JP7389129B2 - resin composition - Google Patents

Description

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

Conventionally, transparent resins such as methacrylic resin and polycarbonate resin (hereinafter sometimes referred to as PC) have been used to produce electrical and electronic parts, optical parts, automobile parts, and mechanical parts in the form of molded products, films, and sheets. 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 often 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 heat-resistant fields is limited. Furthermore, there is a problem of low impact resistance.

Polycarbonate resins made of bisphenol A are widely used in vehicle applications and construction materials because of their excellent heat resistance, impact resistance, flame retardance, and transparency. Among these uses, high weather resistance is particularly required for those used outdoors, but polycarbonate resin generally has poor weather resistance compared to other transparent materials such as acrylic resin, and it tends to yellow due to outdoor exposure. devitrification and devitrification occur. Another problem is that the surface is very soft (pencil hardness 4B to 2B) and easily scratches.

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

In order to solve these problems, a resin composition using polycarbonate with a special structure and an acrylic resin has been reported (Patent Document 2), and the excellent properties of PC and PMMA have been achieved. ing. However, according to studies conducted by the present inventors, it has been found that the resin composition described in Patent Document 2 shows remarkable deterioration of the resin under wet heat environments and dry heat environments. Therefore, in the composition of polycarbonate and acrylic resin, a composition that has both the characteristics of each resin and has good moist heat resistance and dry heat resistance has not been reported so far.

US Patent No. 4319003 Japanese Patent Application Publication No. 2015-232091

An object of the present invention is to provide a resin composition having excellent properties in transparency, heat resistance, impact resistance, weather resistance, surface hardness, wet heat resistance, and dry heat resistance.

As a result of extensive research, the present inventors have found that by including carbodiimide in a composition of polycarbonate resin and acrylic resin, transparency, heat resistance, impact resistance, weather resistance, surface hardness, wet heat resistance, and dry heat resistance can be improved. The present inventors have discovered that a resin composition with excellent properties can be obtained, and have completed the present invention.

That is, according to the present invention, the objects of the invention are achieved as follows.

1. A resin composition containing (A) a polycarbonate resin, (B) an acrylic resin, and (C) a carbodiimide.

2. (A) The resin composition according to item 1, wherein the polycarbonate resin contains 5 to 85 mol% of the repeating unit (a-1) represented by the following formula (1) based on the total repeating units.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R ₁ is a branched or straight-chain alkyl group having 1 to 20 carbon atoms, or has a substituent. represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)
3. (A) The resin composition according to item 1 or 2 above, in which the polycarbonate resin contains 15 to 95 mol% of the repeating unit (a-2) represented by the following formula (2) based on all repeating units.

(In the formula, R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents a branched or straight-chain alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent. represent.)
4. (B) The resin composition according to any one of items 1 to 3 above, in which the acrylic resin contains 10 to 100 mol% of the repeating unit (b) represented by the following formula (3) based on all repeating units.

5. 4. The resin composition according to item 4, wherein the repeating unit (b) is a unit (b) derived from methyl methacrylate and/or methyl acrylate.

6. The resin composition according to any one of items 1 to 5 above, wherein the weight ratio of (A) polycarbonate resin to (B) acrylic resin is 1:99 to 99:1.

7. (C) The resin composition according to any one of items 1 to 6 above, wherein the content of carbodiimide is 0.001 to 20 parts by weight based on a total of 100 parts by weight of the polycarbonate resin and acrylic resin.

8. (C) The resin composition according to any one of items 1 to 7 above, wherein the carbodiimide has a molecular weight of 150 to 13,000.

9. The resin composition according to any one of items 1 to 8 above, wherein the haze of a 9.2 mm thick test piece is 30% or less.

10. A molded article obtained by injection molding the resin composition according to any one of items 1 to 9 above.

11. A film or sheet formed from the resin composition according to any one of items 1 to 9 above.

The present invention provides a resin composition that has excellent properties in transparency, heat resistance, impact resistance, weather resistance, surface hardness, moist heat resistance, and dry heat resistance by containing carbodiimide in a composition of polycarbonate resin and acrylic resin. It became possible to provide. Therefore, its industrial effects are exceptional.

The present invention will be explained in detail below.
[(A) Polycarbonate resin]
The structure of the polycarbonate resin used in the resin composition of the present invention is not particularly limited as long as it has carbonate bonds.

Among the polycarbonate resins, the repeating unit is a polycarbonate resin containing a unit (a-1) represented by the following formula (1) and/or a unit (a-2) represented by the following formula (2). is preferred.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R ₁ is a branched or straight-chain alkyl group having 1 to 20 carbon atoms, or has a substituent. represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)

The unit (a-1) represented by the above formula (1) 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. Examples include alicyclic diol compounds.

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 preferably contains 5 to 85 mol% of the unit (a-1) represented by the above formula (1) in the repeating unit, and 10 to 80 mol% of the total repeating units. The content is more preferably 15 to 75 mol%, and particularly preferably 20 to 70 mol%. When the unit (a-1) is within the above range, the resin composition will not become cloudy due to phase separation during extrusion or molding in the resin composition with the acrylic resin, and will not crystallize during polymerization of the polycarbonate resin. It is preferable because polymerization is easy without any oxidation.

Further, the unit (a-2) represented by the above formula (2) is derived from an aliphatic diol having an ether group.

Examples of the unit (a-2) include units (a-2-1), (a-2-2), and (a-2-3) represented by the following formulas that have a stereoisomeric relationship. .

These are ether diols derived from carbohydrates, substances that can also be obtained from biomass in the natural world, and are one of the so-called renewable resources. Repeating units (a-2-1), (a-2-2) and (a-2-3) are called isosorbide, isomannide and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can also be obtained by the same reaction except for the starting materials.

Among isosorbide, isomannide, and isoidide, repeating units derived from isosorbide (1,4;3,6-dianhydro D-sorbitol) are particularly preferred because they are easy to produce and have excellent heat resistance.

The repeating unit (a-2) preferably contains 15 to 95 mol% of all repeating units, more preferably 20 to 90 mol%, even more preferably 30 to 85 mol%, and 40 to 80 mol%. This is particularly preferred. It is preferable that the unit (a-2) is within the above range because it provides an excellent balance of impact resistance, heat resistance, surface hardness, and weather resistance.

In the present invention, repeating units constituting the copolymerization structural units other than the unit (a-1) and the unit (a-2) include repeating units derived from various diol compounds.

Examples of 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- Examples include 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.

Examples of alicyclic diol compounds include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol, and 1,2-cyclohexane. Dimethanol, cyclohexanedimethanols such as 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, norbornane dimethanols such as 2,3-norbornane dimethanol and 2,5-norbornane dimethanol, tricyclode Examples include candimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalin dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and cyclohexane. Dimethanols, 4,4-tetramethyl-1,3-cyclobutanediol 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 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and bisphenol A are preferably used.

The copolymerization structural units other than these units (a-1) and (a-2) are preferably 50 mol% or less, 40 mol% or less, 35 mol% or less, 30 mol% or less, 25 mol% or less of the total repeating units. mol% or less, 20 mol% or less, 15 mol% or less, 10 mol% or less.
(Production method of polycarbonate resin)
Polycarbonate resins are produced by reaction methods known per se for producing conventional polycarbonate resins, such as a method in which a diol component is reacted with a carbonate precursor such as a carbonic acid diester. Next, basic means for these manufacturing methods will be briefly explained.

The transesterification reaction using a carbonate diester as a carbonate precursor is carried out by stirring a predetermined proportion of a diol component with a carbonate diester under an inert gas atmosphere while heating, and distilling the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage to distill out the alcohol or phenol produced. Further, a terminal capping agent, an antioxidant, etc. may be added as necessary.

Examples of the carbonic diester used in the transesterification reaction include esters of 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 used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the dihydroxy compound in total.

In the melt polymerization method, a polymerization catalyst can be used to speed up 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 alone 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 Examples include dilithium oxyhydrogen, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, and lithium salt of phenol.

Examples of 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, and diacetic acid. Examples include barium, barium stearate, and the like.

Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Can be mentioned. Further examples include tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole. Further, bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate are exemplified.

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

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

Moreover, a catalyst deactivator can also 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 preferred. Further preferred are salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate, and salts of paratoluenesulfonic acid such as tetrabutylammonium paratoluenesulfonic acid.

In addition, as esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl para-toluenesulfonate, ethyl para-toluenesulfonate, butyl para-toluenesulfonate, Octyl para-toluenesulfonate, phenyl para-toluenesulfonate, etc. 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 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: _ηSP )
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 will be good. It is more preferably 0.25 to 1.2, still more preferably 0.3 to 1.0, particularly preferably 0.3 to 0.5.

The specific viscosity in the present invention is 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 )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
Note that specific viscosity can be measured, for example, in the following manner. First, polycarbonate resin is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble content is collected by filtration through Celite.The solution is removed and thoroughly dried to obtain a solid of the methylene chloride soluble content. The specific viscosity at 20° C. of a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride is determined using an Ostwald viscometer.
[(B) Acrylic resin]
The structure of the acrylic resin used in the resin composition of the present invention is not particularly limited.

Among acrylic resins, acrylic resins whose repeating units include a unit (b) represented by the following formula (3) are preferred.

(In the formula, R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents a branched or straight-chain alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent. represent.)
Examples of monomers inducing the unit (b) represented by the above formula (3) include methyl methacrylate, methyl acrylate, benzyl (meth)acrylate, n-butyl (meth)acrylate, and i-butyl (meth)acrylate. ) acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclo Examples include compounds such as pentenyloxyethyl (meth)acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, and cyclododecyl acrylate.

Other monomers that may be used include the following compounds. For example, methacrylic acid, methyl methacrylate, acrylic acid, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate Acrylate, 2-ethoxyethyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-maleate (meth)acryloyloxyethyl, 2-(meth)acryoyloxyethyl phthalate, 2-(meth)acryoyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, Examples include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

These may be used by polymerizing alone, or two or more types may be polymerized and used. Among these, it is preferable to include methyl methacrylate and/or methyl acrylate as a monomer for inducing the unit (b), and it is particularly preferable to include methyl methacrylate.

The acrylic resin of the present invention preferably contains the repeating unit (b) in an amount of 10 to 100 mol%, more preferably 10 to 99 mol%, even more preferably 30 to 95 mol%, and even more preferably 50 to 90 mol% of the repeating unit (b). It is particularly preferred to include. When the repeating unit (b) is within the above range, it has excellent heat decomposition resistance, and molding defects such as silver are less likely to occur during molding. Furthermore, the heat distortion temperature is less likely to decrease. Furthermore, other monomers that can be polymerized with these acrylic monomers, such as polyolefin monomers, vinyl monomers, etc., may 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 flow unevenness will not occur during molding, and mechanical properties will be improved. , it is possible to provide a composition with excellent 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 increases, which may impair moldability.

Further, the glass transition temperature (Tg) of the acrylic resin used in the present invention is preferably 90 to 150°C, more preferably 95 to 145°C, and still more preferably 100 to 140°C. It is preferable that the Tg is 90 to 150°C, since heat resistance stability and moldability are good.

The glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20° C./min.

The acrylic resin of the present invention is not particularly limited, but is preferably an acrylic resin having a melt flow rate of 0.5 to 30 g/10 min as measured at 230°C and a load of 3.8 kg in accordance with JIS K7210. . More preferably, the melt flow rate is 0.7 to 27 g/10 min, and even more preferably, the melt flow rate is 1.0 to 25 g/10 min. An acrylic resin having a melt flow rate within this range has good moldability.
[(C) Carbodiimide]
The carbodiimide used in the resin composition of the present invention is not particularly limited as long as it is a compound having a "-N=C=N-" structure in its molecule. Examples of carbodiimide compounds include monocarbodiimide compounds, polycarbodiimide compounds, cyclic carbodiimide compounds, etc., which are generally widely known, and any of them can be used. Examples of carbodiimide compounds include JP-A-9-309871, JP-A-9-249801, JP-A-9-208649, JP-A-9-296097, JP-A-8-81,533, JP-A-8-27092, JP-A-9-136869, JP 9-124582, JP 9-188807, JP 2005-82642, JP 2005-53870, JP 2012-36392, JP 2010-163203, JP 2011-174094, WO 2008/072514, WO 2010/071211, Examples include those described in JP-A No. 2012-81759, JP-A No. 2012-52014, and JP-A No. 2012-7079.

The molecular weight of the carbodiimide is preferably 150 or more, more preferably 185 or more, and still more preferably 200 or more. Within this range, good storage stability can be obtained in addition to improved moisture resistance. Further, the molecular weight of the carbodiimide is preferably 13,000 or less, more preferably 8,000 or less, still more preferably 4,000 or less. This range is preferable because it has excellent compatibility with polycarbonate resins and acrylic resins and excellent transparency when molded.

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

As the carbodiimide, any of monocarbodiimide, polycarbodiimide and cyclic carbodiimide can be used, but cyclic carbodiimide and polycarbodiimide are more preferred.

As the polycarbodiimide, commercially available products may be used, such as aliphatic polycarbodiimide ("HMV-8CA", "LA-1" manufactured by Nisshinbo Chemical Co., Ltd.), carbodiimide-modified isocyanate ("Carbodilite V-05" manufactured by Nisshinbo Chemical Co., Ltd.) ). Among these, aliphatic polycarbodiimides ("HMV-8CA" and "LA-1" manufactured by Nisshinbo Chemical Co., Ltd.) are preferred.

Examples of the cyclic carbodiimide include the cyclic carbodiimide described in Japanese Patent No. 05484356.
[Method for manufacturing resin composition]
The resin composition of the present invention is preferably prepared by blending (A) a polycarbonate resin, (B) an acrylic resin, and (C) a carbodiimide in a molten state. As a method for blending in a molten state, an extruder is generally used, and the molten resin is kneaded and pelletized at a temperature of 200 to 320°C, preferably 220 to 300°C, more preferably 230 to 290°C. Thereby, pellets of the 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 below 200°C, the resin viscosity may be too high and the extruder may be overloaded.
[Weight ratio]
The weight ratio of (A) polycarbonate resin and (B) acrylic resin is preferably in the range of 1:99 to 99:1, and they can be mixed arbitrarily within that range. More preferably the range is 5:95 to 98:2, still more preferably the range is 10:90 to 97:3, particularly preferably the range is 20:80 to 96:4, and most preferably 30: It is in the range of 70-95:5. By setting it within the above range, a resin composition with excellent heat resistance and impact resistance can be obtained.

Further, (C) carbodiimide is preferably mixed in an amount of 0.001 to 20 parts by weight based on a total of 100 parts by weight of the polycarbonate resin and acrylic resin. It is more preferably in the range of 0.002 to 15 parts by weight, still more preferably in the range of 0.005 to 10 parts by weight, particularly preferably in the range of 0.01 to 5 parts by weight, and most preferably in the range of 0.001 to 5 parts by weight. The range is 0.01 to 2 parts by weight.
[Load deflection temperature: HDT]
The resin composition of the present invention preferably has a deflection temperature under high load (1.8 MPa) defined by ISO75 of 90° C. or higher. The deflection temperature under load is more preferably 95°C or higher, and still more preferably 100°C or higher. Within the above range, thermal deformation in actual environments is small, so it is particularly useful for applications such as electrical/electronic parts, automobile parts, sheets, bottles, containers, and building materials. Although the upper limit is not particularly limited, it is preferably 150°C or less.
[Pencil hardness]
The resin composition of the present invention preferably has a pencil hardness of F or higher. In terms of excellent scratch resistance, it is more preferable that it is H or higher. Note that pencil hardness of 4H or less provides sufficient functionality. Pencil hardness can be increased by increasing the weight ratio of acrylic resin. In the present invention, pencil hardness refers to the hardness that does not leave scratch marks 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 in the surface hardness test of the resulting coating film as an index. Pencil hardness decreases in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, with 9H being the hardest and 9H being the hardest. The soft one is 6B.
[Additive]
The resin composition used in the present invention may include heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, and antibacterial agents, depending on the purpose and necessity. , ultraviolet absorbers, mold release agents, colorants, and other additives may be added.
(thermal stabilizer)
The resin composition used in the present invention particularly preferably contains a heat stabilizer in order to suppress molecular weight reduction and hue deterioration during extrusion and molding. Examples of the heat stabilizer include phosphorus-based heat stabilizers, phenol-based heat stabilizers, and sulfur-based heat stabilizers, and one type of these can be used alone or two or more types can be used in combination. It is preferable to incorporate a phosphite compound as the phosphorus stabilizer. Examples of the phosphite compound include pentaerythritol type phosphite compounds, phosphite compounds that react with dihydric phenols and have a cyclic structure, and phosphite compounds having other structures.

Specifically, the above pentaerythritol type phosphite compounds include, for example, distearyl pentaerythritol 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, Examples include bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and among them, distearylpentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are preferred. Erythritol diphosphite is 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) Examples include -tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol.

Examples of phosphite compounds having other structures mentioned above include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, triotadecyl phosphite, and didecylmonophenyl phosphite. , dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite phyto, 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.

In addition to various phosphite compounds, examples include phosphate compounds, phosphonite compounds, and phosphonate compounds.

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, Examples include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferred.

Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite , 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-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, -n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite etc., tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2, More preferred are 4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Among the above phosphorus-based 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-mentioned phosphorus-based heat stabilizers can be used alone or in combination of two or more. The phosphorus heat stabilizer is preferably blended in an amount of 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 molecular weight reduction and hue deterioration during extrusion and molding. It can also be added in combination with a phosphorus-based heat stabilizer.

The hindered phenol heat stabilizer is not particularly limited as long as it has an antioxidant function, but for example, n-octadecyl-3-(4'-hydroxy-3',5'-di-t- 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-tolyl)tri- Examples include 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 alone 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, and even more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Part is mixed.

Examples of the sulfur-based heat stabilizer include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, and dilauryl-3,3'-thiodipropionic acid ester. 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), etc. . Among the above, pentaerythritol tetrakis (3-laurylthiopropionate) is preferred.

These sulfur-based heat stabilizers may be used alone or in combination of two or more.

The sulfur-based heat stabilizer is preferably blended in 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 together, the total amount of these 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. It is blended in an amount of .01 to 0.3 parts by weight.
(Release agent)
In order to further improve the releasability from the mold during melt molding, 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.

Such mold release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin waxes, olefin waxes containing carboxyl groups and/or carboxylic acid anhydride groups, silicone oils, Examples include organopolysiloxane.

The higher fatty acid ester is preferably a partial or total ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of such partial or total esters of monohydric or polyhydric alcohols and saturated fatty acids include 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, biphenylbiphene -t, sorbitan monostearate, 2-ethylhexyl stearate and the like.

Among these, 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.

These mold release agents may be used alone or in combination of two or more. The amount of the mold release agent blended 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 UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers, and cyanoacrylate-based UV absorbers, among which benzotriazole-based UV absorbers Agents are preferred.

Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, and 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole. '-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 Benzotriazole ultraviolet absorbers typified by a condensate of -tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate and polyethylene glycol can be mentioned.

The proportion of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, and even more preferably 0.2 to 0.5 parts by weight based on 100 parts by weight of the resin composition. It is.
(light stabilizer)
The resin composition used in the present invention can contain a light stabilizer. Containing a light stabilizer has the advantage of good weather resistance and making it difficult for molded products 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 Hindered amines such as -4-piperidyl) phenyl phosphite, nickel such as nickel bis(octylphenyl sulfide, nickel complex -3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate, etc.) Examples include complexes. 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 based on 100 parts by weight of the resin composition. More preferably, it is 0.01 to 0.5 parts by weight.
(Epoxy stabilizer)
In order to improve hydrolyzability, an epoxy compound can be blended into the resin composition used in the present invention within a range that does not impair the purpose of the present invention.

Epoxy 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'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy -6-Methylcyclohexylmethyl-6'-methylsilohexylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxy dicyclo 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-epoxycyclohexylcarboxylate, N-butyl-2 , 2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, Octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3',4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3',4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic 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 from the viewpoint of compatibility.

Such an epoxy stabilizer is preferably 0.0001 to 5 parts by weight, more preferably 0.001 to 1 part by weight, even more preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the resin composition. It is desirable that the amount is within the range of parts by weight.
(Bluing agent)
The resin composition used in the present invention may contain a bluing agent in order to cancel out the yellow tint of the lens due to the polymer or ultraviolet absorber. As the bluing agent, any one used for polycarbonate can be used without any particular problem. Generally, anthraquinone dyes are preferred because they are easily available.

As a specific bluing agent, for example, the common name Solvent Violet 13 [CA. No. (color index No.) 60725], common name Solvent Violet 31 [CA. No. 68210, common name Solvent Violet 33 [CA. No. 60725], common name Solvent Blue94 [CA. No. 61500], common name Solvent Violet36 [CA. No. 68210], generic name Solvent Blue 97 [Bayer AG "Macrolex Violet RR"] and generic name Solvent Blue 45 [CA. No. 61110] is cited as a representative example.

These bluing agents may be used alone or in combination of two or more. These bluing agents are preferably blended in an amount 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 blended into the resin composition used in the present invention. Examples of flame retardants include halogen flame retardants such as brominated epoxy resins, brominated polystyrene, brominated polycarbonates, brominated polyacrylates, and chlorinated polyethylene; phosphate ester flame retardants such as monophosphate compounds and phosphate oligomer compounds; Organophosphorus flame retardants other than phosphate ester flame retardants such as phosphinate compounds, phosphonate compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, organic sulfonic acid alkali (earth) metal salts, boric acid metal salt flame retardants, and organometallic salt flame retardants such as metal stannate flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, triazine flame retardants, and the like. In addition, flame retardant aids (for example, sodium antimonate, antimony trioxide, etc.), anti-dripping agents (polytetrafluoroethylene having fibril-forming ability, etc.), etc. may be separately added and used in combination with the flame retardant.

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

When a flame retardant is added, it is preferably in the range of 0.05 to 50 parts by weight per 100 parts by weight of the resin composition. If it is within the above range, sufficient flame retardancy will be exhibited, and the molded product will have excellent strength and heat resistance.
(Elastic polymer)
An elastic polymer can be used as an impact modifier in the resin composition used in the present invention, and examples of the elastic polymer include natural rubber or a rubber component having a glass transition temperature of 10°C or less, Examples include graft copolymers in which one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic esters, methacrylic esters, and vinyl compounds copolymerizable with these are copolymerized. can. A more suitable elastic polymer is a core-shell type graft copolymer in which one or more shells of the monomers mentioned above are graft copolymerized onto a core of a rubber component.

Also included are block copolymers of such rubber components and the above monomers. Specific examples of such block copolymers include thermoplastic elastomers such as styrene/ethylene propylene/styrene elastomer (hydrogenated styrene/isoprene/styrene elastomer) and hydrogenated styrene/butadiene/styrene elastomer. Furthermore, it is also possible to use various other elastic polymers known as thermoplastic elastomers, such as polyurethane elastomers, polyester elastomers, polyetheramide elastomers, and the like.

More suitable as an impact modifier are core-shell type graft copolymers. In the core-shell type graft copolymer, the particle size of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and more preferably 0.1 to 0.5 μm in weight average particle size. is even more preferable. Better impact resistance is achieved in the range of 0.05 to 0.8 μm. The elastic polymer preferably contains a rubber component of 40% or more, more preferably 60% or more.

Rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, and ethylene-propylene rubber. Examples include acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those with hydrogen added to their unsaturated bond parts, but due to concerns about the generation of harmful substances during combustion, rubbers that do not contain halogen atoms It is preferable to use a rubber component that does not contain any rubber components in terms of environmental impact.

The glass transition temperature of the rubber component is preferably -10°C or lower, more preferably -30°C or lower, and the rubber component is particularly preferably butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, or acrylic-silicone composite rubber. Composite rubber refers to a rubber that is a copolymerization of two rubber components, or a rubber that is polymerized to have an IPN structure in which they are intertwined with each other so that they cannot be separated.

Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene, with styrene being particularly preferred. Examples of acrylate esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of methacrylate ester include methyl methacrylate, ethyl methacrylate, and methacrylate. Examples include butyl, cyclohexyl methacrylate, octyl methacrylate, and methyl methacrylate is particularly preferred. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in 100% by weight of the shell in the case of a core-shell type polymer), preferably 10% by weight or more, more preferably 15% by weight or more. be done.

The elastic polymer containing a rubber component with a glass transition temperature of 10°C or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be It may be a single-stage graft or a multi-stage graft. Alternatively, it may be a mixture of only a graft component produced as a by-product during production with a copolymer. Furthermore, examples of the polymerization method include, in addition to the general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, a two-step swelling polymerization method, and the like. In addition, in the suspension polymerization method, the aqueous phase and the monomer phase are held separately and both are accurately supplied to a continuous dispersion machine, and the particle size is controlled by the rotation speed of the dispersion machine. In the method, a method may be used in which the monomer phase is supplied into an aqueous liquid having dispersibility by passing it through a small orifice or porous filter with a diameter of several to several tens of μm to control the particle size. In the case of a core-shell type graft polymer, the reaction may be carried out in one stage or in multiple stages for both the core and shell.

Such elastic polymers are commercially available and can be easily obtained. For example, examples of rubber components that mainly include butadiene rubber, acrylic rubber, or butadiene-acrylic composite rubber include the Kane Ace B series (for example, B-56) manufactured by Kanebuchi Chemical Co., Ltd., and the Metablen rubber manufactured by Mitsubishi Rayon Co., Ltd. C series (for example, C-223A, etc.), W series (for example, W-450A, etc.), Pararoid EXL series (for example, EXL-2602, etc.) of Kureha Chemical Co., Ltd., HIA series (for example, HIA-15, etc.), BTA series (e.g. BTA-III, etc.), KCA series, Rohm & Haas' Pararoid EXL series, KM series (e.g. KM-336P, KM-357P, etc.), and Ube Scicon Co., Ltd.'s UCL Modifier Resin series (UMG - UMG AXS resin series by ABS Co., Ltd., etc., and products whose rubber component is mainly acrylic-silicone composite rubber are commercially available from Mitsubishi Rayon Co., Ltd. under the product names Metablane S-2001 or SRK-200. The following are examples of what has been done.

The composition ratio of the impact modifier is preferably 0.2 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 1.5 to 20 parts by weight per 100 parts by weight of the resin composition. Such a composition range can provide the composition with good impact resistance while suppressing a decrease in rigidity.
[Molding]
The resin composition of the present invention can be molded and processed by any method such as an injection molding method, a compression molding method, an injection compression molding method, a melt film forming method, a casting method, etc., and can be used to produce optical lenses, optical discs, optical films, plastic cell substrates, etc. It can be used as molded products such as optical cards, liquid crystal panels, headlamp lenses, light guide plates, diffusion plates, protective films, OPC binders, front plates, casings, trays, water tanks, lighting covers, signboards, and resin windows. In particular, it can be used as members that require high surface hardness, such as front panels, housings, trays, water tanks, lighting covers, signboards, and resin windows.
[transparency]
The resin composition of the present invention preferably has a haze of 2 mm thick molded pieces of 30% or less, more preferably 20% or less, even more preferably 10% or less, and even more preferably 5% or less. It is particularly preferable, and most preferably 2% or less. It is preferable that the haze is within the above range because the range of use as various transparent members is not limited.
[Impact strength]
The resin composition of the present invention preferably has a notched Charpy impact strength of 1.5 kJ/m ² or more, more preferably 2.0 kJ/m ² or more, and 3.0 kJ/m 2 or more, as measured in accordance with ISO179. More preferably, it is m ² or more. Note that the notched Charpy impact strength is 100 kJ/m ² or less and has sufficient functionality.
[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 adding a new layer to the surface of a resin molded product, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. A commonly used method can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water/oil repellent coat, ultraviolet absorbing coat, infrared absorbing coat, and metallizing (vapor deposition, etc.). A hard coat is a particularly preferred and required surface treatment.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight." The resins used in the examples and the evaluation methods are as follows.
(Evaluation of polycarbonate resin)
1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR using JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.

2. Specific viscosity It was determined using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C.

Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
(Evaluation of resin composition)
3. Charpy impact strength with notch After drying the pellet at 80 to 110°C for 12 hours, bending test piece using JSWJ-75EIII manufactured by Japan Steel Works, Ltd. at cylinder temperature of 230 to 280°C and mold temperature of 80 to 90°C. was molded. Notched Charpy impact tests were measured according to ISO179.

4. Deflection temperature under load (1.8MPa)
Above 3. The bending temperature under high load (1.8 MPa) specified by ISO75 was measured using the bending test piece prepared in .

5. After drying the pellets of the haze polycarbonate resin composition at 80 to 110°C for 12 hours, they were molded using an injection molding machine (Japan Steel Works, Ltd., JSW J-75EIII) at a mold temperature of 240 to 280°C. The width is 50 mm, the length is 90 mm, and the thickness is 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm) from the gate side at 80 ° C. and a molding cycle of 50 seconds. A three-stage plate with an arithmetic mean roughness (Ra) of 0.03 μm was molded. A 2 mm thick portion of the molded three-tiered plate was measured using a haze meter 300A manufactured by Nippon Denshoku Industries Co., Ltd.

6. Pencil hardness Based on JIS K5400, using the prepared three-tiered plate, the pencil was held at a 45 degree angle to the surface of the composition in a constant temperature room at an ambient temperature of 23°C, and a 750g load was applied. The surface condition was visually evaluated.

7. Weather Resistance Discoloration In accordance with JIS B7753, use Sunshine Weatherometer S80 manufactured by Suga Test Instruments Co., Ltd., and set the discharge voltage to 50V and discharge current to 60A with a sunshine carbon arc (4 pairs of ultra long life carbon) light source, and perform irradiation and surface spraying. The square surface of a flat plate of injection molded piece (width 60mm x length 60mm x thickness 3mm) was irradiated for 500 hours under the conditions of black panel temperature 63℃ and relative humidity 50% (rainfall). Ta. The surface spray (rainfall) time was 12 minutes/1 hour. A type A glass filter was used. The color difference ΔE was measured for the test piece before and after the test using a spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries. The smaller ΔE is, the smaller the discoloration is.

8. Dry heat resistance test A 2 mm section of the created three-tiered plate was cut out to a size of 50 mm x 45 mm, and this molded plate was subjected to a vacuum oven VOS-301SD manufactured by Tokyo Rika Kikai Co., Ltd. at 110°C and reduced pressure. It was left to stand for 500 hours under the condition that it was not heated. About the sample after processing 2. The specific viscosity was measured using the method measured in , and Δη _SP before and after the treatment was calculated.

In this evaluation, the smaller the Δη _SP value, the smaller the molecular weight change during long-term use in a high-temperature dry environment, indicating that the dry heat resistance is excellent.

In addition, regarding the YI change (ΔYI) before and after treatment, the YI of the injection molded plate was measured in accordance with JIS K7136 (2000) using a colorimeter "CE-7000" manufactured by Macbeth Co., Ltd. with C light source. did.

In this evaluation, the smaller the ΔYI value, the smaller the change in color tone during long-term use in a high-temperature dry environment, indicating that the dry heat resistance is excellent.

9. Moisture and heat resistance test A 2 mm section of the prepared three-tiered plate was cut into a size of 50 mm x 45 mm, and this molded plate was tested at 85°C and 85% RH using a small environmental tester SH-241 manufactured by ESPEC Co., Ltd. The sample was left standing for 500 hours. About the sample after processing 2. The specific viscosity was measured using the method measured in , and Δη _SP before and after the treatment was calculated.

In this evaluation, the smaller the Δη _SP value, the smaller the molecular weight change during long-term use in a high-temperature, moist-heat environment, and the better the moist-heat resistance.
[Polycarbonate resin]
PC1 (Example):
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 / structural unit derived from 1,9-nonanediol (hereinafter referred to as ND) = 75/20/5 (mol%), specific viscosity 0.396
PC2 (Example):
Structural unit derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter referred to as BCF)/structural unit derived from SPG = 34/66 (mol%), specific viscosity 0.359
PC3 (Example):
Structural unit derived from bisphenol A/structural unit derived from SPG = 85/15 (mol%), specific viscosity 0.385
PC4 (comparative example):
Teijin Co., Ltd. Panlight L-1225
PC5 (comparative example):
Structural unit derived from ISS/structural unit derived from 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM) = 70/30, specific viscosity 0.378
PC6 (Example, Comparative Example):
Structural unit derived from ISS/structural unit derived from CHDM = 50/50 (mol%), specific viscosity 0.337
[acrylic resin]
PMMA (Example)
Acrypet VH-001 manufactured by Mitsubishi Rayon (acrylic resin copolymerized with 95 mol% methyl methacrylate and 5 mol% methyl acrylate)
[Carbodiimide]
C1 (Example):
Nisshinbo aliphatic polycarbodiimide HMV-8CA, molecular weight 3000
C2 (Example):
A cyclic carbodiimide (see structure below), molecular weight 516, was prepared by the same synthesis method as Example 2 described in Patent No. 5,484,356.

[Example 1]
<Production of polycarbonate resin>
354 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) ), 28 parts of 1,9-nonanediol (hereinafter abbreviated as ND), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 0.8×10 ^-2 parts of tetramethylammonium hydroxide and barium stearate as a catalyst. 0.6×10 ⁻⁴ parts were heated to 200° C. under a nitrogen atmosphere to melt them. Thereafter, the temperature was raised to 220° C. over 30 minutes, and the degree of pressure reduction was adjusted to 20.0 kPa. Thereafter, the temperature was raised to 240° C. and the degree of pressure reduction was adjusted to 10 kPa over a further 30 minutes. After holding at that temperature for 10 minutes, the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. After the reaction was completed, nitrogen was discharged from the bottom of the reaction tank under pressure, and while cooling in a water tank, the mixture was cut with a pelletizer to obtain pellets (PC1). Various evaluations were performed on the obtained pellets. The evaluation results are listed in Table 1.
<Manufacture of resin composition>
Polycarbonate resin PC1 and acrylic resin PMMA1: Mitsubishi Rayon's Acrypet VH-001 (copolymerized acrylic resin of methyl methacrylate and methyl acrylate) was used, and after drying each resin at 80°C for 12 hours or more, the weight ratio was 70. :30, and then 0.01 part by weight of carbodiimide C1 was added to 100 parts by weight of the resin. Thereafter, both the cylinder and die were melt-kneaded at 240° C. using a vented twin-screw extruder [KZW15-25MG manufactured by Technobel Co., Ltd.] to obtain blended pellets of acrylic resin and polycarbonate resin. A portion of the obtained pellets was dried at 90° C. for 12 hours or more, and then molded into test pieces for various evaluations using an injection molding machine. The evaluation results are shown in Table 1.
[Example 2]
<Manufacture of resin composition>
Except for adding 0.2 parts by weight of carbodiimide C1 to 100 parts by weight of the resin, the same operations as in Example 1 were performed, and the same evaluations were performed. The results are listed in Table 1.
[Example 3]
<Manufacture of resin composition>
The blend weight ratio was set to PC1:PMMA1 = 50/50, and 0.2 parts by weight of carbodiimide C1 was added to 100 parts by weight of resin, but the same operation as in Example 1 was performed and the same evaluation was performed. . The results are listed in Table 1.
[Example 4]
Except that 0.5 parts by weight of carbodiimide C1 was added to 100 parts by weight of the resin, the same operation as in Example 1 was performed, and the same evaluations were performed. The results are listed in Table 1.
[Example 5]
Except that 0.5 parts by weight of carbodiimide C2 was added to 100 parts by weight of the resin, the same operation as in Example 1 was performed, and the same evaluations were performed. The results are listed in Table 1.
[Example 6]
Except that 1.5 parts by weight of carbodiimide C2 was added to 100 parts by weight of the resin, the same operation as in Example 1 was performed, and the same evaluations were performed. The results are listed in Table 1.
[Example 7]
<Production of polycarbonate resin>
445 parts of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as BCF), 695 parts of SPG, 750 parts of DPC, and 0.6 x 10 ^-4 parts of sodium bicarbonate as a catalyst were added at 200 parts under a nitrogen atmosphere. It was heated to 0.degree. C. to melt it. Thereafter, the temperature was raised to 240° C. over 30 minutes, and the degree of pressure reduction was adjusted to 20.0 kPa. Thereafter, the temperature was raised to 270° C. and the degree of pressure reduction was adjusted to 10 kPa over a further 30 minutes. After holding at that temperature for 10 minutes, the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. After the reaction was completed, nitrogen was discharged from the bottom of the reaction tank under pressure, and while cooling in a water tank, the mixture was cut with a pelletizer to obtain pellets (PC2). Various evaluations were performed on the obtained pellets. The evaluation results are listed in Table 1.
<Manufacture of resin composition>
Polycarbonate resin PC2 and acrylic resin PMMA1: Mitsubishi Rayon's Acrypet VH-001 (copolymerized acrylic resin of methyl methacrylate and methyl acrylate) was used, and after drying each resin at 90°C for 12 hours or more, the weight ratio was 70. :30, and then 0.2 parts by weight of carbodiimide C1 was added to 100 parts by weight of the resin. Thereafter, both the cylinder and die were melt-kneaded at 270° C. using a vented twin-screw extruder [KZW15-25MG manufactured by Technovel Co., Ltd.] to obtain blended pellets of acrylic resin and polycarbonate resin. A portion of the obtained pellets was dried at 90° C. for 12 hours or more, and then molded into test pieces for various evaluations using an injection molding machine. The evaluation results are shown in Table 1.
[Example 8]
672 parts of bisphenol A (hereinafter abbreviated as BPA), 158 parts of SPG, 750 parts of DPC, and 0.6×10 ⁻⁴ parts of sodium hydrogen carbonate as a catalyst were heated to 200° C. and melted under a nitrogen atmosphere. Thereafter, the temperature was raised to 240° C. over 30 minutes, and the degree of pressure reduction was adjusted to 20.0 kPa. Thereafter, the temperature was raised to 280° C. and the degree of pressure reduction was adjusted to 10 kPa over a further 30 minutes. After holding at that temperature for 10 minutes, the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. After the reaction was completed, nitrogen was discharged from the bottom of the reaction tank under pressure, and while cooling in a water tank, it was cut with a pelletizer to obtain pellets (PC3). Various evaluations were performed on the obtained pellets. The evaluation results are listed in Table 1.
<Manufacture of resin composition>
Polycarbonate resin PC3 and acrylic resin PMMA1: Mitsubishi Rayon's Acrypet VH-001 (copolymerized acrylic resin of methyl methacrylate and methyl acrylate) was used, and after drying each resin at 90°C for 12 hours or more, the weight ratio was 70. :30, and then 0.2 parts by weight of carbodiimide C1 was added to 100 parts by weight of the resin. Thereafter, both the cylinder and die were melt-kneaded at 280° C. using a vented twin-screw extruder [KZW15-25MG manufactured by Technobel Co., Ltd.] to obtain blended pellets of acrylic resin and polycarbonate resin. A portion of the obtained pellets was dried at 90° C. for 12 hours or more, and then molded into test pieces for various evaluations using an injection molding machine. The evaluation results are shown in Table 1.
[Example 9]
Except for using 253 parts of ISS, 250 parts of CHDM, and 750 parts of DPC as raw materials, the same operation as in Example 1 was performed, and the same evaluation was performed (PC6). The results are listed in Table 1.
[Comparative example 1]
The same operation as in Example 1 was performed, except that carbodiimide C1 was not added, and the same evaluation was performed. The results are listed in Table 1. The decrease in η _SP before and after the wet heat test and the dry heat test was large and inferior to Example 1.
[Comparative example 2]
The same operation as in Example 7 was performed, except that carbodiimide C1 was not added, and the same evaluation was performed. The results are listed in Table 1. The decrease in η _SP before and after the wet heat test and the dry heat test was large and inferior to Example 7.
[Comparative example 3]
The same operation as in Example 8 was performed, except that carbodiimide C1 was not added, and the same evaluation was performed. The results are listed in Table 1. The decrease in η _SP before and after the wet heat test and dry heat test was large and inferior to Example 8.
[Comparative example 4]
Evaluation was carried out in exactly the same manner as in Example 1, except that only Panlite L-1225 (PC4) manufactured by Teijin Ltd. was used and the extrusion temperature and molding temperature were 280°C. It was inferior to the Examples in terms of surface hardness and weather resistance.
[Comparative example 5]
Evaluations were conducted in exactly the same manner as in Example 1, except that only Acrypet VH-001 (copolymerized acrylic resin of methyl methacrylate and methyl acrylate) manufactured by Mitsubishi Rayon Co., Ltd. was used, and the extrusion temperature and molding temperature were 250°C. It was inferior to the Examples in terms of impact resistance and deflection temperature under load.
[Comparative example 6]
<Production of polycarbonate resin>
The same operation as in Example 1 was performed, except that 354 parts of ISS, 150 parts of CHDM, and 750 parts of DPC were used as raw materials, and carbodiimide C1 was not added, and the same evaluation was performed (PC5). The results are listed in Table 1.
<Manufacture of resin composition>
Extrusion was carried out in exactly the same manner as in Example 1, but whitened pellets were obtained. The molded product after molding also turned white and could not maintain its transparency at all.
[Comparative Example 7]
The same operation as in Example 9 was performed, except that carbodiimide C1 was not added, and the same evaluation was performed. The results are listed in Table 1. Although the molded product maintained its transparency after molding, it was inferior to Example 9, with a large decrease in η _SP before and after the wet heat test and the dry heat test.

The resin composition of the present invention is applicable to optical lenses, optical discs, optical films, plastic cell substrates, optical cards, liquid crystal panels, headlamp lenses, light guide plates, diffusion plates, protective films, OPC binders, front plates, housings, trays, water tanks, etc. It is useful as a member for lighting covers, signboards, resin windows, etc.

Claims (9)

(A) Contains 5 to 85 mol% of the repeating unit ( a-1 ) represented by the following formula (a-1) in all repeating units , and contains the repeating unit (a-1) represented by the following formula (a-2) as other repeating units. polycarbonate resin containing repeating units (a-2), repeating units derived from aliphatic diols, repeating units derived from alicyclic diols, or repeating units derived from aromatic dihydroxy compounds, (B) methacrylic An acrylic resin containing 10 to 100 mol% of repeating units (b) derived from methyl acid and/or methyl acrylate in all repeating units, and (C) a carbodiimide, comprising (A) a polycarbonate resin and (B) an acrylic resin. A resin composition in which the weight ratio of (C) carbodiimide is 30:70 to 95:5 , and the content of carbodiimide (C) is 0.001 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin and acrylic resin.
(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, and R ₁ is a branched or straight-chain alkyl group having 1 to 20 carbon atoms, or has a substituent. represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)
The resin composition according to claim 1 , wherein the specific viscosity of the polycarbonate resin (A) is in the range of 0.2 to 1.5. The resin composition according to claim 1 or 2, wherein the weight average molecular weight of the acrylic resin (B) is in the range of 30,000 or more and 300,000 or less. The resin composition according to any one of claims 1 to 3 , wherein the acrylic resin (B) has a specific viscosity in the range of 0.12 to 0.55. The resin composition according to any one of claims 1 to 4, wherein the acrylic resin (B) has a glass transition temperature (Tg) of 90 to 150°C. The resin composition according to any one of claims 1 to 5 , wherein the carbodiimide (C) has a molecular weight of 150 to 13,000. The resin composition according to any one of claims 1 to 6 , wherein the haze of a 2 mm thick test piece is 30% or less. A molded article obtained by injection molding the resin composition according to any one of claims 1 to 7 . A film or sheet formed from the resin composition according to any one of claims 1 to 7 .