JP2022137821A - Resin composition and molded article of the same - Google Patents

Abstract

To provide a resin composition which suppresses yellow discoloration due to a thermal history in molding, and has characteristics excellent in transparency, surface hardness, impact resistance, moist heat resistance and light resistance.SOLUTION: A resin composition contains 10-30 pts.wt. of a methyl methacrylate-alkyl acrylate-styrene copolymer (C), and 1-30 pts.wt. of an epoxy resin (D) based on 100 pts.wt. of the sum of a polycarbonate resin (A) containing 5-85 mol% of units (a) whose repeating unit is represented by a following formula (1), and a methyl methacrylate-methyl acrylate copolymer (B), and has a refraction index of the methyl methacrylate-alkyl acrylate-styrene copolymer (C) of 1.485 or more and 1.495 or less. (W is a 1-20C alkylene group, or a 6-20C cycloalkylene group, R is a 1-20C branched or linear alkyl group, or a 6-20C cycloalkylene group which may have a substituent group, and m is an integral number of 0-10.)SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing a specific polycarbonate resin, a methyl methacrylate-methyl acrylate copolymer, a methyl methacrylate-alkyl acrylate-styrene copolymer and an epoxy resin, and a molded article thereof.

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 polycarbonate resin generally does not have excellent weather resistance compared to other transparent materials such as acrylic resins. Yellowing 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, it has been found that the resin composition described in Patent Document 2 has a problem in impact resistance and has a low Charpy impact strength. Furthermore, it has been found that the resin composition described in Patent Document 2 is remarkably deteriorated in wet heat resistance and light resistance. Therefore, in the resin composition of a polycarbonate resin and an acrylic resin, a resin composition that suppresses yellowing during molding and has good transparency, surface hardness, impact resistance, moist heat resistance and light resistance has been reported so far. was not

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

An object of the present invention is to provide a resin composition that suppresses yellowing due to heat history during molding and has excellent properties such as transparency, surface hardness, impact resistance, moist heat resistance and light resistance.

As a result of extensive research, the present inventors have found that polycarbonate resins containing a specific spiro ring structure include methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-alkyl acrylate-styrene copolymer and epoxy resin. By containing a resin, it was found that a resin composition having excellent properties such as suppression of yellowing due to heat history during molding, transparency, surface hardness, impact resistance, moist heat resistance and light resistance, and the present invention. was completed.

That is, according to the present invention, the objects of the invention are achieved by the following.

1. A total of 100 weights of a polycarbonate resin (A) containing 5 to 85 mol% of units (a) whose repeating units are represented by the following formula (1) and a methyl methacrylate-methyl acrylate copolymer (B) 10 to 30 parts by weight of methyl methacrylate-alkyl acrylate-styrene copolymer (C) and 1 to 30 parts by weight of epoxy resin (D), and the methyl methacrylate-alkyl acrylate - A resin composition, wherein the styrene copolymer (C) has a refractive index of 1.485 or more and 1.495 or less.

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

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

3. 3. The resin composition according to item 1 or 2, wherein the weight ratio of the polycarbonate resin (A) and the methyl methacrylate-methyl acrylate copolymer (B) is 50:50 to 99:1.

4. 4. The resin composition according to any one of 1 to 3 above, wherein the methyl methacrylate-methyl acrylate copolymer (B) contains 40 to 100 mol % of repeating units derived from methyl methacrylate.

5. 5. The resin composition according to any one of 1 to 4 above, wherein the epoxy resin (D) has a molecular weight of 3,000 to 20,000.

6. The resin composition according to any one of 1 to 5 above, wherein a test piece having a thickness of 6.2 mm has a haze of 10% or less.

7. A molded article obtained by molding the resin composition according to any one of 1 to 6 above.

8. A film or sheet formed from the resin composition according to any one of the preceding Items 1 to 6.

The present invention provides a composition of a polycarbonate resin containing a specific spiro ring structure and a methyl methacrylate-methyl acrylate copolymer, a methyl methacrylate-alkyl acrylate-styrene copolymer (C) and an epoxy resin ( By including D), it has become possible to provide a resin composition having excellent properties such as transparency, surface hardness, impact resistance, moist heat resistance and light resistance. Therefore, its industrial effect is exceptional.

The present invention will be described in detail below.

(polycarbonate resin)
The polycarbonate resin used in the resin composition of the present invention is a polycarbonate resin (A) containing 5 to 85 mol % of carbonate units (a) whose repeating units are represented by the following formula (1) in all repeating 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 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 repeating unit (a) represented by the above formula (1) in the total repeating units, and may contain 10 to 80 mol%. Preferably, it is contained in an amount of 15 to 75 mol%, more preferably 20 to 70 mol%. When the unit (a) is within the above range, the resin composition does not become cloudy due to phase separation during extrusion or molding of the resin composition with the acrylic resin, and crystallizes during polymerization of the polycarbonate resin. It is preferable because polymerization is easy without

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

The carbonate unit (b) is preferably a carbonate unit (b) derived from at least one compound selected from the group consisting of aliphatic diol compounds, alicyclic diol compounds and aromatic dihydroxy compounds. Further, the carbonate unit (b) is a carbonate 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. is preferred.

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.

Carbonate unit (b) preferably contains 15 to 95 mol% of all repeating units, more preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and 30 to 80 mol%. is particularly preferred. When the unit (b) is within the above range, a resin composition having a more excellent balance of transparency, surface hardness and impact resistance can be obtained.

(Method for producing polycarbonate resin)
The polycarbonate resin 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. It is selected in the range of 10 ⁻⁷ to 1×10 ⁻³ equivalents.

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

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

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

(Specific viscosity: 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.

(Methyl methacrylate-methyl acrylate copolymer)
As the acrylic resin used in the resin composition of the present invention, a methyl methacrylate-methyl acrylate copolymer (B), which is an acrylic resin as a thermoplastic resin, is used.

Monomers other than methyl methacrylate and methyl acrylate can also be used, and examples of monomers used for copolymerization include the following compounds. For example, methacrylic acid, acrylic acid, benzyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate Acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate , isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, acrylic ( meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, hexa 2-(meth)acryloyloxyethyl hydrophthalate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, Examples include cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, cyclododecyl acrylate and the like. In addition, other monomers that can be polymerized with these acrylic monomers, such as polyolefin monomers and vinyl monomers (excluding styrene), may be used in combination. These may be used by polymerizing two or more kinds.

The methyl methacrylate-methyl acrylate copolymer (B) preferably contains 40 to 100 mol%, more preferably 50 to 100 mol%, more preferably 60 to 99 mol% of methyl methacrylate as a monomer component. preferable. When the ratio of methyl methacrylate as a monomer component is within the above range, the heat decomposition resistance is excellent, molding defects such as silver are less likely to occur during molding, and the heat distortion temperature is favorable.

The molecular weight of the methyl methacrylate-methyl acrylate copolymer is not particularly limited. It is possible to provide a composition excellent in mechanical properties and heat resistance without causing poor appearance.

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.

(Methyl methacrylate-alkyl acrylate-styrene copolymer)
The resin composition of the present invention contains a methyl methacrylate-alkyl acrylate-styrene copolymer (C) as an impact modifier. The methyl methacrylate-alkyl acrylate-styrene copolymer is preferably of a core-shell type consisting of a core that is a rubber-like polymer and a shell obtained by graft polymerization to the rubber-like polymer. By using a core-shell type impact modifier of methyl methacrylate-alkyl acrylate-styrene copolymer, dispersibility in polycarbonate is improved, and high impact strength and good light resistance tend to be obtained.

The average particle size of the impact modifier is preferably 5-500 nm. It is more preferably 7 to 300 nm, still more preferably 9 to 200 nm, and most preferably 10 to 180 nm. When the average particle size is 5 nm or more, sufficient impact strength can be obtained. Moreover, when the average particle size is 500 nm or less, the obtained resin composition is more excellent in transparency. Incidentally, the average particle size is measured in the latex state of the rubber-like polymer and the graft copolymer. As a measuring device, MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. can be used to measure the volume average particle size.

The rubber-like polymer corresponding to the core of the impact modifier contains a methyl methacrylate-alkyl acrylate copolymer, so that both transparency and impact resistance of the resin composition of the present invention can be achieved. It is preferable from the viewpoint of raw material cost.

Specific examples of alkyl acrylates include ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

Monomers other than methyl methacrylate and alkyl acrylate can also be used, and examples of monomers used for copolymerization include acrylic acid, methacrylic acid, ethyl methacrylate, butyl methacrylate, methacrylic acid 2-hydroxyethyl, glycidyl methacrylate and the like.

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 methyl methacrylate-alkyl acrylate-styrene copolymer (C) preferably contains a styrene polymer. Monomers other than styrene can also be used, and aromatic vinyl compounds such as α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, are preferred. unsaturated carboxylic acids such as acrylic acid esters and methacrylic acid esters having alkyl esters of , unsaturated carboxylic acid esters, and the like. The shell portion can be formed by graft polymerizing the monomers described above.

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

The impact modifier used in the present invention has a refractive index of 1.485 or more and 1.495 or less, preferably 1.487 or more and 1.494 or less, more preferably 1.490 or more and 1.493 or less. be. When the refractive index of the methyl methacrylate-alkyl acrylate-styrene copolymer is within the above range, the resin composition is excellent in transparency and impact resistance.

As a method for producing the methyl methacrylate-alkyl acrylate-styrene copolymer, 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, monomers, a polymerization initiator, and water are added, and if necessary, a chain transfer agent and a redox agent are added, and the mixture is heated and stirred.

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 by emulsion polymerization, the polymerization emulsifier 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 salt of a phosphoric acid compound. Conventionally known polymerization emulsifiers such as sulfonic acid and alkali metal salts of sulfuric acid compounds can be used.

When the impact modifier is obtained by emulsion polymerization, for example, a latex of the impact modifier and an acid such as hydrochloric acid, or a divalent or higher metal such as calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride, calcium acetate, etc. After coagulation by mixing the salt, the impact modifier can be separated from the aqueous medium by heat treatment, dehydration, washing and drying according to known methods (also referred to as coagulation method). 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. 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 to extract the impact modifier component in the latex into the organic solvent layer. is separated, and then mixed with water or the like to precipitate the impact modifier component. Alternatively, the latex can be directly pulverized by a spray drying method.

(Epoxy resin)
The epoxy resin (D) used in the resin composition of the present invention is not particularly limited as long as it is a compound having an "epoxy group" structure. Epoxy compounds include epoxy group-containing polymers, polyfunctional epoxy compounds, and the like, which are generally widely known, and any of them can be used. Examples of epoxy compounds include those described in Japanese Patent No. 6146989 and the like.

The epoxy resin preferably has a molecular weight of 300 to 20,000, more preferably 500 to 15,000, even more preferably 1,000 to 13,000, and most preferably 2,000 to 12,000. Within such a range, the compatibility with the polycarbonate resin is excellent, the transparency of the molded product is excellent, the deterioration of the hue due to the decomposition of the epoxy resin itself during molding is suppressed, and the moisture resistance and heat resistance are excellent. Provides light resistance.

In this specification, when the epoxy resin is a polymer, the molecular weight of the epoxy resin means "weight average molecular weight". Here, the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC). Specifically, the polystyrene equivalent weight mass average molecular weight of the epoxy resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Co., Ltd. as a column, chloroform etc. as a mobile phase, column temperature It can be measured at 40° C. and calculated using a standard polystyrene calibration curve.

As the epoxy resin, a commercially available product may be used, for example, an epoxy group-containing polymer ("G-0150M" manufactured by NOF, "UG-4010" manufactured by Toa Gosei, an epoxy group-containing acrylic-styrene polymer (manufactured by Toa Gosei " UG-4035”) and the like.

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

(weight ratio)
The weight ratio of the polycarbonate resin and the methyl methacrylate-methyl acrylate copolymer is preferably in the range of 50:50 to 99:1. It is more preferably in the range of 52:48 to 95:5, still more preferably in the range of 54:46 to 93:7, particularly preferably in the range of 56:35 to 90:10, most preferably 60: It ranges from 40 to 88:12. By setting the amount in the above range, a resin composition having excellent surface hardness and impact resistance can be obtained.

The methyl methacrylate-alkyl acrylate-styrene copolymer is mixed in the range of 10 to 30 parts by weight with respect to a total of 100 parts by weight of the polycarbonate resin and the methyl methacrylate-methyl acrylate copolymer. It is preferably in the range of 11 to 28 parts by weight, more preferably in the range of 12 to 26 parts by weight, still more preferably in the range of 13 to 23 parts by weight, and particularly preferably in the range of 14 to 20 parts by weight. . A resin composition having excellent transparency, surface hardness, and impact resistance can be obtained by setting the amount within the above range.

The epoxy resin is mixed in an amount of 1 to 30 parts by weight with respect to a total of 100 parts by weight of the polycarbonate resin and the methyl methacrylate-methyl acrylate copolymer. It is preferably in the range of 2 to 25 parts by weight, more preferably in the range of 3 to 20 parts by weight, still more preferably in the range of 4 to 15 parts by weight, and most preferably in the range of 5 to 10 parts by weight. By setting it as the said range, the resin composition excellent in transparency, impact resistance, wet heat resistance, and dry heat resistance can be obtained.

(Additive)
The resin composition used in the present invention contains a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, and an antibacterial agent, depending on the application and need. , UV absorbers, release agents, colorants, and other additives may be added.

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

Specific examples of the pentaerythritol-type phosphite compound include, for example, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6 -di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like, 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'-biphenylenediphosphonite, 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 '-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenyl phosphonite, 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, tetrakis(di-tert -butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite, bis(2 ,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable.

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

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

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

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

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

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

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

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

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

One of these sulfur-based heat stabilizers may be used alone, or two or more of them may be used in combination.

The sulfur-based heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. be done.

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

(Release agent)
The resin composition used in the present invention may contain a mold release agent within a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding.

Examples of such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefinic waxes, olefinic waxes containing carboxy groups and/or carboxylic acid anhydride groups, silicone oils, organopolysiloxane and the like.

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

Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

As higher fatty acids, saturated fatty acids having 10 to 30 carbon atoms are preferred. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

One of these release agents may be used alone, or two or more thereof may be used in combination. The amount of the release agent to be added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the resin composition.

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

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

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

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

Examples of light stabilizers include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, didecanoic acid bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, 2,4- bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-2-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (2,2,6,6- tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl Oxy-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- Hindered amines such as piperidyl)phenyl phosphite, nickel complexes such as nickel bis(octylphenyl sulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, and nickel dibutyl dithiocarbamate. 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, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the resin composition. 01 to 0.5 parts by weight.

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

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

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

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

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

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

(Molding)
The resin composition of the present invention can be molded and processed into various molded articles (including sheets and films) by any method such as injection molding, compression molding, injection compression molding, melt film-forming, and casting. 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.

(transparency)
The resin composition of the present invention preferably has a haze of 10% or less, more preferably 8% or less, even more preferably 5% or less, and 3% or less in a molded piece having a thickness of 2 mm. Especially preferred. When the haze is within the above range, the range of use as an optical member is not limited, which is preferable.

(YI)
The resin composition of the present invention preferably has a YI of 10 or less, more preferably 9 or less, and particularly preferably 8 or less for a molded piece having a thickness of 2 mm. When YI is within the above range, the range of use as an optical member is not limited, which is preferable.

(Damp heat resistance)
The resin composition of the present invention has a ΔYI of 10 or less, preferably 9 or less, which indicates a hue change before and after a wet heat test in which a 2 mm-thick molded piece is left for 500 hours under conditions of 80 ° C. and 95% RH. is more preferable, and 8 or less is particularly preferable. When ΔYI is within the above range, the range of use as an optical member is not limited, which is preferable.

(Impact strength)
The resin composition of the present invention preferably has a notched Charpy impact strength measured in accordance with ISO 179 of 6 kJ/m ² or more, more preferably 7 kJ/m ² or more, and 8 kJ/m ² or more. is more preferred. A notched Charpy impact strength of 100 kJ/m ² or less provides a sufficient function.

(light resistance)
The resin composition of the present invention preferably has a ΔYI of 10 or less, which indicates a change in hue before and after a light resistance test in which a molded piece having a thickness of 2 mm is left to stand for 200 hours under the conditions of 63° C. and 150 mW/cm ² . , is more preferably 8 or less, and particularly preferably 6 or less. When YI is within the above range, the range of use as an optical member is not limited, which is preferable.

(Pencil hardness)
The resin composition of the present invention preferably has a pencil hardness of F or higher, more preferably H or higher. From the viewpoint of excellent scratch resistance, it is more preferably 2H or more. 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 the hardness that does not leave a scratch even when the resin of the present invention is rubbed with a pencil having a specific pencil hardness, and is measured according to JIS K-5600. It is preferable to use the pencil hardness used for the surface hardness test of the coating film which can be formed 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.

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

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

1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR of JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.

2. Specific Viscosity Determined from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]

3. Haze A 2-mm-thick portion of the three-stage plate obtained by the following method was measured using a haze meter 300A manufactured by Nippon Denshoku Industries Co., Ltd.

4. YI
A 2 mm portion of the three-stage plate obtained by the following method was cut into a size of 45 mm long×50 mm wide×2 mm thick, and YI was measured using a spectral color difference meter SE-2000 manufactured by Nippon Denshoku Industries. A smaller YI indicates a smaller yellowness.

5. Humidity and heat resistance test A 2 mm portion of the three-stage plate obtained by the following method was cut into a size of 45 mm long × 50 mm wide × 2 mm thick, and this molded plate was measured using a small environmental tester S manufactured by Espec Co., Ltd.
H-241 was left to stand for 500 hours under conditions of 80° C. and 95% RH. ΔYI was measured for the test pieces before and after the test using a spectral color difference meter SE-2000 manufactured by Nippon Denshoku Industries. A smaller ΔYI indicates a smaller discoloration.

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.

7. Light resistance test A 2 mm portion of the three-stage plate obtained by the following method was cut into a size of 45 mm in length × 50 mm in width × 2 mm in thickness, and this molded plate was tested with a metal halide lamp tester (eye super) manufactured by Iwasaki Electric Co., Ltd. It was left to stand for 200 hours under conditions of 63° C. and 150 mW/cm ² using a UV tester SUV-W161). ΔYI was measured for the test pieces before and after the test using a spectral color difference meter SE-2000 manufactured by Nippon Denshoku Industries. A smaller ΔYI indicates a smaller discoloration.

8. Pencil hardness Based on JIS K5400, a line is drawn on the surface of the molded product in a constant temperature room with an ambient temperature of 23 ° C. while a pencil is kept at an angle of 45 degrees and a load of 750 g is applied, and the surface condition is visually observed. evaluated.

[Polycarbonate resin (A)]
A-1: structural unit derived from isosorbide (hereinafter referred to as ISS)/3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter referred to as SPG) / structural unit derived from 1,9-nonanediol (hereinafter referred to as ND) = 58/38/4 (mol%), specific viscosity 0.425
A-2: structural unit derived from ISS/structural unit derived from SPG/structural unit derived from ND = 72/21/7 (mol%), specific viscosity 0.396
A-3: structural unit derived from ISS/structural unit derived from ND = 96/4 (mol%) decanol terminal modified resin, specific viscosity 0.366
A-4: Structural unit derived from ISS/structural unit derived from 1,4-cyclohexanedimethanol (CHDM) = 70/30 (mol%), specific viscosity 0.378

[Methyl methacrylate-methyl acrylate copolymer (B)]
Mitsubishi Chemical ACRYPET VH001 (acrylic resin obtained by copolymerizing 95 mol% of methyl methacrylate and 5 mol% of methyl acrylate)

[Methyl methacrylate-alkyl acrylate-styrene copolymer (C)]
Kaneka Kaneace M-230 (refractive index: 1.492)

[Epoxy resin (D)]
D-1: NOF Corporation epoxy group-containing polymer Marproof G-0150M (molecular weight: 10000, epoxy equivalent: 310)
D-2: Epoxy group-containing polymer ARUFON UG-4010 manufactured by Toagosei Co., Ltd. (molecular weight: 2900, epoxy equivalent: 710)
D-3: Toagosei Co., Ltd. epoxy group-containing acrylic-styrene polymer ARUFON UG-4035 (molecular weight: 11000, epoxy equivalent weight: 560)

[Mixture (E) of methyl methacrylate-methyl acrylate copolymer and butadiene-alkyl acrylate-alkyl methacrylate copolymer]
Mitsubishi Chemical ACRYPET VRL40

[Example 1]
<Production of polycarbonate resin (A)>
294 parts of isosorbide (hereinafter abbreviated as ISS), 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter abbreviated as SPG ) 400 parts, 1,9-nonanediol (hereinafter abbreviated as ND) 22 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, the reactor was discharged under pressure from the bottom of the reactor, and cooled in a water bath, cut with a pelletizer to obtain polycarbonate resin (A-1) pellets.

<Production of resin composition>
Polycarbonate resin A-1, methyl methacrylate-methyl acrylate copolymer B: Mitsubishi Chemical Acrylpet VH001, methyl methacrylate-alkyl acrylate-styrene copolymer C: Kaneace M230 manufactured by Kaneka Corporation, epoxy resin D -1: Epoxy-terminated acrylic G-0150M manufactured by NOF CORPORATION was used, mixed in a weight ratio of 66.2:10:20:3.8, and fed to an extruder. Extrusion is carried out using a vented twin-screw extruder [Kobe Steel, Ltd. KTX-30] with a diameter of 30 mmφ, a screw rotation speed of 150 rpm, a discharge rate of 20 kg / hr, and a vent vacuum degree of 3 kPa to obtain pellets by melt kneading. rice field. The extrusion temperature was 250° C. from the supply port to the die. A part of the obtained pellets was dried at 90° C. for 6 hours or more in a hot air circulation dryer, and then using an injection molding machine, a cylinder temperature of 250° C. and a mold temperature of 85° C. Test pieces for evaluation. (ISO bending test piece (ISO178, ISO179, ISO75-1 and ISO75-2 compliant), 3-step plate (1 mmt, 2 mmt, 3 mmt)) was molded. The evaluation results are shown in Table 1.

[Example 2]
<Production of resin composition>
Polycarbonate resin (A-2) pellets were obtained using 364 parts of ISS, 221 parts of SPG, 39 parts of ND, and 750 parts of DPC as raw materials, and the blend weight ratio A-2: B: C: D-1 = 66.2: 18: 12: The same operation as in Example 1 was performed except that the extrusion was performed so as to have a value of 3.8, and the same evaluation was performed. The results are shown in Table 1.

[Example 3]
<Production of resin composition>
Except for extruding so that the blend weight ratio A-2: B: C: D-1 = 66.2: 15: 15: 3.8, the same operation as in Example 1 was performed, and the same evaluation was performed. gone. The results are shown in Table 1.

[Example 4]
<Production of resin composition>
Except for extruding so that the blend weight ratio A-2: B: C: D-1 = 65.2: 15: 15: 4.8, the same operation as in Example 1 was performed, and the same evaluation was performed. gone. The results are shown in Table 1.

[Example 5]
<Production of resin composition>
The same operation as in Example 1 was performed except that the blend weight ratio was A-2:B:C:D-2:D-3 = 66.2:18:12:2.1:1.7. , made a similar evaluation. The results are shown in Table 1.

[Example 6]
<Production of resin composition>
The same operation as in Example 1 was performed except that the blend weight ratio PC: B: C: D-2: D-3 = 63.2: 18: 12: 4.5: 2.3 was extruded. was evaluated. The results are shown in Table 1.

[Example 7]
<Production of resin composition>
The same operation as in Example 1 was performed except that the blend weight ratio was A-2:B:C:D-2:D-3 = 65.2:15:15:3.2:1.6. , made a similar evaluation. The results are shown in Table 1.

[Example 8]
<Production of resin composition>
The same operation as in Example 1 was performed except that the blend weight ratio was A-2:B:C:D-2:D-3 = 63.2:15:15:4.5:2.3. , made a similar evaluation. The results are shown in Table 1.

[Comparative Example 1]
<Production of polycarbonate resin>
Isosorbide (hereinafter abbreviated as ISS) 478 parts, 1,9-nonanediol (hereinafter abbreviated as ND) 33.5 parts, decanol 27.6 parts, diphenyl carbonate (hereinafter abbreviated as DPC) 750 parts, and barium stearate as a catalyst A 0.0025 part portion was heated to 120° C. under a nitrogen atmosphere to melt. After that, the solution was sent to the reaction tank, the temperature of the heat medium in the condenser was adjusted to 40° C., the internal temperature of the resin was adjusted to 170° C., and the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. After that, the degree of pressure reduction was adjusted to 3.4 kPa over 20 minutes, and the temperature was maintained for 10 minutes. Further, the degree of pressure reduction is reduced to 0.9 kPa over 30 minutes, the internal temperature of the resin is adjusted to 180 ° C., and after holding that temperature for 10 minutes, the degree of vacuum is reduced to 0.2 kPa, and the resin temperature is increased from 180 ° C. to 225 ° C. for 30 minutes. After reaching a specified viscosity, the solution was discharged from the bottom of the reaction tank under nitrogen pressure, and cut with a pelletizer while cooling in a water tank to obtain polycarbonate resin (A-3) pellets.

<Production of resin composition>
Except for extruding with a blend weight ratio of A-3:B:C:D-1=66.2:18:12:3.8, the same operation as in Example 1 was performed, and the same evaluation was performed. . The results are shown in Table 1.

[Comparative Example 2]
<Production of resin composition>
Using 354 parts of ISS, 150 parts of CHDM, and 750 parts of DPC as raw materials, polycarbonate resin (A-4) pellets were obtained, and the Brent weight ratio was A-4:B:C:D-1 = 66.2:18:12:3. The same operation as in Example 1 was carried out, except for extruding as .8, and the same evaluation was carried out. The results are shown in Table 1.

[Comparative Example 3]
<Production of resin composition>
Except for extruding with a Brent weight ratio of A-2:B:C=70:18:12, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 4]
<Production of resin composition>
Except for extruding with a Brent weight ratio of A-2:B:C:D-1=66.2:22:8:3.8, the same operation as in Example 1 was performed, and the same evaluation was performed. . The results are shown in Table 1.

[Comparative Example 5]
<Production of resin composition>
Except for extruding at a Brent weight ratio of A:E=70:30, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 6]
<Production of resin composition>
Except for extruding with a Brent weight ratio of A:D-1:E=66.2:3.8:30, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 7]
<Production of resin composition>
Except for extruding with a Brent weight ratio of A: D-2, D-3: E = 66.2: 2.1: 1.7: 30, the same operation as in Example 1 was performed, and the same evaluation was performed. gone. The results are shown in Table 1.

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 (8)

A total of 100 weights of a polycarbonate resin (A) containing 5 to 85 mol% of units (a) whose repeating units are represented by the following formula (1) and a methyl methacrylate-methyl acrylate copolymer (B) 10 to 30 parts by weight of methyl methacrylate-alkyl acrylate-styrene copolymer (C) and 1 to 30 parts by weight of epoxy resin (D), and the methyl methacrylate-alkyl acrylate - A resin composition, wherein the styrene copolymer (C) has a refractive index of 1.485 or more and 1.495 or less.

(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 unit (a) whose repeating unit is represented by the formula (1) and another carbonate unit (b), and the carbonate unit (b) is an aliphatic diol compound, an alicyclic 2. The resin composition according to claim 1, wherein the carbonate unit (b) is derived from at least one compound selected from the group consisting of diol compounds and aromatic dihydroxy compounds. 3. The resin composition according to claim 1, wherein the weight ratio of the polycarbonate resin (A) and the methyl methacrylate-methyl acrylate copolymer (B) is 50:50 to 99:1. The resin composition according to any one of claims 1 to 3, wherein the methyl methacrylate-methyl acrylate copolymer (B) contains 40 to 100 mol% of repeating units derived from methyl methacrylate. The resin composition according to any one of claims 1 to 4, wherein the epoxy resin (D) has a molecular weight of 3,000 to 20,000. 6. The resin composition according to any one of claims 1 to 5, wherein a test piece having a thickness of 2 mm has a haze of 10% or less. A molded article obtained by molding the resin composition according to any one of claims 1 to 6. A film or sheet formed from the resin composition according to any one of claims 1 to 6.