′-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di -n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2, 4-di-tert-butylphenyl)-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable.

Phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like.

Among the above phosphorus heat stabilizers, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol The diphosphite bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is preferably used.

The above phosphorus-based heat stabilizers may be used alone or in combination of two or more. Phosphorus-based heat stabilizer is blended in an amount of preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and even more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. be done.

The resin composition used in the present invention contains a hindered phenol-based heat stabilizer or a sulfur-based heat stabilizer as a heat stabilizer for the purpose of suppressing a decrease in molecular weight and a deterioration in color during extrusion and molding. It can also be added in combination with a phosphorus heat stabilizer.

The hindered phenol-based heat stabilizer is not particularly limited as long as it has an antioxidant function. butylphenyl)propionate, tetrakis{methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl)propionate}methane, distearyl(4-hydroxy-3-methyl-5-t-butylbenzyl ) malonate, 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}, pentaerythrityl-tetrakis {3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2-thiodiethylenebis{3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2-thiobis(4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3 ,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 2,4-bis{(octylthio)methyl}-o - cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl ) chroman-6-ol, 3,3′,3″,5,5′,5″-hexa-t-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri- and p-cresol.

Among these, n-octadecyl-3-(4′-hydroxy-3′,5′-di-t-butylphenyl)propionate, pentaerythrityl-tetrakis{3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate}, 3,3′,3″,5,5′,5″-hexa-t-butyl-a,a′,a′-(mesitylene-2,4,6-triyl) Tri-p-cresol, 2,2-thiodiethylenebis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate} and the like are preferred.

These hindered phenol heat stabilizers may be used singly or in combination of two or more.

The hindered phenol heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, still more preferably 0.01 to 0.3 part by weight, per 100 parts by weight of the resin composition. Partially blended.

Examples of sulfur-based heat stabilizers include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, di Stearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetrakis(3-laurylthiopropionate), bis[2-methyl-4-(3 -laurylthiopropionyloxy)-5-tert-butylphenyl]sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis(2-naphthol), and the like. . Among the above, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred.

One of these sulfur-based heat stabilizers may be used alone, or two or more of them may be used in combination.
The sulfur-based heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. be done.

When a phosphite-based heat stabilizer, a phenol-based heat stabilizer, and a sulfur-based heat stabilizer are used in combination, the total amount of these is preferably 0.001 to 1 part by weight, more preferably 0, per 100 parts by weight of the resin composition. 0.01 to 0.3 parts by weight.

(Release agent)
The resin composition used in the present invention may contain a mold release agent within a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding.
Examples of such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefinic waxes, olefinic waxes containing carboxy groups and/or carboxylic acid anhydride groups, silicone oils, organopolysiloxane and the like.

Preferred higher fatty acid esters are partial or full esters of monohydric or polyhydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms. Partial or full esters of monohydric or polyhydric alcohols with saturated fatty acids include, for example, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, and behenic acid. Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene -to, sorbitan monostearate, 2-ethylhexyl stearate and the like.
Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

As higher fatty acids, saturated fatty acids having 10 to 30 carbon atoms are preferred. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.
One of these release agents may be used alone, or two or more thereof may be used in combination. The amount of the release agent to be added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the resin composition.

(Ultraviolet absorber)
The resin composition used in the present invention can contain an ultraviolet absorber. Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. agents are preferred.

Examples of benzotriazole-based UV absorbers include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-tert-butylphenyl)benzotriazole, 2-(2 '-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5′-di-tert-amylphenyl)benzotriazole, 2-(2′-hydroxy-3′-dodecyl-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-bis (α,α'-dimethylbenzyl)phenylbenzotriazole, 2-[2'-hydroxy-3'-(3″,4″,5″,6″-tetraphthalimidomethyl)-5′-methylphenyl]benzotriazole , 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,2′methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], methyl-3-[3 -tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate-polyethylene glycol condensate, exemplified by benzotriazole-based UV absorbers.

The proportion of such an ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, and still more preferably 0.2 to 0.5 parts by weight with respect to 100 parts by weight of the resin composition. is.

(light stabilizer)
The resin composition used in the present invention can contain a light stabilizer. When a light stabilizer is contained, there is an advantage that the weather resistance is good and the molded article is less likely to crack.

Examples of light stabilizers include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, didecanoic acid bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, 2,4- bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-2-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (2,2,6,6- tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4 -benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl ) diphenylmethane-p,p'-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)benzene-1,3-disulfonate, bis(2,2,6,6-tetramethyl -4-piperidyl)phenyl phosphite and other hindered amines, nickel bis(octylphenyl sulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate and other nickel These light stabilizers may be used alone or in combination of two or more.The content of the light stabilizer is preferably 0.001 to 1 part by weight per 100 parts by weight of the resin composition. More preferably 0.01 to 0.5 parts by weight.

(epoxy stabilizer)
In order to improve the hydrolyzability of the resin composition used in the present invention, an epoxy compound can be blended within a range that does not impair the object of the present invention.

Epoxy-based stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl carboxylate. , 3,4-epoxy-6-methylcyclohexylmethyl-3′,4′-epoxy-6′-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3′,4′-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl)butyl-3′,4′-epoxycyclohexyl carboxylate, 3,4-epoxycyclohexyl ethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, 3,4-epoxy -6-methylcyclohexylmethyl-6'-methylsilohexyl carboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclo Pentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3, 5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2 , 2-dimethyl-3,4-epoxycyclohexyl carboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexyl carboxylate, octadecyl-3,4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3′,4′-epoxycyclohexyl carboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3′,4′-epoxycyclohexyl carboxylate, 4,5-epoxy tetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxy tetrahydrophthalic anhydride, diethyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, di-n-butyl -3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate and the like. Bisphenol A diglycidyl ether is preferred in terms of compatibility and the like.

Such an epoxy stabilizer is used in an amount of 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the resin composition. It is desirable to be blended in the range.

(Bluing agent)
The resin composition used in the present invention can contain a bluing agent in order to cancel the yellowness of the lens due to the polymer or the ultraviolet absorber. As the bluing agent, any bluing agent that is used for polycarbonate can be used without any particular problem. In general, anthraquinone dyes are readily available and preferred.

Specific bluing agents include, for example, general name Solvent Violet 13 [CA. No (color index No) 60725], general name Solvent Violet 31 [CA. No 68210, generic name Solvent Violet 33 [CA. No 60725], generic name Solvent Blue 94 [CA. No 61500], generic name Solvent Violet 36 [CA. No 68210], generic name Solvent Blue 97 [Bayer "Macrolex Violet RR"] and generic name Solvent Blue 45 [CA. No. 61110] is a typical example.

These bluing agents may be used alone or in combination of two or more. These bluing agents are preferably blended in a proportion of 0.1×10 ⁻⁴ to 2×10 ⁻⁴ parts by weight per 100 parts by weight of the resin composition.

(Flame retardants)
A flame retardant can also be added to the resin composition used in the present invention. Flame retardants include halogen flame retardants such as brominated epoxy resins, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, and chlorinated polyethylene; phosphate ester flame retardants such as monophosphate compounds and phosphate oligomer compounds; Phosphinate compounds, phosphonate compounds, phosphonitrile oligomer compounds, organic phosphorus flame retardants other than phosphoric acid ester flame retardants such as phosphonic acid amide compounds, organic sulfonic acid alkali (earth) metal salts, borate metal salt flame retardants, and organic metal salt flame retardants such as metal stannate flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, and triazine flame retardants. Separately, a flame retardant auxiliary (for example, sodium antimonate, antimony trioxide, etc.) or an anti-dripping agent (polytetrafluoroethylene having fibril-forming ability, etc.) may be blended together with the flame retardant.

Among the above flame retardants, compounds that do not contain chlorine atoms or bromine atoms reduce the factors that are considered unfavorable when incinerated or thermally recycled. It is more suitable as a flame retardant in the molded article of the present invention.

When blending a flame retardant, it is preferably in the range of 0.05 to 50 parts by weight per 100 parts by weight of the resin composition. When the amount is 0.05 parts by weight or more, sufficient flame retardancy is easily exhibited, and when the amount is 50 parts by weight or less, the strength and heat resistance of the molded product are excellent.

(Molding)
The resin composition of the present invention can be molded and processed into molded articles (including sheets and films) by any method such as injection molding, compression molding, injection compression molding, melt film forming, casting, etc. Lenses, optical discs, optical films, plastic substrates, optical cards, liquid crystal panels, headlamp lenses, light guide plates, diffusion plates, protective films, OPC binders, front plates, housings, trays, water tanks, lighting covers, signboards, resin windows, It can be used as a molded product such as a carrier tape. In particular, it can be used as members requiring antistatic performance, such as front plates, housings, trays, lighting covers, signboards, resin windows, and carrier tapes.

(transparency)
The haze of a 2 mm-thick molded piece of the resin composition of the present invention is preferably 15 or less, more preferably 14 or less, even more preferably 13 or less, and particularly preferably 12 or less. preferable. When the haze is within the above range, the range of use as an optical member is not limited, which is preferable.

(Impact strength)
The resin composition of the present invention preferably has a notched Charpy impact strength measured in accordance with ISO 179 of 8 kJ/m ² or more, more preferably 9 kJ/m ² or more, and 10 kJ/m ² or more. is more preferable, and 11 kJ/m ² or more is particularly preferable. A notched Charpy impact strength of 100 kJ/m ² or less provides a sufficient function.

(Antistatic property)
The resin composition of the present invention has a surface specific resistivity of 1×10 ¹⁰ Ω/□ or less measured at a measurement voltage of 1000 V using a high resistance resistivity meter MCP-HT450 manufactured by Mitsubishi Chemical Analic Co., Ltd. It is preferably 5×10 ⁹ Ω/□ or less, more preferably 1×10 ⁹ Ω/□ or less.

(surface treatment)
A molded article formed from the resin composition of the present invention can be subjected to various surface treatments. Surface treatment here refers to deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. It is to be formed, and a commonly used method can be applied. Specific examples of the surface treatment include hard coating, water-repellent/oil-repellent coating, ultraviolet-absorbing coating, infrared-absorbing coating, and various surface treatments such as metallizing (vapor deposition, etc.). A hard coat is a particularly preferred and required surface treatment.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto. In addition, "parts" in the examples means "parts by weight". The resins used in the examples and the evaluation methods are as follows.

1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR of JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.
2. Specific Viscosity Determined from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
3. Haze A 2-mm-thick portion of the three-stage plate obtained by the following method was measured using a haze meter 300A manufactured by Nippon Denshoku Industries Co., Ltd.
4. Notched Charpy Impact Strength An ISO bending test piece obtained by the following method was measured for notched Charpy impact strength according to ISO 179.
5. Antistatic Performance A flat plate of length 45 mm x width 50 mm x thickness 2 mm obtained under the same conditions as in the following method was conditioned in an environment of 23°C and 50% humidity for one week. After that, the surface specific resistivity (Ω/□) of the molded product was measured using a resistivity meter (high resistance resistivity meter MCP-HT450 manufactured by Mitsubishi Chemical Analic Co., Ltd.) at a measurement voltage of 1000V. A smaller value indicates better antistatic performance.

[Polycarbonate resin (A)]
PC-1 (Example):
Structural unit derived from isosorbide (hereinafter ISS)/3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter SPG) Structural unit derived from / Structural unit derived from 1,9-nonanediol (hereinafter ND) = 72/21/7 (mol%), specific viscosity 0.396
PC-2 (Example):
Structural unit derived from ISS/structural unit derived from SPG/structural unit derived from ND = 58/38/4 (mol%), specific viscosity 0.425
PC-3 (comparative example)
Structural unit derived from ISS/structural unit derived from ND = 88/12 (mol%), specific viscosity 0.366
PC-4 (comparative example)
Structural unit derived from ISS/structural unit derived from 1,4-cyclohexanedimethanol (CHDM) = 70/30 (mol%), specific viscosity 0.378
PC-5 (comparative example)
Aromatic polycarbonate resin having a structural unit derived from bisphenol A, L-1225WP manufactured by Teijin Limited

[Acrylic resin (B)]
B-1 (Example): Acrypet VH001 manufactured by Mitsubishi Chemical Corporation (acrylic resin obtained by copolymerizing 95 mol% of methyl methacrylate and 5 mol% of methyl acrylate)
[Impact modifier composite acrylic resin (B + C)]
B+C (Example): Mitsubishi Chemical Corporation ACRYPET VRL40 (refractive index of impact modifier: 1.492)
[Impact modifier (C)]
C-1 (Example): Kaneace M-230 manufactured by Kaneka (refractive index: 1.492)
C-2 (Example): Metabrene W-377 manufactured by Mitsubishi Chemical Corporation (refractive index: 1.492)
C-3 (comparative example): Metabrene W-450A manufactured by Mitsubishi Chemical Corporation (refractive index: 1.472)

[Antistatic agent (D)]
D-1 (Example): Block polymer having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded Plectron PVL manufactured by Sanyo Chemical Industries Co., Ltd. (surface resistance value: 3×10 ⁶ Ω)
D-2 (Example): Block polymer having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded Pelestat 230 manufactured by Sanyo Chemical Industries, Ltd. (surface resistance value: 5×10 ⁷ Ω)
D-3 (Example): Block polymer having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded Pelestat 300 manufactured by Sanyo Chemical Industries, Ltd. (surface resistance value: 1×10 ⁸ Ω)
D-4 (Comparative Example): Block polymer having a structure in which polyamide blocks and polyether blocks are ester-bonded Pelestat NC6321 manufactured by Sanyo Chemical Industries, Ltd. (surface resistance: 1×10 ⁹ Ω)

[Example 1]
<Production of polycarbonate resin>
Isosorbide (hereinafter abbreviated as ISS) 364 parts, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter abbreviated as SPG ) 221 parts, 1,9-nonanediol (hereinafter abbreviated as ND) 39 parts, diphenyl carbonate (hereinafter abbreviated as DPC) 750 parts, and 0.8×10 ⁻² parts of tetramethylammonium hydroxide and barium stearate as a catalyst A 0.6×10 ⁻⁴ part was heated to 200° C. in a nitrogen atmosphere and melted. After that, the temperature was raised to 220° C. over 30 minutes and the degree of pressure reduction was adjusted to 20.0 kPa. After that, the temperature was raised to 240° C. over 30 minutes, and the degree of pressure reduction was adjusted to 10 kPa. After holding at that temperature for 10 minutes, the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. After completion of the reaction, nitrogen was discharged from the bottom of the reaction tank under pressure, and while cooling in a water tank, pellets were obtained by cutting with a pelletizer (PC-1).

<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-1, and block polymer D-1 are used, mixed in a weight ratio of 56:12:12:20, and then extruded. supplied to the machine. Extrusion is carried out using a vented twin-screw extruder [Kobe Steel, Ltd. KTX-30] with a diameter of 30 mmφ, with a screw rotation speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum degree of 3 kPa to obtain pellets by melt kneading. Ta. The extrusion temperature was 230° C. from the supply port to the die. A portion of the obtained pellets was dried at 80°C for 6 hours or more in a hot air circulating dryer, and then an injection molding machine was used to set a cylinder temperature of 230°C and a mold temperature of 60°C to prepare a test piece for evaluation. (ISO bending test piece (ISO 178, ISO 179, ISO 75-1 and ISO 75-2 compliant), 3-step plate (1 mmt, 2 mmt, 3 mmt)) and a flat plate of 45 mm long × 50 mm wide × 2 mm thick were molded. The evaluation results are shown in Table 1.

[Example 2]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-1:B-1:C-1:D-1=53:11:11:25, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 1.

[Example 3]
<Production of resin composition>
The same operation as in Example 1 was performed except that the blend weight ratio was PC-1: B-1: C-1: D-1 = 49: 10.5: 10.5: 30. made an evaluation. The results are shown in Table 1.

[Example 4]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-1:B-1:C-1:D-1=45:10:10:35, the same operation as in Example 1 was performed, and the same evaluation was performed. . The results are shown in Table 1.

[Example 5]
<Production of resin composition>
Except for extruding the blend weight ratio PC-1: B-1: C-1: D-1 = 42: 9: 9: 40, exactly the same operation as in Example 1 was performed, and the same evaluation was performed. . The results are shown in Table 1.

[Example 6]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-1: B-1: C-1: D-2 = 53: 11: 11: 25, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 1.

[Example 7]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-1: B-1: C-1: D-3 = 53: 11: 11: 25, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 1.

[Example 8]
<Production of resin composition>
Extrusion was performed with a blend weight ratio of PC-1:B+C:D-1=53:22:25. The results are shown in Table 1.

[Example 9]
<Production of resin composition>
Except for extruding the blend weight ratio PC-1: B-1: C-2: D-1 = 56: 12: 12: 20, exactly the same operation as in Example 1 was performed, and the same evaluation was performed. . The results are shown in Table 1.

[Example 10]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-1:B-1:C-1:D-1=35:20:25:20, the same operation as in Example 1 was performed, and the same evaluation was performed. . The results are shown in Table 1.

[Example 11]
<Production of polycarbonate resin>
Using 294 parts of ISS, 400 parts of SPG, 22 parts of ND and 750 parts of DPC as raw materials, the same operation as in Example 1 was performed to obtain pellets (PC-2).
<Production of resin composition>
Except for extruding the blend weight ratio PC-2: B-1: C-1: D-1 = 56: 10: 14: 20, exactly the same operation as in Example 1 was performed, and the same evaluation was performed. . The results are shown in Table 1.

[Comparative Example 1]
<Production of resin composition>
The same operation as in Example 1 was performed except that the blend weight ratio was extruded with PC-1: B-1: C-1: D-1 = 63: 13.5: 13.5: 10. made an evaluation. The results are shown in Table 2.

[Comparative Example 2]
<Production of resin composition>
The same operation as in Example 1 was performed except that the blend weight ratio was PC-1: B-1: C-1: D-1 = 60: 12.5: 12.5: 15. made an evaluation. The results are shown in Table 2.

[Comparative Example 3]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-1: B-1: C-1: D-4 = 56: 12: 12: 20, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 2.

[Comparative Example 4]
<Production of polycarbonate resin>
450 parts of isosorbide (hereinafter abbreviated as ISS), 67 parts of 1,9-nonanediol (hereinafter abbreviated as ND), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 0.0033 parts of barium stearate as a catalyst under a nitrogen atmosphere. It was heated to 150° C. and melted. After that, the solution was sent to the reaction tank, the temperature of the heat medium in the condenser was adjusted to 40° C., the internal temperature of the resin was adjusted to 170° C., and the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. After that, the degree of pressure reduction was adjusted to 3.4 kPa over 20 minutes, and the temperature was maintained for 10 minutes. Further, the degree of pressure reduction is reduced to 0.9 kPa over 30 minutes, the internal temperature of the resin is adjusted to 220 ° C., and after holding that temperature for 10 minutes, the degree of vacuum is reduced to 0.2 kPa, and the resin temperature is increased from 220 ° C. to 240 ° C. for 30 minutes. After reaching a specified viscosity, the solution was discharged from the bottom of the reactor under nitrogen pressure and cut with a pelletizer while cooling in a water bath to obtain pellets (PC-3).
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-3: B-1: C-1: D-1 = 56: 12: 12: 20, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 2.

[Comparative Example 5]
<Production of polycarbonate resin>
Except for using 354 parts of ISS, 150 parts of 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM) and 750 parts of DPC as starting materials, the same operation as in Example 1 was performed to obtain pellets (PC-4).
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-4: B-1: C-1: D-1 = 56: 12: 12: 20, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 2.

[Comparative Example 6]
<Production of resin composition>
Extrusion was carried out with a blend weight ratio of PC-1:B-1:D-1=56:24:20, but the same operation as in Example 1 was carried out, and the same evaluation was carried out. The results are shown in Table 2.

[Comparative Example 7]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-1: B-1: C-3: D-1 = 56: 12: 12: 20, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 2.

[Comparative Example 8]
<Production of resin composition>
Extrusion was performed with a blend weight ratio of PC-3:D-1=80:20, but the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 9]
<Production of resin composition>
Extrusion was performed with a blend weight ratio of PC-2:D-1=80:20, but the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 10]
<Production of resin composition>
Extrusion was performed with a blend weight ratio of PC-4:D-1=80:20, but the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 11]
<Production of resin composition>
Polycarbonate resin PC-5 and block polymer D-1 were mixed at a weight ratio of 80:20, and then supplied to an extruder. Extrusion is carried out using a vented twin-screw extruder [Kobe Steel, Ltd. KTX-30] with a diameter of 30 mmφ, with a screw rotation speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum degree of 3 kPa to obtain pellets by melt kneading. Ta. The extrusion temperature was 280° C. from the supply port to the die. After drying a part of the obtained pellets at 120 ° C. for 6 hours or more in a hot air circulation dryer, using an injection molding machine, a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. Test pieces for evaluation. (ISO bending test piece (ISO 178, ISO 179, ISO 75-1 and ISO 75-2 compliant), 3-step plate (1 mmt, 2 mmt, 3 mmt)) and a flat plate of 45 mm long × 50 mm wide × 2 mm thick were molded. Table 2 shows the evaluation results.

[Comparative Example 12]
<Production of resin composition>
Extrusion was performed with a blend weight ratio of PC-1:B-1:C-1=70:15:15. The results are shown in Table 2.

[Comparative Example 13]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-2:C-1:D-2=53:22:25, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 2.

[Comparative Example 14]
<Production of resin composition>
Except for extruding with a blend weight ratio of PC-2: B-1: C-1: D-2 = 20: 17: 28: 35, the same operation as in Example 1 was performed and the same evaluation was performed. . The results are shown in Table 2.

[Comparative Example 15]
<Production of resin composition>
Except for extruding the blend weight ratio PC-1: B-1: C-1: D-1 = 35: 7.5: 7.5: 50, the same operation as in Example 1 was performed. made an evaluation. The results are shown in Table 2.

The resin composition of the present invention can be used for optical lenses, optical discs, optical films, plastic substrates, optical cards, liquid crystal panels, headlamp lenses, light guide plates, diffusion plates, protective films, OPC binders, front plates, housings, trays, and water tanks. , lighting covers, signboards, resin windows, and carrier tapes.

Claims (9)

Based on a total of 100 parts by weight of a polycarbonate resin (A) and an acrylic resin (B) containing 5 to 85 mol% of a carbonate structural unit (a) represented by the following formula (1) out of 100 mol% of all carbonate structural units , 5 to 60 parts by weight of an impact modifier (C) having a refractive index of 1.485 or more and 1.495 or less, and a block polymer (D ) containing 22 to 100 parts by weight.
(Wherein, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R is a branched or linear alkyl group having 1 to 20 carbon atoms, or having a substituent represents a cycloalkyl group having 6 to 20 carbon atoms, and m is an integer of 0 to 10.) The polycarbonate resin (A) is composed of a carbonate structural unit (a) represented by the formula (1) and another carbonate structural unit (b), and the carbonate structural unit (b) is an aliphatic diol compound, an alicyclic 2. The resin composition according to claim 1, wherein the carbonate structural unit (b) is derived from at least one compound selected from the group consisting of diol compounds of the formula and aromatic dihydroxy compounds. 3. The resin composition according to claim 1, wherein the weight ratio of the polycarbonate resin (A) and the acrylic resin (B) is 30:70 to 99:1. 4. The resin composition according to any one of claims 1 to 3, wherein the acrylic resin (B) contains 40 to 100 mol% of structural units derived from methyl methacrylate. 5. The resin composition according to any one of claims 1 to 4, wherein a test piece having a thickness of 2 mm has a haze of 15 or less. The resin composition according to any one of claims 1 to 5, which has a notched Charpy impact strength measured according to ISO 179 of 8 kJ/m ² or more. 7. The resin composition according to any one of claims 1 to 6, wherein the molded article has a surface resistivity of 1×10 ¹⁰ (Ω/□) or less. A molded article obtained by injection molding the resin composition according to any one of claims 1 to 7. A film or sheet formed from the resin composition according to any one of claims 1 to 7.