JP2021134295A - Resin composition - Google Patents

Abstract

To provide a resin composition which combines excellent tensile characteristics with a low water absorption ratio and contains polycarbonate resin and an ethylene-(meth)acrylate copolymer.SOLUTION: A resin composition contains a polycarbonate resin (A) including 15-75 mol% of a repeating unit represented by the following formula (a-1) in the total repeating unit, and a copolymer (B) having an ethylene-derived structural unit and a (meth)acrylate-based monomer-derived structural unit. In the formula, W represents an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 6 to 20 carbon atoms; R1 represents a branched or straight-chain alkyl group having 1 to 20 carbon atoms or a cycloalkylene group which may have a substituent and has 6 to 20 carbon atoms; and m represents an integer of 0-10.SELECTED DRAWING: None

Description

The present invention relates to a composition containing a polycarbonate resin and a copolymer having a structural unit derived from ethylene and a structural unit derived from a (meth) acrylate-based monomer.

Conventionally, a polycarbonate resin made of bisphenol A is widely used for vehicle applications and building materials because it is excellent in heat resistance, impact resistance, flame retardancy, and transparency. On the other hand, in use for these applications, the polycarbonate resin may have problems in solvent resistance and moldability. In order to solve these problems, polycarbonate resin compositions containing polyolefins and polyesters have been reported so far (Patent Documents 1 and 2). However, since these compositions use a special polyethylene having an epoxy group introduced in order to enhance the compatibility between the resins, the applications that can be used have been limited.

In recent years, due to concerns about the depletion of petroleum resources and the problem of an increase in carbon dioxide in the air that causes global warming, carbon neutrality has been established that does not depend on oil for raw materials and does not increase carbon dioxide even when burned. Biomass resources have attracted a great deal of attention, and in the field of polymers, biomass plastics produced from biomass resources are being actively developed. In particular, polycarbonate mainly containing isosorbide as a monomer is excellent in heat resistance, weather resistance, surface hardness, and chemical resistance, and is attracting attention because it has characteristics different from those of general bisphenol A polycarbonate. (Patent Documents 3 and 4). While these isosorbide-based polycarbonates have excellent characteristics, they have a problem of high water absorption. From such a background, a composition with polyethylene having a low water absorption rate can be considered, but since these resins are essentially incompatible, they do not exhibit excellent properties as a resin composition.

In order to solve these problems, a composition with an acrylic resin using a polycarbonate having a special structure having a spiro ring has been reported (Patent Document 5), and both the excellent properties of the polycarbonate and the acrylic resin are compatible. Has been achieved.

However, in the composition of the resin containing various polycarbonate and polyethylene components without using a special functional group, a composition exhibiting excellent physical properties and low water absorption has not been reported so far.

Japanese Unexamined Patent Publication No. 5-39415 Japanese Unexamined Patent Publication No. 2004-14328 Japanese Unexamined Patent Publication No. 2006-36954 JP-A-2009-46519 Japanese Unexamined Patent Publication No. 2015-232091

An object of the present invention is to provide a resin composition having excellent tensile properties and low water absorption properties.

As a result of intensive studies, the present inventors have made a composition containing a polycarbonate resin having a specific structure and a copolymer having a structural unit derived from ethylene and a structural unit derived from a (meth) acrylate-based monomer. It has been clarified that the product is a resin composition having excellent tensile properties and low water absorption, and the present invention has been completed.

（式中、Ｗは炭素数１〜２０のアルキレン基または炭素数６〜２０のシクロアルキレン基を表し、Ｒ_１は炭素数１〜２０の分岐または直鎖のアルキル基、もしくは置換基を有してもよい炭素数６〜２０のシクロアルキル基を表し、ｍは０〜１０の整数を示す。）
２．共重合体（Ｂ）がエチレンに由来する構成単位とメタクリル酸メチルモノマーに由来する構成単位とを有する前項１に記載の樹脂組成物。
３．共重合体（Ｂ）に含まれる（メタ）アクリレート系モノマーに由来する構成単位の含有量が１０〜５０重量％である前項１または２に記載の樹脂組成物。
４．前記ポリカーボネート樹脂（Ａ）は、下記式（ａ−２）で表される単位を含有する、前項１〜３のいずれかに記載の樹脂組成物。

５．ポリカーボネート樹脂（Ａ）と共重合体（Ｂ）との重量比が５０：５０〜９９：１である前項１〜４のいずれかに記載の樹脂組成物。
６．２０℃の塩化メチレン溶液で測定された比粘度が０．１５〜１．５であるポリカーボネート樹脂（Ａ）を含む前項１〜５のいずれかに記載の樹脂組成物。
７．飽和吸水率が２．０重量％以下である前項１〜６のいずれかに記載の樹脂組成物。
８．前項１〜７のいずれかに記載の樹脂組成物を射出成形して得られる成形品。
９．前項１〜７のいずれかに記載の樹脂組成物から形成されるフィルムまたはシート。 That is, according to the present invention, the subject of the invention is achieved by the following.
1. 1. Polycarbonate resin (A) containing 15 to 75 mol% of the repeating units represented by the following formula (a-1) in all the repeating units.
A copolymer (B) having a structural unit derived from ethylene and a structural unit derived from a (meth) acrylate-based monomer.
A resin composition containing.

(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 has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)
2. The resin composition according to item 1 above, wherein the copolymer (B) has a structural unit derived from ethylene and a structural unit derived from a methyl methacrylate monomer.
3. 3. The resin composition according to item 1 or 2 above, wherein the content of the structural unit derived from the (meth) acrylate-based monomer contained in the copolymer (B) is 10 to 50% by weight.
4. The resin composition according to any one of items 1 to 3 above, wherein the polycarbonate resin (A) contains a unit represented by the following formula (a-2).

5. The resin composition according to any one of the above items 1 to 4, wherein the weight ratio of the polycarbonate resin (A) to the copolymer (B) is 50:50 to 99: 1.
6. The resin composition according to any one of the above items 1 to 5, which comprises a polycarbonate resin (A) having a specific viscosity of 0.15 to 1.5 measured in a methylene chloride solution at 20 ° C.
7. The resin composition according to any one of items 1 to 6 above, wherein the saturated water absorption rate is 2.0% by weight or less.
8. A molded product obtained by injection molding the resin composition according to any one of the above items 1 to 7.
9. A film or sheet formed from the resin composition according to any one of the preceding items 1 to 7.

The present invention has a tensile property and low water absorption by containing a polycarbonate resin having a specific structure and a copolymer having a structural unit derived from ethylene and a structural unit derived from a (meth) acrylate-based monomer. It has become possible to provide a resin composition having excellent properties. Therefore, the industrial effect it produces is exceptional.

（式中、Ｗは炭素数１〜２０のアルキレン基または炭素数６〜２０のシクロアルキレン基を表し、Ｒ₁は炭素数１〜２０の分岐または直鎖のアルキル基、もしくは置換基を有してもよい炭素数６〜２０のシクロアルキル基を表し、ｍは０〜１０の整数を示す。） Hereinafter, the present invention will be described in detail.
[Polycarbonate resin (A)]
The polycarbonate resin used in the resin composition of the present invention is a polycarbonate resin whose repeating unit contains a unit represented by the following formula (a-1).

(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 has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It represents a cycloalkyl group having 6 to 20 carbon atoms, and m represents an integer of 0 to 10.)

The unit represented by the above formula (a-1) is derived from a diol having a spiro ring structure. Examples of the diol compound having such a spiro ring structure include 3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane and 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. An alicyclic diol compound can be 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 preferably contains 15 to 85 mol% of the repeating units represented by the above formula (a-1) in all the repeating units, and contains 20 to 80 mol%. More preferably, it further preferably contains 30 to 70 mol%. When the unit represented by the formula (a-1) is within the above range, the tensile properties are remarkably improved by improving the affinity between the resins in the resin composition, and the polycarbonate resin crystallizes during polymerization. It is preferable because the polymerization is easy without any problem.

The polycarbonate resin used in the resin composition of the present invention is preferably a polycarbonate resin containing a unit represented by the formula (a-1) and a unit represented by the following formula (a-2). ..

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

The unit represented by the above formula (a-2) is represented by the following formulas (a-2-1), (a-2-2) and (a-2-3) having a stereoisomeric relationship. Units are illustrated.

These are sugar-derived ether diols, which are also obtained from natural biomass, and are one of the so-called renewable resources. The repeating units represented by the formulas (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 be obtained by the same reaction except for the starting material.

Among isosorbide, isomannide, and isosorbide, the repeating unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because it is easy to manufacture and has excellent heat resistance.

The repeating unit represented by the formula (a-2) preferably contains 15 to 85 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol% in all the repeating units. When the repeating unit represented by the formula (a-2) is within the above range, the balance between tensile properties and low water absorption is excellent, which is preferable.

In the present invention, the repeating unit derived from various diol compounds is used as a repeating unit constituting a copolymerization structural unit other than the repeating unit represented by the formula (a-1) and the repeating unit represented by the formula (a-2). The unit is mentioned.

Examples of the aliphatic diol compound include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1.9-nonanediol, and 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-hexaneglycol, 1,2-octylglycol, 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 and the like. Therefore, 1,8-octanediol, 1.9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferably used.

Examples of the alicyclic diol compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and 1,2-cyclohexane. Cyclohexanedimethanol such as dimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, norbornanedimethanol such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, tricyclode Examples thereof include candimethanol, pentacyclopentadecanedimethanol, 1,3-adamantandiol, 2,2-adamantandiol, decalindimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and cyclohexane. Dimethanol and 4,4-tetramethyl-1,3-cyclobutanediol are preferably used.

Examples of the aromatic dihydroxy compound include α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 1,1-. Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 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) ), 1,1-Bis (4-hydroxyphenyl) decane and the like, and bisphenol A is preferably used.

The content of the copolymerization constituent units other than the repeating unit represented by the formula (a-1) and the repeating unit represented by the formula (a-2) is preferably 50 mol% or less, 40, among all the repeating units. Mol% or less, 35 mol% or less, 30 mol% or less, 25 mol% or less, 20 mol% or less, 15 mol% or less, 10 mol% or less.

(Manufacturing method of polycarbonate resin)
The polycarbonate resin is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a diol component with a carbonic acid precursor such as a carbonic acid diester. Next, the basic means for these manufacturing methods will be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonic acid precursor is carried out by a method in which a predetermined proportion of the diol component is stirred with the carbonic acid diester while heating under an inert gas atmosphere to distill off the produced alcohol or phenols. 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 by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. Further, if necessary, a terminal terminator, an antioxidant or the like may be added.

Examples of the carbonic acid diester used in the transesterification reaction include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples thereof include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferable. The amount of the diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, based on 1 mol of the total dihydroxy compound.
Further, in the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate, and examples of such a polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

As such a compound, an organic acid salt, an inorganic salt, an oxide, a hydroxide, a hydride, an alkoxide, a quaternary ammonium hydroxide, or the like of an alkali metal or an alkaline earth metal is preferably used, and these compounds are used. It can be used alone or in combination.

Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, etc. Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples thereof include 2 lithium hydrogen acid, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium phenol salt, potassium salt, cesium salt, lithium salt and the like.

Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, strontium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and diacetic acid. Examples thereof include barium and barium stearate.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having alkyl and aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide. Can be mentioned. Examples thereof 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, tetrabutylammoniumtetraphenylborate, tetraphenylammoniumtetraphenylborate and the like are exemplified.
Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin 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, and more preferably 1 × 10 to 1 mol of the diol component. It is selected in the range of ^10-7 to 1 × 10 ^{-3 equivalents.}

It is also possible to add a catalytic deactivator in the latter stage of the reaction. As the catalyst deactivating agent to be used, known catalyst deactivating agents are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acids are preferable. Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as paratoluenesulfonic acid tetrabutylammonium salt are preferable.

As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenylbenzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluene sulfonate, phenyl paratoluene sulfonate and the like are preferably used. Of these, the tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is most preferably used.

The amount of these catalyst deactivators used is preferably 0.5 to 50 mol per mole of the catalyst when at least one polymerization catalyst selected from the alkali metal compound and / or the alkaline earth metal compound is used. It can be used in proportions, more preferably 0.5 to 10 mol, and even more preferably 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 good. It is more preferably 0.25 to 1.2, still more preferably 0.3 to 1.0, and particularly preferably 0.3 to 0.5.

The specific viscosity referred to in the present invention was obtained from a solution prepared by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]

The specific specific viscosity can be measured, for example, as follows. First, the polycarbonate resin is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and sufficiently dried to obtain a solid of methylene chloride soluble component. The specific viscosity at 20 ° C. of a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride is determined using an Ostwald viscometer.

[Copolymer (B)]
The copolymer (B) used in the resin composition of the present invention has a structural unit derived from ethylene and a structural unit derived from a (meth) acrylate-based monomer.

Examples of the (meth) acrylate-based monomer include methyl methacrylate, methacrylic acid, methyl acrylate, acrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (. Meta) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) Acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy Ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acroyloxy maleate Ethyl, 2- (meth) acroyloxyethyl phthalate, 2- (meth) aclioil oxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) Examples thereof include acrylate, diethylaminoethyl (meth) acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, and cyclododecyl acrylate. These may be used alone or in two or more types. Of these, methyl (meth) acrylate is particularly preferable from the viewpoint of being particularly excellent in affinity with the polycarbonate resin (A) and industrial utility.

The content of the structural unit derived from the (meth) acrylate-based monomer in the copolymer (B) is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, and particularly preferably 20 to 40% by weight. be. If this content ratio is less than 10% by weight, the compatibility of the copolymer (B) with the polycarbonate resin (A) is excessively lowered, and sufficient tensile properties cannot be obtained. On the other hand, when this content ratio exceeds 50% by weight, the water absorption rate increases.

The molecular weight of the copolymer (B) 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 do not occur during molding. , A composition having excellent mechanical properties and heat resistance can be provided.

[Manufacturing method of resin composition]
The resin composition of the present invention is preferably produced by blending the polycarbonate resin (A) and the copolymer (B) in a molten state. As a method of blending in a molten state, an extruder or a laboplast mill is generally used, and kneading is performed at a molten resin temperature of 200 to 320 ° C., preferably 220 to 300 ° C., more preferably 230 to 290 ° C. As a result, a resin composition in which both resins are uniformly blended can be obtained. The configuration of the extruder, the configuration of the screw, and the like are not particularly limited. If the temperature of the molten resin in the extruder exceeds 320 ° C, the resin may be colored or thermally decomposed. On the other hand, if the resin temperature is lower than 200 ° C., the resin viscosity may be too high and the extruder may be overloaded.

[Weight ratio]
The weight ratio of the polycarbonate resin (A) and the copolymer resin (B) is preferably in the range of 50:50 to 99: 1, and can be arbitrarily mixed in that range. It is more preferably in the range of 60:40 to 95: 5, still more preferably in the range of 70:30 to 90:10, and particularly preferably in the range of 75:25 to 85:15. Within the above range, a resin composition having excellent tensile properties and low water absorption can be obtained.

[Additive]
The resin composition of the present invention includes a heat stabilizer, a plasticizer, a light stabilizer, a polymer metal inactivating agent, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, and ultraviolet rays, depending on the application and need. Additives such as absorbents, mold release agents, and colorants can be added.

(Heat stabilizer)
The resin composition of the present invention preferably contains a heat stabilizer in order to suppress a decrease in molecular weight and deterioration of hue 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 of these can be used alone or in combination of two or more. As the phosphorus-based stabilizer, it is preferable to add a phosphite compound. Examples of the phosphite compound include a pentaerythritol-type phosphite compound, a phosphite compound that reacts with divalent phenols and has a cyclic structure, and a phosphite compound having another structure.

Specific examples of the above-mentioned pentaerythritol-type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and 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 thereof include bis (nonylphenyl) pentaerythritol diphosphite and dicyclohexylpentaerythritol diphosphite, and among them, distearyl pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) penta are preferable. Examples include erythritol diphosphite.

Examples of the phosphite compound having a cyclic structure by reacting with the above divalent 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) octylphosphite, 6-tert-butyl-4- [3-[(2,4,8,10)) -Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl) oxy] propyl] -2-methylphenol and the like can be mentioned.

Examples of the phosphite compound having the above other structure include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, and didecylmonophenylphosphite. , Dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyldiphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphos Fight, 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 and the like.
In addition to various phosphite compounds, for example, phosphate compounds, phosphonite compounds, and phosphonate compounds can be mentioned.

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 thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.
Phosphonite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrakiss (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di) -N-Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more.

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

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

The above phosphorus-based heat stabilizers can be used alone or in combination of two or more. The phosphorus-based 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 further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Will be done.

The resin composition of the present invention uses 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 deterioration of hue during extrusion / molding, and a phosphorus-based heat. It can also be added in combination with a stabilizer.

The hindered phenol-based heat stabilizer is not particularly limited as long as it has an antioxidant function, and is, 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, triethireglycol-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- (3,3) 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 "-(mesitylen-2,4,6-triyl) tri- Examples thereof 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'-(mesitylen-2,4,6-triyl) Tri-p-cresol, 2,2-thiodiethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} and the like are preferable.

One of these hindered phenolic heat stabilizers may be used alone, or two or more thereof may be used in combination.

The hindered phenolic heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Partially 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 di-dipropionic acid ester. Stearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3) -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis (2-naphthol) and the like. .. Of the above, pentaerythritol tetrakis (3-laurylthiopropionate) is preferable.

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

The sulfur-based 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 further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Will 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 of these is preferably 0.001 to 1 part by weight, more preferably 0, based on 100 parts by weight of the resin composition. .01 to 0.3 parts by weight is blended.

(Release agent)
In the resin composition of the present invention, in order to further improve the mold release property from the mold during melt molding, it is possible to add 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 monovalent or polyhydric alcohols, higher fatty acids, paraffin waxes, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic acid anhydride groups, silicone oils, etc. Organopolysiloxane and the like can be mentioned.

As the higher fatty acid ester, a partial ester or a total ester of a monovalent or polyvalent alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of the partial ester or total ester of the monovalent or polyvalent alcohol and the saturated fatty acid 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, biphenyl biphene -To, sorbitan monostearate, 2-ethylhexyl stearate and the like.
Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

These release agents may be used alone or in combination of two or more. The blending amount of the release agent is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin composition.

(UV absorber)
The resin composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like, among which benzotriazole-based ultraviolet absorbers are used. Agents are preferred.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, and 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" -tetraphthalimidemethyl) -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-benzotriazole-2-yl) phenol], methyl-3- [3 Examples thereof include benzotriazole-based ultraviolet absorbers typified by a condensate of −tert-butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol.

The ratio of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, and further preferably 0.2 to 0.5 part by weight with respect to 100 parts by weight of the resin composition. Is.

(Light stabilizer)
The resin composition of the present invention can contain a light stabilizer. When a light stabilizer is contained, it is good in terms of weather resistance and has an advantage that cracks are less likely to occur in the molded product.

Examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis didecanoate (2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, and the like. 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-tetramethylpiperidine-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) phenylphosphite, nickel such as nickelbis (octylphenylsulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzylphosphate monoethylate, nickeldibutyldithiocarbamate) Examples thereof 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, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin composition.

(Epoxy stabilizer)
In order to improve the hydrolyzability, the resin composition of the present invention can contain an epoxy compound as long as the object of the present invention is not impaired.

Epoxide-based stabilizers include epoxidized soybean oil, epoxidized flaxseed oil, phenylglycidyl ether, allylglycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'-epoxide cyclohexylcarboxylate. , 3,4-Epoxide-6-methylcyclohexylmethyl-3', 4'-epoxide-6'-methylcyclohexylcarboxylate, 2,3-epoxidecyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3,4-Epoxide-5-methylcyclohexyl) Butyl-3', 4'-epoxycyclohexylcarboxylate, 3,4-epoxidecyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxide -6-Methylcyclohexylmethyl-6'-methylsilohexyl carboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxide dicyclo Pentazienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadienediepoxide, tetraphenylethyleneepoxide, octyl epoxide, 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-epoxidecyclohexylcarboxylate, N-butyl-2 , 2-Dimethyl-3,4-epoxide cyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxide-5-methylcyclohexylcarboxylate, Octadecyl-3,4-epoxide cyclohexylcarboxylate, 2-ethylhexyl-3', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxide cyclohexyl-3', 4'-epoxide cyclohexylcarboxylate, 4,5-Epoxide tetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxide tetrahydrophthalic anhydride, diethyl-4,5 -Epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate and the like can be mentioned. Bisphenol A diglycidyl ether is preferable from the viewpoint of compatibility and the like.

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

(Bluing agent)
In the resin composition of the present invention, a bluing agent can be added to counteract the yellowness of the lens based on the polymer or the ultraviolet absorber. As the bluing agent, any one used for polycarbonate can be used without any particular problem. Generally, anthraquinone dyes are easily available and preferable.

Specific examples of the brewing agent include, for example, the generic name Solvent Violet 13 [CA. No (color index No) 60725], generic name Solvent Violet31 [CA. No 68210, generic name Solvent Violet33 [CA. No 60725], generic name Solvent Blue94 [CA. No 61500], generic name Solvent Violet36 [CA. No 68210], generic name Solvent Blue97 [Bayer's "Macrolex Violet RR"] and generic name Solvent Blue45 [CA. No61110] is a typical example.

These brewing agents may be used alone or in combination of two or more. These bluing agents are preferably blended in a ratio of ^{0.1 × 10 -4} to 2 × 10 ^-4 parts by weight with respect to 100 parts by weight of the resin composition.

(Flame retardants)
A flame retardant can also be added to the resin composition of the present invention. Flame retardants include halogen-based flame retardants such as brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, and chlorinated polyethylene, and phosphate ester-based flame retardants such as monophosphate compounds and phosphate oligomeric compounds. Organic phosphorus flame retardants other than phosphoric acid ester flame retardants such as phosphinate compounds, phosphonate compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, organic sulfonic acid alkali (earth) metal salts, borate metal salt flame retardants, Includes organic metal salt flame retardants such as metal tinic acid flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, triazine flame retardants and the like. Separately, a flame retardant aid (for example, sodium antimonyate, antimony trioxide, etc.), a drip inhibitor (polytetrafluoroethylene having a fibril-forming ability, etc.) and the like may be blended in combination with the flame retardant.

Among the above-mentioned flame retardants, compounds that do not contain chlorine atoms and bromine atoms are one of the features that reduce the environmental load because they reduce the factors that are considered unfavorable when incinerating waste or thermal recycling. It is more suitable as a flame retardant in the molded product of the present invention.

When the flame retardant is blended, it is preferably in the range of 0.05 to 50 parts by weight per 100 parts by weight of the resin composition. Within the above range, sufficient flame retardancy is exhibited, and the strength and heat resistance of the molded product are excellent.

(Elastic polymer)
In the resin composition of the present invention, an elastic polymer can be used as an impact improver, and examples of the elastic polymer include natural rubber or a rubber component having a glass transition temperature of 10 ° C. or less, and aromatic vinyl. , Vinyl cyanide, acrylic acid ester, methacrylic acid ester, and a graft copolymer in which one or more of the monomers selected from the vinyl compounds copolymerizable therewith are copolymerized. A more suitable elastic polymer is a core-shell type graft copolymer in which one or more shells of the above-mentioned monomers are graft-copolymerized on the core of the rubber component.

In addition, a block copolymer of such a rubber component and the above-mentioned monomer can also be mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomer (hydrogenated styrene / isoprene / styrene elastomer) and hydrogenated styrene / butadiene / styrene elastomer. Furthermore, various elastic polymers known as other thermoplastic elastomers, such as polyurethane elastomers, polyester elastomers, and polyetheramide elastomers, can also be used.

A more suitable impact improver is a core-shell type graft copolymer. 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 0.1 to 0.5 μm in terms of 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 40% or more of a rubber component, and 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, ethylene- Acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bond portions can be mentioned, but they contain halogen atoms from the viewpoint of concern about the generation of harmful substances during combustion. A non-rubber component is preferable in terms of environmental load.

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. The composite rubber refers to a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure in which they are intertwined with each other so as not to be separated.

Examples of aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene, and the like, and styrene is particularly preferable. Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate, and examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and methacrylic acid. Butyl, cyclohexyl methacrylate, octyl methacrylate and the like can be mentioned, and methyl methacrylate is particularly preferable. 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, and more preferably 15% by weight or more. Will be done.

The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or lower may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method is as follows. It does not matter whether it is a one-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during production. Further, as the polymerization method, 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 can be mentioned. Further, in the suspension polymerization method, a method in which the aqueous phase and the monomer phase are individually held and both are accurately supplied to a continuous disperser, and the particle size is controlled by the rotation speed of the disperser, and continuous production. In the method, a method of controlling the particle size by supplying the monomer phase into an aqueous liquid having dispersibility by passing it through a small-diameter orifice or a porous filter having a diameter of several to several tens of μm may be used. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

Such elastic polymers are commercially available and easily available. For example, as the rubber component, butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber is mainly used as Kaneace B series (for example, B-56) of Kanebuchi Chemical Industry Co., Ltd. and Metabren of Mitsubishi Rayon Co., Ltd. C series (eg C-223A etc.), W series (eg W-450A etc.), Kureha Chemical Industry Co., Ltd. Pararoid EXL series (eg EXL-2602 etc.), HIA series (eg HIA-15 etc.), BTA series (For example, BTA-III, etc.), KCA series, Rohm & Hearth's Pararoid EXL series, KM series (for example, KM-336P, KM-357P, etc.), and Ube Psycon Co., Ltd.'s UCL modifier resin series (UMG).・ UMG AXS resin series of ABS Co., Ltd.), etc., and those containing acrylic-silicone composite rubber as the rubber component are commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of Metabren S-2001 or SRK-200. Some are listed.

The composition ratio of the impact improver 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 give good impact resistance to the composition while suppressing a decrease in rigidity.

[Molding]
The resin composition of the present invention is 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, and a casting method, and is a member for electrical and electronic applications, vehicle interior / exterior applications, and the like. Can be used as a molded product of.

[Tensile fracture strain]
The tensile fracture strain of the resin composition of the present invention is a value measured at 23 ° C. in accordance with JIS K7127, and specifically, a value measured by the method described in Examples described later. From the viewpoint of mechanical strength, the tensile fracture strain (%) of the resin composition of the present embodiment is preferably higher, preferably 15% or more, and more preferably 20% or more.

[Fracture toughness]
The fracture toughness of the resin composition of the present invention is an area value of a stress strain curve measured at 23 ° C. according to JIS K7127. Specifically, it is a value measured by the method described in Examples described later. ^{From the viewpoint of mechanical strength, the fracture toughness (MJ / m 3} ) of the resin composition of the present embodiment is preferably higher, preferably 5 or more, and more preferably 8% or more.

[Saturated water absorption rate]
The saturated water absorption rate of the resin composition of the present invention is preferably 2.0% or less, more preferably 1.5% or less. When the water absorption rate is 2.0% or less, dimensional change and warpage due to water absorption can be reduced in the molded product, which is preferable.

[surface treatment]
Various surface treatments can be applied to the molded product formed from the resin composition of the present invention. Surface treatment here means a new layer on the surface layer of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, 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 various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metallizing (evaporation, etc.). Hard coat is a particularly preferred and required surface treatment.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the examples, "part" means "part by weight". The resin used and the evaluation method used in the examples are as follows.

(Evaluation of polycarbonate resin)
1. 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. It was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at a specific viscosity of 20 ° C.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
(Evaluation of composition film)
3. 3. Tensile Fracture Strain The obtained film was subjected to a tensile test at a speed of 10 mm / min with a tensile tester manufactured by A & D Co., Ltd., and the elongation at break was defined as the tensile fracture strain.
4. Fracture toughness The obtained film was subjected to a tensile test at a speed of 10 mm / min with a tensile tester manufactured by A & D Co., Ltd., and the area value of the obtained stress strain curve was defined as the fracture toughness.
5. Saturated water absorption rate The obtained film was dried at 80 ° C. for 12 hours, then immersed in water at 25 ° C. for 240 hours, and then the weight increase was measured, and the water absorption rate was determined by the following formula.
Water absorption rate (%) = {(weight of resin after water absorption-weight of resin before water absorption) / weight of resin before water absorption} x 100

[Polycarbonate resin]
PC1 (Example):
Structural unit derived from isosorbide (ISS) / 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane (SPG) Structural unit derived from = 70/30 (mol%), specific viscosity 0.366

PC2 (Example):
Structural unit derived from ISS / structural unit derived from SPG = 40/60 (mol%), specific viscosity 0.392

PC3 (comparative example):
Structural unit derived from ISS / structural unit derived from SPG = 90/10 (mol%), specific viscosity 0.342

PC4 (comparative example):
Polycarbonate consisting of structural units derived from the ISS, specific viscosity 0.312

PC5 (comparative example):
Structural unit derived from bisphenol A (BPA) / structural unit derived from SPG = 10/90 (mol%)

PC6 (Example):
Structural unit derived from bisphenol A (hereinafter BPA) / structural unit derived from SPG = 70/30 (mol%), specific viscosity 0.386

PC7 (comparative example):
Structural unit derived from BPA / structural unit derived from SPG = 90/10 (mol%), specific viscosity 0.326

[Ethylene-methylmethacrylate copolymer]
EMMA: Sumitomo Chemical's Aklift WK307 (weight ratio: ethylene / methyl methacrylate = 75/25)

[Polyethylene (low density polyethylene)]
LDPE: ULT-ZEX (C6-LLDPE) 20100J manufactured by Prime Polymer Co., Ltd.

[Example 1]
<Manufacturing of polycarbonate resin>
ISS354 parts, SPG316 parts, (hereinafter abbreviated as DPC) diphenyl carbonate 750 parts, and tetramethylammonium hydroxide 0.8 × ^{10 -2} parts of barium stearate 0.6 × ^{10 -4} parts 200 under a nitrogen atmosphere as a catalyst It was heated to ° C and melted. Then, the temperature was raised to 220 ° C. and the degree of decompression was adjusted to 20.0 kPa over 30 minutes. Then, the temperature was raised to 240 ° C. and the degree of decompression was adjusted to 10 kPa over another 30 minutes. After holding at that temperature for 10 minutes, the degree of decompression was set to 133 Pa or less over 1 hour. After completion of the reaction, the mixture was discharged from the bottom of the reaction tank under nitrogen pressurization, cooled in a water tank, and cut with a pelletizer to obtain pellets (PC1). Various evaluations were performed on the obtained pellets.

<Preparation of kneaded composition film>
Knead PC1 and EMMA at a weight ratio of 80:20 with a lab plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd. under the conditions of a kneading temperature of 250 ° C., a kneading time of 7 minutes, a kneading speed of 100 rpm, and nitrogen. went. Then, a film having a thickness of 0.3 mm was produced under the conditions of a press temperature of 250 ° C. and a press time of 5 minutes using a hot press machine. Table 1 shows various evaluations of the obtained films.

[Example 2]
Except for using 202 parts of ISS, 632 parts of SPG, and 750 parts of DPC as raw materials, exactly the same operation as in Example 1 was performed, and the same evaluation was performed (PC2). The results are shown in Table 1.

[Comparative Example 1]
Exactly the same operation as in Example 1 was performed except that ISS455 parts, SPG105 parts, and DPC750 parts were used as raw materials, and the same evaluation was performed (PC3). The results are shown in Table 1.

[Comparative Example 2]
Except for using 506 parts of ISS and 750 parts of DPC as raw materials, exactly the same operation as in Example 1 was performed, and the same evaluation was performed (PC4). The results are shown in Table 1.

[Comparative Example 3]
Except for using LDPE instead of EMMA, 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]
Except for using LDPE instead of EMMA, the same operation as in Example 2 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 5]
Except for using LDPE instead of EMMA, the same operation as in Comparative Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 6]
Except that the film was produced only with PC1, 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]
Except that the film was produced only with PC2, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 8]
Except that the film was produced only with PC3, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 9]
Except that the film was produced only with PC4, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 10]
<Manufacturing of polycarbonate resin>
ISS101 parts, SPG843 parts, (hereinafter abbreviated as DPC) diphenyl carbonate 750 parts, and tetramethylammonium hydroxide 0.8 × ^{10 -2} parts of barium stearate 0.6 × ^{10 -4} parts 200 under a nitrogen atmosphere as a catalyst It was heated to ° C and melted. Then, the temperature was raised to 220 ° C. and the degree of decompression was adjusted to 20.0 kPa over 30 minutes. Then, the temperature was raised to 240 ° C. and the degree of decompression was adjusted to 10 kPa over another 30 minutes. After holding at that temperature for 10 minutes, the degree of decompression was set to 133 Pa or less over 1 hour. The resin crystallized and whitened at the stage of high vacuum, and subsequent evaluation was not possible (PC5).

[Example 3]
Except that 553 parts of BPA, 316 parts of SPG, and 750 parts of DPC were used as raw materials, exactly the same operation as in Example 1 was performed, and the same evaluation was performed (PC6). The results are shown in Table 1.

[Comparative Example 11]
Except for using LDPE instead of EMMA, the same operation as in Example 3 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 12]
Exactly the same operation as in Example 3 was performed except that 711 parts of BPA, 105 parts of SPG, and 750 parts of DPC were used as raw materials, and the same evaluation was performed (PC7). The results are shown in Table 1.

[Comparative Example 13]
Except for using LDPE instead of EMMA, the same operation as in Comparative Example 12 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 14]
Except that the film was produced only with PC6, the same operation as in Example 3 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 15]
Except that the film was produced only with PC7, the same operation as in Example 3 was performed, and the same evaluation was performed. The results are shown in Table 1.

Since the resin composition of the present invention has excellent tensile properties and low water absorption, it is useful as a member for electrical and electronic applications, vehicle interior and exterior applications, and the like.

Claims (9)

Polycarbonate resin (A) containing 15 to 75 mol% of the repeating units represented by the following formula (a-1) in all the repeating units.
A copolymer (B) having a structural unit derived from ethylene and a structural unit derived from a (meth) acrylate-based monomer.
A resin composition containing.

(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 has a branched or linear alkyl group having 1 to 20 carbon atoms or a substituent. It 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 copolymer (B) has a structural unit derived from ethylene and a structural unit derived from a methyl methacrylate monomer. The resin composition according to claim 1 or 2, wherein the content of the structural unit derived from the (meth) acrylate-based monomer contained in the copolymer (B) is 10 to 50% by weight. The resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin (A) contains a unit represented by the following formula (a-2).

The resin composition according to any one of claims 1 to 4, wherein the weight ratio of the polycarbonate resin (A) to the copolymer (B) is 50:50 to 99: 1. The resin composition according to any one of claims 1 to 5, which comprises a polycarbonate resin (A) having a specific viscosity of 0.15 to 1.5 measured in a methylene chloride solution at 20 ° C. The resin composition according to any one of claims 1 to 6, wherein the saturated water absorption rate is 2.0% by weight or less. A molded product 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.