JP2022137822A - Resin composition and its molding - Google Patents

Abstract

To provide a resin composition having a sustainable antistatic property without deteriorating surface hardness compared with a resin to be a base material, while having excellent thermal stability and surface hardness, and impact resistance, and to provide its molding.SOLUTION: A resin composition containing 5 to 60 pts.mass of an impact resistance modifier (C), and 0.1 to 10 pts.mass of an ion pair compound (D) based on a total of 100 pts.mass of a polycarbonate resin (A) and an acrylic resin (B) containing 5 to 85 mol% of a carbonate structural unit (a) represented by a following formula (1) out of 100 mol% of all carbonate structural units, in which the ion pair compound has a melting point of 100°C or less, a 10% weight loss temperature of 250°C or higher as measured by TG-TDA and, satisfies a following formula [I]. RI>RD-30 [I] (RI is a contact angle (°) of a water droplet of a resin composition containing 2 pts.mass of a content of an ion-pair compound, and RD is the contact angle (°) of a water droplet of a polycarbonate resin.)SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing a specific polycarbonate resin, an acrylic resin, an 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.

These polycarbonate resins and acrylic resins have poor antistatic properties, and have the problem that dust tends to adhere to the surface of the molded article due to static electricity. Therefore, in order to solve these problems, there is known a method of adding a hydrophilic polyamide-based polymer such as polyetheresteramide or polyetheramide to impart antistatic performance (Patent Document 3). However, although hydrophilic polyamide-based polymers have the advantage of imparting long-lasting antistatic properties, they have the problem of lowering surface hardness and deflection temperature under load. As another method for solving the problem of antistatic property, a method of adding a surfactant, for example, a method of using a phosphonium sulfonate (Patent Document 4), or a method of using a surfactant such as glycerin fatty acid ester. (Patent Document 5) has been proposed. A method using a specific ion-pair compound has also been proposed (Patent Document 6). However, the methods described in Patent Documents 4 to 6 have not been sufficiently verified because there are no reports on their effects on sustained antistatic properties and surface hardness. In addition, some surfactants and ion pair compounds have a low thermal decomposition temperature, so during processing, not only the antistatic agent decomposes, but also the decomposition product of the antistatic agent decomposes the polycarbonate resin. , The verification of stability against heat (hereinafter referred to as thermal stability) is also insufficient.

Therefore, in the polycarbonate resin composition, a composition that has good thermal stability, surface hardness, and impact resistance without lowering the surface hardness compared to the base resin and has persistent antistatic properties. not previously reported.

U.S. Pat. No. 4,319,003 JP 2015-232091 A JP-A-2002-129026 Japanese Patent No. 4606762 Japanese Patent No. 6215717 Japanese Patent No. 6724737

An object of the present invention is to provide a resin composition that has good thermal stability, surface hardness, and impact resistance, and that has sustained antistatic properties without lowering the surface hardness compared to the base resin, and It is to provide the molded product.

As a result of intensive research, the present inventors have found that a polycarbonate resin containing a specific spiro ring structure contains an acrylic resin, an impact modifier, and an ion pair compound having a specific structure. The inventors have found that a resin composition having excellent stability, surface hardness, impact resistance, and long-lasting antistatic property can be obtained, and have completed the present invention.

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), and 0.1 to 10 parts by weight of an ion pair compound (D), wherein the ion pair compound has a melting point of 100 ° C. or less. A resin composition characterized by having a 10% weight loss temperature of 250° C. or higher as measured by TG-TDA and satisfying the following formula [I].
R _I >R _D −30[I]
(In the formula, _{RI is the contact angle (°) of a water droplet of a resin composition containing 2 parts by weight of an ion-pair compound with respect to 100 parts by weight of a polycarbonate resin, and RD is} the water droplet of the polycarbonate resin. is the contact angle (°) of

(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) is a carbonate structural unit represented by the formula (1) (
a) and another carbonate structural unit (b), wherein the carbonate structural unit (b) is at least one compound selected from the group consisting of aliphatic diol compounds, alicyclic diol compounds and aromatic dihydroxy compounds 2. The resin composition according to the preceding item 1, which is a derived carbonate structural unit (b).

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 the preceding items 1 to 3, wherein the acrylic resin (B) contains 40 to 100 mol% of structural units derived from methyl methacrylate.

5. 5. Any one of the preceding items 1 to 4, wherein the ion pair compound has a 10% weight loss temperature of 270° C. or higher as measured by TG-TDA and satisfies the following formula [II]. of the resin composition.
R _I >R _D -20 [II]
(In the formula, R ₁ is the contact angle (°) of a water droplet of a resin composition containing 2 parts by weight of an ion-pair compound with respect to 100 parts by weight of a polycarbonate resin, and _RD is a water droplet of the polycarbonate resin. is the contact angle (°) of

6. The cation of the ion pair compound contains an organic ammonium ion or an organic phosphonium ion represented by the following formula (3), or the anion of the ion pair compound is a sulfonylimide ion represented by the following formula (4) or the following formula The resin composition according to any one of the preceding items 1 to 5, containing the fluorosulfonate ion represented by (5).

［式中、Ｒ_１、Ｒ_２は炭化水素基、ＭはＮ原子もしくはＰ原子を示す。］

[In the formula, R ₁ and R ₂ represent a hydrocarbon group, and M represents an N atom or a P atom. ]

［式中、Ｒ_３、Ｒ_４はそれぞれパーフルオロアルキル基を示す。］

[In the formula, R ₃ and R ₄ each represent a perfluoroalkyl group. ]

［式中、Ｒ_５はパーフルオロアルキル基を示す。］

[In the formula, R ₅ represents a perfluoroalkyl group. ]

7. The cation of the ion pair compound contains an organic phosphonium ion represented by the following formula (6), or the anion of the ion pair compound is a sulfonylimide ion represented by the following formula (7) or the following formula (8) 7. The resin composition according to any one of the preceding items 1 to 6, containing the fluorosulfonate ion shown.

［式中、Ｒ_１は炭素数１以上のアルキル基、Ｒ_２は炭素数４以上のアルキル基を示す。］

[In the formula, R ₁ represents an alkyl group having 1 or more carbon atoms, and R ₂ represents an alkyl group having 4 or more carbon atoms. ]

［式中、Ｒ_３、Ｒ_４はそれぞれ炭素数１～４のパーフルオロアルキル基を示す。］

[In the formula, R ₃ and R ₄ each represent a perfluoroalkyl group having 1 to 4 carbon atoms. ]

［式中、Ｒ_５は炭素数１～４のパーフルオロアルキル基を示す。］

[In the formula, R ₅ represents a perfluoroalkyl group having 1 to 4 carbon atoms. ]

8. The cation of the ion pair compound contains an organic phosphonium ion represented by the following formula (9), or the anion of the ion pair compound is a sulfonylimide ion represented by the following formula (10) or the following formula (11) 8. The resin composition according to any one of the preceding items 1 to 7, containing the fluorosulfonate ion shown.

［式中、Ｒ_１は炭素数４以上のアルキル基、Ｒ_２は炭素数１２以上のアルキル基を示す。］

[In the formula, R ₁ represents an alkyl group having 4 or more carbon atoms, and R ₂ represents an alkyl group having 12 or more carbon atoms. ]

［式中、Ｒ_３、Ｒ_４はそれぞれトリフルオロメチル基を示す。］

[In the formula, R ₃ and R ₄ each represent a trifluoromethyl group. ]

［式中、Ｒ_５はパーフルオロブチル基を示す。］

[In the formula, R ₅ represents a perfluorobutyl group. ]

9. 9. The resin composition according to any one of the preceding items 1 to 8, having a notched Charpy impact strength measured according to ISO 179 of 10 kJ/m ² or more.

10. 10. The resin composition according to any one of the preceding items 1 to 9, which has a pencil hardness of H or higher as measured according to JIS K5400.

11. 11. The resin composition according to any one of the preceding items 1 to 10, wherein the molded article has a surface resistivity of 1×10 ¹⁵ (Ω/□) or less.

12. A molded article obtained by injection molding the resin composition according to any one of the preceding items 1 to 11.

13. A film or sheet formed from the resin composition according to any one of the preceding items 1 to 11.

According to the present invention, by including an impact modifier and an ion-pair compound having a specific structure in resin components of a polycarbonate resin containing a specific spiro ring structure and an acrylic resin, thermal stability and surface hardness are improved. , impact resistance, and long-lasting 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) preferably contains 15 to 95 mol% in 100 mol% of the total carbonate structural units, more preferably 20 to 90 mol%, more preferably 25 to 85 mol%, 30 to It is particularly preferred to contain 80 mol %. When the carbonate structural unit (b) is within the above range, a resin composition having excellent balance of thermal stability, surface hardness, impact resistance and long-lasting 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. 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. Further examples include bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like.

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. 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 1.0, still more preferably 0.3 to 0.7, 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 improved. 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 having excellent 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 nm or more. It is more preferably 30 nm or more, and still more preferably 50 nm or more. If the average particle size is less than 10 nm, there is a tendency that sufficient impact strength cannot be obtained. 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, that the vinyl-based monomer is at least one selected from (meth)acrylic acid monomers and (meth)acrylic acid alkyl ester monomers, so that the impact strength of the resin composition of the present invention can be improved; Furthermore, it is preferable from the viewpoint of raw material cost.

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.

Further, the impact modifier (C) used in the present invention can impart transparency by using those having a refractive index of 1.485 or more and 1.495 or less. In that case, the refractive index is preferably 1.487 or more and 1.494 or less, more preferably 1.490 or more and 1.493 or less.

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 the acrylic resin (B) contains the impact modifier (C) in advance, and the polycarbonate resin contains the impact modifier (C). 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.

(Ion pair compound (D))
The ion pair compound used in the present invention is used as an antistatic agent, has a melting point of 100° C. or lower, a 10% weight loss temperature measured by TG-TDA of 250° C. or higher, and has the following formula [I]: Be satisfied.
R _I >R _D −30[I]
(In the formula, _{RI is the contact angle (°) of a water droplet of a resin composition containing 2 parts by weight of an ion-pair compound with respect to 100 parts by weight of a polycarbonate resin, and RD is} the water droplet of the polycarbonate resin. is the contact angle (°) of

The necessity for the ion-pair compound to have a melting point of 100° C. or less will be explained below. It is known that the addition of an ion-pair compound having a low melting point, especially an ion-pair compound that is liquid at room temperature, to the resin will impart antistatic properties to the resin composition. The reason for this is that the ion-pair compound with a low melting point has an organic compound site with a relatively large size. It is believed that it disperses appropriately in the resin composition and exhibits antistatic properties. In particular, when considering addition to polycarbonate resin, those having a melting point of 100° C. or less are suitable for imparting good antistatic properties. On the contrary, the ion-pair compound having a melting point exceeding 100° C. has a strong Coulomb force or a small organic compound site and low affinity with the resin, so that it is difficult to disperse in the aromatic polycarbonate resin and has good antistatic properties. does not demonstrate The melting point of the ion pair compound is preferably 90° C. or less.

The necessity for the 10% weight loss temperature measured by TG-TDA to be 250° C. or higher will be explained below. If this temperature is low, thermal decomposition of the ion-pair compound is likely to occur in an environment where the resin compound is exposed to high temperatures such as melt-kneading and injection molding, and the compound generated by the thermal decomposition is the heat of the resin polymer. It also contributes to decomposition, causing problems such as molding instability and deterioration of mechanical properties due to a decrease in molecular weight. The 10% weight loss temperature of the ion pair compound measured by TG-TDA is preferably 260° C. or higher, more preferably 270° C. or higher.

The reason why the formula [1] should be satisfied will be explained below. The more hydrophobic the ion-pair compound is, the more the ion-pair compound is prevented from being eluted into water when the resin composition containing the ion-pair compound comes into contact with water, thereby improving the sustained antistatic property. The degree of hydrophobicity of the ion-pair compound can be defined by the contact angle of a water droplet with respect to the resin composition to which the ion-pair compound is added. If the formula [I] is not satisfied, it means that the ion-pair compound exhibits more hydrophilicity, so when the resin composition contacts water, the ion-pair compound is more eluted into water, and the Antistatic property cannot be secured. Furthermore, it is more preferable that the following formula [II] is satisfied in order to secure a better lasting antistatic property.
R _I >R _D -20 [II]
(In the formula, _{RI is the contact angle (°) of a water droplet of a resin composition containing 2 parts by weight of an ion-pair compound with respect to 100 parts by weight of a polycarbonate resin, and RD is} the water droplet of the polycarbonate resin. is the contact angle (°) of

An ion-pair compound having a melting point of 100° C. or lower, a 10% weight loss temperature measured by TG-TDA of 250° C. or higher, and satisfying the formula [1] has a cation represented by the following formula (3). or the anion preferably contains a sulfonylimide ion represented by the following formula (4) or a fluorosulfonate ion represented by the following formula (5).

［式中、Ｒ_１、Ｒ_２は炭化水素基、ＭはＮ原子もしくはＰ原子を示す。］

[In the formula, R ₁ and R ₂ represent a hydrocarbon group, and M represents an N atom or a P atom. ]

［式中、Ｒ_３、Ｒ_４はそれぞれパーフルオロアルキル基を示す。］

[In the formula, R ₃ and R ₄ each represent a perfluoroalkyl group. ]

［式中、Ｒ_５はパーフルオロアルキル基を示す。］

[In the formula, R ₅ represents a perfluoroalkyl group. ]

In formula (3), M is preferably a P atom, R ₁ is preferably an alkyl group having 1 or more carbon atoms, and R ₂ is preferably an alkyl group having 4 or more carbon atoms. More preferably, R ₁ is an alkyl group with 4 or more carbon atoms, and R ₂ is an alkyl group with 12 or more carbon atoms. R ₁ is preferably an alkyl group having 10 or less carbon atoms, and R ₂ is preferably an alkyl group having 20 or less carbon atoms.

In formula (4), each of R ₃ and R ₄ is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a trifluoromethyl group. In formula (5), R ₅ is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a perfluorobutyl group.

(Method for Producing Resin Composition Containing Polycarbonate Resin, Acrylic Resin, Impact Modifier, and Ion Pair Compound)
The resin composition of the present invention is preferably a blend of a polycarbonate resin, an acrylic resin, an impact modifier and an antistatic agent 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 temperature of the molten resin 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 the amount in the above range, a resin composition having excellent surface hardness 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 the amount in the above range, it is possible to obtain a resin composition having excellent surface hardness and impact resistance.

The ion pair compound (D) used in the present invention is contained in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the polycarbonate resin and the acrylic resin. It is preferably in the range of 0.3 to 8 parts by weight, more preferably in the range of 0.5 to 7 parts by weight, still more preferably in the range of 1 to 6 parts by weight. A resin composition having excellent stability, surface hardness, impact resistance, and long-lasting antistatic properties can be obtained.

(Additive)
The resin composition of the present invention may contain a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, a surfactant, an antibacterial agent, an ultraviolet absorber, and a separator according to the application and need. Additives such as a mold agent and a coloring agent can be added.

(Heat stabilizer)
The resin composition of 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, among which 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 of the present invention may be blended with a releasing agent in order to further improve the releasability from the mold during melt molding, as long as the object of the present invention is not impaired.

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 of 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 of 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 of the present invention, an epoxy compound can be blended as long as the object of the present invention is not impaired.

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-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate 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 of the present invention can be blended with a bluing agent in order to cancel the yellow tint of the lens due to the polymer or 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 of 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, etc. can be used as a molded product. In particular, it can be used as members requiring high surface hardness, such as front plates, housings, trays, water tanks, lighting covers, signboards, and resin windows.

(Impact strength)
The resin composition of the present invention preferably has a notched Charpy impact strength of 10 kJ/m ² or more, more preferably 11 kJ/m ² or more, and 12 kJ/m ² or more, measured according to ISO 179. is more preferable, and 13 kJ/m ² or more is particularly preferable. A notched Charpy impact strength of 100 kJ/m ² or less provides a sufficient function.

(Pencil hardness)
The resin composition of the present invention preferably has a pencil hardness of H or higher. It is more preferably 2H or more in terms of better scratch resistance. A pencil hardness of 4H or less has sufficient functions. The pencil hardness can be increased by increasing the weight ratio of the acrylic resin. In the present invention, the pencil hardness is a hardness that does not leave a scratch mark even when the resin composition of the present invention is rubbed with a pencil having a specific pencil hardness.
It is preferable to use the pencil hardness used for the surface hardness test of the coating film, which can be measured according to K-5600, as an index. Pencil hardness is 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B in order of softness, with 9H being the hardest and 9H being the hardest. A soft one is 6B.

(Antistatic property)
The resin composition of the present invention has a surface specific resistivity of 1×10 ¹⁵ 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 1×10 ¹⁴ Ω/□ or less, more preferably 1×10 ¹³ 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.

[Evaluation method]
<Evaluation of polycarbonate resin>
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]

<Evaluation of ion pair compound>
1. Melting point A liquid at room temperature (20°C) is described as <20°C. For those that are not liquid at room temperature, a DSC analyzer (NETZSCH DSC214) is used, and the peak position corresponding to the melting point is read from the chart of the amount of heat versus temperature obtained under the conditions of a heating rate of 10 ° C./min. described as

2. Heat resistance Using a TG-DTA analyzer (Rigaku Thermo plus EVO2), the 10% weight loss temperature was measured in an air atmosphere at a heating rate of 20°C/min.

<Evaluation of Resin Composition>
1. Hydrophilicity of molded product surface Using a contact angle measurement device (GI-1000 manufactured by Elma Sales Co., Ltd.), the water droplet contact angle (R _D ) of the polycarbonate resin and the polycarbonate resin 100 under the conditions of 23 ° C. × 50% A water droplet contact angle (R _I ) of a resin composition containing 2 parts by weight of each ion-pair compound per part by weight was measured by dropping a water droplet onto a flat test piece obtained by injection molding.

2. Antistatic property (before wiping with water)
A flat test piece of 45 mm x 50 mm x 2 mm was prepared by injection molding under the above conditions and measured under the following conditions. That is, after preparing a flat test piece under the conditions of 23 ° C. and 50% relative humidity for 48 hours or more, a resistivity meter (Mitsubishi Chemical Analic high resistance resistivity meter MCP-HT450) was used. , the surface specific resistivity was measured under the conditions of a measurement voltage of 1000V. A smaller value indicates better antistatic performance. A when the surface resistivity is 1×10 ¹⁴ Ω/□ or less, ○ when the surface resistivity is greater than 1×10 ¹⁴ Ω/□ and 1×10 ¹⁵ Ω/□ or less, and greater than 1×10 ¹⁵ Ω/□. In case x.

3. Antistatic property (after wiping with water)
A 500 g cylindrical weight was wrapped in water-wet Kimtowel (manufactured by Nippon Paper Crecia Co., Ltd.), placed on the flat test piece, and slid 10 times to wipe the surface with water. The surface was then lightly wiped three times with a dry Kimwipe to wipe off water droplets. After that, the above 2. The surface resistivity was evaluated by the same method. ◎ when the surface resistivity is 1×10 ¹⁴ Ω/□ or less, 1×10
When the resistance was greater than ¹⁴ Ω/□ and 1×10 ¹⁵ Ω/□ or less, it was evaluated as ○, and when it was greater than 1×10 ¹⁵ Ω/□, it was evaluated as ×.

4. Thermal Stability In injection molding, the viscosity-average molecular weight (M ₁ ) of the molded product injected after the resin was retained in the cylinder for 10 minutes and the viscosity-average molecular weight (M ₀ ) of the melt-kneaded pellet were measured. A case where M ₀ −M ₁ ≦1,000 was satisfied was evaluated as ○, and a case where it was not satisfied was evaluated as ×.

The viscosity-average molecular weight referred to in the present invention is obtained by first measuring the specific viscosity (η _SP ) calculated by the following formula [III] at 20° C. with an Ostwald viscometer using a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride. and the viscosity-average molecular weight M was calculated from the obtained specific viscosity (η _SP ) by the following formulas [IV] and [V].
Specific viscosity (η _SP ) = (tt ₀ )/t ₀ [III]
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity) [IV]
[η]=1.23×10 ⁻⁴ M ^0.83 [V]

5. Surface hardness (pencil hardness)
Based on JIS K5400, a line was drawn on the surface of the molded product in a constant temperature room with an ambient temperature of 23 ° C. while a pencil was kept at an angle of 45 degrees and a load of 750 g was applied, and the surface condition was visually evaluated. . Those with a pencil hardness of 2H or more were evaluated as ⊚, those with H were evaluated as O, and those with F or less were evaluated as X.

6. 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. A sample with a Charpy impact strength of 10 kJ/m ² or more was rated ○, and a sample with a Charpy impact strength of less than 10 kJ/m ² was rated x.

[Resins and additives used]
<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

<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

<Impact modifier (C)>
C-1 (Example): Kaneace M-230 manufactured by Kaneka
C-2 (Example): Metabrene W-377 manufactured by Mitsubishi Chemical Corporation
C-3 (Example): Metabrene E-870A manufactured by Mitsubishi Chemical Corporation

<Ion pair compound (D)>
D-1: trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide (manufactured by Kanto Chemical Co., Ltd.)
D-2: tributyl (dodecyl) phosphonium bis (trifluoromethylsulfonyl) imide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
D-3: 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (P12N111 manufactured by Mitsubishi Materials Corporation)
D-4: 1-ethylpyridinium bis(trifluoromethylsulfonyl)imide (EPYN111 manufactured by Mitsubishi Materials Corporation)
D-5: 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIN111 manufactured by Mitsubishi Materials Corporation)
D-6: 1-butyl-3-methylimidazolium perfluorobutanesulfonate (BMIEF41 manufactured by Mitsubishi Materials Corporation)
D-7: 1-butyl-3-methylimidazolium dicyanamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-8 (comparative example): 1-butyl-3-methylimidazolium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
D-9 (Comparative Example): Potassium perfluorobutanesulfonate (Dainippon Ink and Chemicals Co., Ltd. Megafac F-114P)
D-10 (comparative example): dodecylbenzenesulfonic acid tetrabutylphosphonium salt (DBS-P) (manufactured by Takemoto Yushi Co., Ltd.)

<Other ingredients>
E: Surfactant-type antistatic agent (non-ionic pair) (Poem DL-100 manufactured by Riken Vitamin Co., Ltd.)
F: A block polymer having a structure in which polyamide blocks and polyether blocks are ester-bonded (Pelestat NC6321 manufactured by Sanyo Chemical Industries, Ltd.)

[Reference 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 reactor under pressure, and while cooling in a water bath, pellets were obtained by cutting with a pelletizer (PC-1).

<Production of resin composition>
Polycarbonate resin PC-1 and ion pair compound D-1 were used and mixed in a weight ratio of 100:2, and fed to an extruder. For extrusion, a vented twin-screw extruder [Kobe Steel, Ltd. KTX-30] with a diameter of 30 mmφ is used, and the screw rotation speed is 150 rpm, the discharge rate is 20 kg / h, and the vacuum degree of the vent is 3 kPa to obtain pellets by melt kneading. rice field. The extrusion temperature was 250° C. from the supply port to the die. After drying a part of the obtained pellets at 90°C for 6 hours or more in a hot air circulation dryer, using an injection molding machine, the cylinder temperature is 250°C and the mold temperature is 70°C. A plate (1 mmt, 2 mmt, 3 mmt)) was molded, and the hydrophilicity of the surface of the molded product was evaluated by a water drop contact angle drop test. The evaluation results are shown in Table 1.

[Reference Examples 2 to 7]
<Production of resin composition>
Except that the polycarbonate resin PC-1 and the ion pair compounds D-2 to D-7 were used and mixed so that the weight ratio was 100:2, the same operation as in Reference Example 1 was performed, and the same evaluation was performed. did In addition, Reference Example 2 is ion-pair compound D-2, Reference Example 3 is ion-pair compound D-3, Reference Example 4 is ion-pair compound D-4, Reference Example 5 is ion-pair compound D-5, Reference Example 6 corresponds to the case of using the ion-pair compound D-6, and Reference Example 7 corresponds to the case of using the ion-pair compound D-7. The evaluation results are shown in Table 1.

[Reference Comparative Examples 1 to 3]
<Production of resin composition>
Except that the polycarbonate resin PC-1 and the ion pair compounds D-8 to D-10 were used and mixed so that the weight ratio was 100:2, the same operation as in Reference Example 1 was performed, and the same evaluation was performed. did Incidentally, Reference Comparative Example 1 corresponds to the case of using the ion-pair compound D-8, Reference Comparative Example 2 to the case of using the ion-pair compound D-9, and Reference Comparative Example 3 to the case of using the ion-pair compound D-10. The evaluation results are shown in Table 1. When the ion-pair compound D-8 was used, thermal decomposition occurred during molding, and a molded product could not be obtained.

[Examples 1 to 5, Comparative Example 1]
<Production of resin composition>
Polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion-pair compound D-1 were used and mixed in a weight ratio of 70:30:1 to 70:30:11. Melt-kneading and injection molding were carried out in exactly the same manner as in 1 to form a three-stage plate (1 mmt, 2 mmt, 3 mmt) for evaluation. Antistatic properties, surface hardness, and impact resistance were evaluated using the molded three-stage plate based on the evaluation methods described above. In addition, during injection molding, a molded product (retention molded product) that was injected after the resin was retained in the cylinder for 10 minutes was also produced, and the viscosity average molecular weight of the melt-kneaded pellet and the retention molded product was measured. Thermal stability was evaluated. As the polymerization ratio of the ion pair compound D-1, Example 1 has a polymerization ratio of 1, and Example 2
is a polymerization ratio of 2, Example 3 has a polymerization ratio of 3, Example 4 has a polymerization ratio of 5, Example 5 has a polymerization ratio of 8, and Comparative Example 1 has a polymerization ratio of 11. The evaluation results are shown in Tables 2 and 3.

[Example 6]
<Production of resin composition>
Exactly the same as in Example 1 except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-2 were used and mixed in a weight ratio of 70:30:2. Operation was performed, and the same evaluation was performed. The evaluation results are shown in Table 2.

[Examples 7-8]
<Production of resin composition>
Polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-3 were used and mixed in a weight ratio of 70:30:2 to 70:30:5. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. As for the polymerization ratio of the ion pair compound D-3, Example 7 corresponds to the polymerization ratio of 2, and Example 8 corresponds to the polymerization ratio of 5. The evaluation results are shown in Table 2.

[Example 9]
<Production of resin composition>
Exactly the same as in Example 1 except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion-pair compound D-4 were used and mixed in a weight ratio of 70:30:2. Operation was performed, and the same evaluation was performed. The evaluation results are shown in Table 2.

[Examples 10-11]
<Production of resin composition>
Polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-5 were used and mixed in a weight ratio of 70:30:2 to 70:30:5. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. As for the polymerization ratio of the ion pair compound D-5, Example 10 corresponds to the polymerization ratio of 2, and Example 11 corresponds to the polymerization ratio of 5. The evaluation results are shown in Table 2.

[Examples 12-13]
<Production of resin composition>
Polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-6 were used and mixed in a weight ratio of 70:30:2 to 70:30:5. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. As for the polymerization ratio of the ion pair compound D-6, Example 12 corresponds to a polymerization ratio of 2, and Example 13 corresponds to a polymerization ratio of 5. The evaluation results are shown in Table 2.

[Example 14]
<Production of resin composition>
Exactly the same as in Example 1 except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-7 were used and mixed in a weight ratio of 70:30:2. Operation was performed, and the same evaluation was performed. The evaluation results are shown in Table 2.

[Comparative Example 2]
<Production of resin composition>
Exactly the same as in Example 1 except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-8 were used and mixed in a weight ratio of 70:30:2. attempted the operation. However, the resin deteriorated greatly due to the heat during processing, and a sample could not be obtained.

[Comparative Example 3]
<Production of resin composition>
Exactly the same as in Example 1 except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-9 were used and mixed in a weight ratio of 70:30:2. Operation was performed, and the same evaluation was performed. The evaluation results are shown in Table 3.

[Comparative Example 4]
<Production of resin composition>
Exactly the same as in Example 1 except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and ion pair compound D-10 were used and mixed in a weight ratio of 70:30:2. Operation was performed, and the same evaluation was performed. The evaluation results are shown in Table 3.

[Comparative Example 5]
<Production of resin composition>
Exactly the same operation as in Example 1 was performed except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and antistatic agent E were used and mixed in a weight ratio of 70:30:2. and performed the same evaluation. The evaluation results are shown in Table 3.

[Comparative Examples 6-7]
<Production of resin composition>
Example 1 except that polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and antistatic agent F were used and mixed at a weight ratio of 70:30:4 to 70:30:10. Exactly the same operation was performed and the same evaluation was performed. As for the polymerization ratio of the antistatic agent F, Comparative Example 6 corresponds to the polymerization ratio of 4, and Comparative Example 7 corresponds to the polymerization ratio of 10. The evaluation results are shown in Table 3.

[Examples 15-16]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-1, and ion pair compound D-1 are used, and the weight ratio is 70:15:15:2 to 70:15:15:5. Except that the mixture was mixed to obtain As for the polymerization ratio of the ion pair compound D-6, Example 15 corresponds to a polymerization ratio of 2, and Example 16 corresponds to a polymerization ratio of 5. The evaluation results are shown in Table 4.

[Example 17]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-1, and ion pair compound D-3 were used and mixed in a weight ratio of 70:15:15:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 4.

[Example 18]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-1, and ion pair compound D-6 were used and mixed in a weight ratio of 70:15:15:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 4.

[Example 19]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-2, and ion-pair compound D-1 were used and mixed at a weight ratio of 70:15:15:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 4.

[Example 20]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-3, and ion pair compound D-1 were used and mixed in a weight ratio of 70:15:15:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 4.

[Example 21]
<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 Reference Example 1 was performed to obtain pellets (PC-2).
<Production of resin composition>
Polycarbonate resin PC-2, acrylic resin B-1, impact modifier C-1, and ion pair compound D-1 were used and mixed in a weight ratio of 70:10:20:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 4.
Further, the polycarbonate resin PC-2 and the ion pair compound D-1 were mixed at a ratio of 100:2, and the same operation as in Reference Example 1 was performed. When the properties were evaluated, the water droplet contact angle _R1 was 70°. The water droplet contact angle _RD on the surface of the molded article obtained only from the polycarbonate resin PC-2 was 76°.

[Example 22]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-1, and ion-pair compound D-1 were used and mixed in a weight ratio of 40:30:30:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 4.

[Example 23]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-1, and ion pair compound D-1 were used and mixed in a weight ratio of 80:10:10:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 4.

[Comparative Example 8]
<Production of resin composition>
Polycarbonate resin PC-1, acrylic resin B-1, impact modifier C-1, and ion pair compound D-10 were used and mixed in a weight ratio of 70:15:15:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 5.

[Comparative Example 9]
<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 was reduced to 0.9 kPa over 30 minutes, the internal temperature of the resin was adjusted to 220 ° C., and after holding at that temperature for 10 minutes, the degree of vacuum was 0.2 k.
Pa, the resin temperature is raised from 220 ° C. to 240 ° C. over 30 minutes, and after reaching a specified viscosity, the resin is discharged from the bottom of the reaction tank under nitrogen pressure, cooled in a water tank, and cut with a pelletizer to form pellets. obtained (PC-3). Using the obtained pellets, injection molding was performed in the same manner as in Example 1, and the same evaluation was performed. The evaluation results are shown in Table 5.

[Comparative Example 10]
<Production of resin composition>
Except that polycarbonate resin PC-3 and ion-pair compound D-1 were used and mixed in a weight ratio of 100:2, the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 5.

[Comparative Example 11]
Exactly the same operation as in Example 1 except that polycarbonate resin PC-3, impact modifier C-1, and ion-pair compound D-1 were used and mixed in a weight ratio of 70:30:2. and evaluated in the same way. The evaluation results are shown in Table 5.

[Comparative Example 12]
Exactly the same as in Example 1 except that polycarbonate resin PC-3, impact modifier composite acrylic resin B+C, and ion pair compound D-1 were used and mixed in a weight ratio of 70:30:2. Operation was performed, and the same evaluation was performed. The evaluation results are shown in Table 5.

[Comparative Example 13]
Polycarbonate resin PC-3, acrylic resin B-1, impact modifier C-1, and ion-pair compound D-1 were used and mixed at a weight ratio of 70:15:15:2. Exactly the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 5.

[Comparative Example 14]
Exactly the same operation as in Example 1 was performed, except that polycarbonate resin PC-1, acrylic resin B-1, and ion pair compound D-1 were used and mixed in a weight ratio of 70:30:2. A similar evaluation was performed. The evaluation results are shown in Table 5.

[Comparative Example 15]
<Production of resin composition>
Except that polycarbonate resin PC-1 and ion-pair compound D-1 were used and mixed at a weight ratio of 100:2, the same operation as in Example 1 was performed and the same evaluation was performed. The evaluation results are shown in Table 5.

[Comparative Example 16]
<Production of resin composition>
Exactly the same operation as in Example 1, except that polycarbonate resin PC-1, impact modifier C-1, and ion pair compound D-1 were used and mixed in a weight ratio of 70:30:2. and evaluated in the same way. The evaluation results are shown in Table 5.

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, and resin windows.

Claims (13)

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), and 0.1 to 10 parts by weight of an ion pair compound (D), wherein the ion pair compound has a melting point of 100 ° C. or less. A resin composition characterized by having a 10% weight loss temperature of 250° C. or higher as measured by TG-TDA and satisfying the following formula [I].
R _I >R _D −30[I]
(In the formula, _{RI is the contact angle (°) of a water droplet of a resin composition containing 2 parts by weight of an ion-pair compound with respect to 100 parts by weight of a polycarbonate resin, and RD is} the water droplet of the polycarbonate resin. is the contact angle (°) of

(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) 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 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. The ion pair compound according to any one of claims 1 to 4, wherein the 10% weight loss temperature measured by TG-TDA is 270 ° C. or higher and satisfies the following formula [II]. The described resin composition.
R _I >R _D -20 [II]
(In the formula, R ₁ is the contact angle (°) of a water droplet of a resin composition containing 2 parts by weight of an ion-pair compound with respect to 100 parts by weight of a polycarbonate resin, and _RD is a water droplet of the polycarbonate resin. is the contact angle (°) of The cation of the ion pair compound contains an organic ammonium ion or an organic phosphonium ion represented by the following formula (3), or the anion of the ion pair compound is a sulfonylimide ion represented by the following formula (4) or the following formula 6. The resin composition according to any one of claims 1 to 5, comprising a fluorosulfonate ion represented by (5).

[In the formula, R ₁ and R ₂ represent a hydrocarbon group, and M represents an N atom or a P atom. ]

[In the formula, R ₃ and R ₄ each represent a perfluoroalkyl group. ]

[In the formula, R ₅ represents a perfluoroalkyl group. ] The cation of the ion pair compound contains an organic phosphonium ion represented by the following formula (6), or the anion of the ion pair compound is a sulfonylimide ion represented by the following formula (7) or the following formula (8) A resin composition according to any one of claims 1 to 6, comprising the indicated fluorosulfonate ion.

[In the formula, R ₁ represents an alkyl group having 1 or more carbon atoms, and R ₂ represents an alkyl group having 4 or more carbon atoms. ]

[In the formula, R ₃ and R ₄ each represent a perfluoroalkyl group having 1 to 4 carbon atoms. ]

[In the formula, R ₅ represents a perfluoroalkyl group having 1 to 4 carbon atoms. ] The cation of the ion pair compound contains an organic phosphonium ion represented by the following formula (9), or the anion of the ion pair compound is a sulfonylimide ion represented by the following formula (10) or the following formula (11) A resin composition according to any one of claims 1 to 7, comprising the indicated fluorosulfonate ion.

[In the formula, R ₁ represents an alkyl group having 4 or more carbon atoms, and R ₂ represents an alkyl group having 12 or more carbon atoms. ]

[In the formula, R ₃ and R ₄ each represent a trifluoromethyl group. ]

[In the formula, R ₅ represents a perfluorobutyl group. ] The resin composition according to any one of claims 1 to 8, wherein the notched Charpy impact strength measured according to ISO 179 is 10 kJ/m ² or more. The resin composition according to any one of claims 1 to 9, which has a pencil hardness of H or higher as measured according to JIS K5400. The resin composition according to any one of claims 1 to 10, wherein the molded product has a surface resistivity of 1 × 10 ¹⁵ (Ω/□) or less. A molded article obtained by injection molding the resin composition according to any one of claims 1 to 11. A film or sheet formed from the resin composition according to any one of claims 1 to 11.