JP7450876B2 - resin composition - Google Patents

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 monomer.

Conventionally, polycarbonate resins made of bisphenol A have been widely used in vehicle applications and construction materials because of their excellent heat resistance, impact resistance, flame retardance, and transparency. On the other hand, when used in these applications, polycarbonate resins may have problems with solvent resistance and moldability. In order to solve these problems, polycarbonate resin compositions containing polyolefins and polyesters have been reported (Patent Documents 1 and 2). However, since these compositions use special polyethylene into which epoxy groups have been introduced in order to increase the compatibility between the resins, the applications for which they can be used have been limited.

In addition, in recent years, due to concerns about the depletion of petroleum resources and the problem of increasing carbon dioxide in the air, which causes global warming, carbon neutrality is becoming a reality, which does not rely on petroleum as a raw material and does not increase carbon dioxide even when burned. Biomass resources are attracting a lot of attention, and in the field of polymers, biomass plastics produced from biomass resources are being actively developed. In particular, polycarbonate mainly using isosorbide as a monomer has been attracting attention because it has excellent heat resistance, weather resistance, surface hardness, and chemical resistance, and has different characteristics from polycarbonate made of general bisphenol A. has been studied (Patent Documents 3 and 4). Although these isosorbide polycarbonates have excellent characteristics, they have a problem of high water absorption. From this background, a composition with polyethylene having a low water absorption rate is 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 with a special structure having a spiro ring has been reported (Patent Document 5), and it is possible to achieve both the excellent properties of a polycarbonate and an acrylic resin. has been achieved.

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

Japanese Patent Application Publication No. 5-39415 Japanese Patent Application Publication No. 2004-143282 Japanese Patent Application Publication No. 2006-36954 Japanese Patent Application Publication No. 2009-46519 Japanese Patent Application 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 extensive research, the present inventors have developed a composition containing a polycarbonate resin having a specific structure, a copolymer having structural units derived from ethylene and structural units derived from a (meth)acrylate monomer. The present inventors have discovered that this resin composition can be made into a resin composition with excellent tensile properties and low water absorption, and have completed the present invention.

（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 objects of the invention are achieved as follows.
1. A polycarbonate resin (A) containing 15 to 75 mol% of repeating units represented by the following formula (a-1) out of all repeating units;
Copolymer (B) having a structural unit derived from ethylene and a structural unit derived from a (meth)acrylate 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 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.)
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. The resin composition according to item 1 or 2 above, wherein the copolymer (B) contains 10 to 50% by weight of structural units derived from a (meth)acrylate monomer.
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. 5. The resin composition according to any one of items 1 to 4 above, 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 items 1 to 5 above, comprising a polycarbonate resin (A) having a specific viscosity of 0.15 to 1.5 as measured in a methylene chloride solution at 20°C.
7. 7. The resin composition according to any one of items 1 to 6 above, which has a saturated water absorption rate of 2.0% by weight or less.
8. A molded article obtained by injection molding the resin composition according to any one of items 1 to 7 above.
9. A film or sheet formed from the resin composition according to any one of items 1 to 7 above.

The present invention improves tensile properties 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 monomer. It has become possible to provide a resin composition with excellent properties. Therefore, its industrial effects are 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。） The present invention will be explained in detail below.
[Polycarbonate resin (A)]
The polycarbonate resin used in the resin composition of the present invention is a polycarbonate resin whose repeating units include units 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 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 represented by the above formula (a-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 15 to 85 mol%, and preferably 20 to 80 mol%, of units represented by the above formula (a-1) in the repeating units. It is more preferable to contain 30 to 70 mol%. When the unit represented by formula (a-1) is within the above range, the tensile properties are significantly improved due to the improved affinity between the resins in the resin composition, and the polycarbonate resin crystallizes during polymerization. It is preferable because polymerization is easy without any problems.

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

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

The units represented by the above formula (a-2) are represented by the following formulas (a-2-1), (a-2-2) and (a-2-3), which have stereoisomeric relationships. Examples of units are shown below.

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. The repeating units represented by 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 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 represented by formula (a-2) is preferably contained in an amount of 15 to 85 mol% of all repeating units, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%. It is preferable that the repeating unit represented by formula (a-2) is within the above range because it provides an excellent balance between tensile properties and low water absorption.

In the present invention, repeating units derived from various diol compounds are used as repeating units constituting copolymerized constitutional units other than the repeating unit represented by formula (a-1) and the repeating unit represented by formula (a-2). Units are listed.

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, among which bisphenol A is preferably used.

The content of copolymerized structural units other than the repeating unit represented by formula (a-1) and the repeating unit represented by formula (a-2) is preferably 50 mol% or less, 40% by mole or less of all 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.

(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 polycarbonate resin used in the resin composition of the present invention preferably has a specific viscosity (η _SP ) of 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.

[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 monomer.

Examples of (meth)acrylate monomers include methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid, benzyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl ( meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, glycidyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2-methoxyethyl(meth)acrylate 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)acryloyloxy maleate Ethyl, 2-(meth)acryoyloxyethyl phthalate, 2-(meth)acryoyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth) Examples include acrylate, diethylaminoethyl (meth)acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, cyclododecyl acrylate. These may be used alone or in combination of two or more. Among these, methyl (meth)acrylate is particularly preferred from the viewpoint of particularly excellent affinity with the polycarbonate resin (A) and industrial applicability.

The content of the structural unit derived from the (meth)acrylate monomer in the copolymer (B) is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, particularly preferably 20 to 40% by weight. be. If this content is less than 10% by weight, the compatibility of the copolymer (B) with the polycarbonate resin (A) will be excessively reduced, making it impossible to obtain sufficient tensile properties. On the other hand, when this content 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 uneven flow will not occur during molding. , a composition with excellent mechanical properties and heat resistance can be provided.

[Method for manufacturing 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 for blending in a molten state, an extruder or a laboplasto mill is generally used, and kneading is carried out at a molten resin temperature of 200 to 320°C, preferably 220 to 300°C, more preferably 230 to 290°C. As a result, a resin composition in which both resins are uniformly blended can be 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 the polycarbonate resin (A) and the copolymer resin (B) is preferably in the range of 50:50 to 99:1, and they can be mixed as desired within that range. More preferably, the range is 60:40 to 95:5, still more preferably 70:30 to 90:10, particularly preferably 75:25 to 85:15. By setting it within the above range, a resin composition with excellent tensile properties and low water absorption can be obtained.

[Additive]
The resin composition of the present invention may contain heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet rays, etc., depending on the purpose and necessity. Additives such as an absorbent, a mold release agent, and a coloring agent can be added.

(thermal stabilizer)
It is particularly preferable that the resin composition of the present invention 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, Bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc. are mentioned, among which preferred are distearylpentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite. 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.

In the resin composition of the present invention, a hindered phenol-based heat stabilizer or a sulfur-based heat stabilizer is added to a phosphorus-based 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 stabilizers.

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 of 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 of 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 of 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, 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 hydrolyzability, an epoxy compound can be blended into the resin composition of 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 of 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 added to the resin composition of 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)
In the resin composition of the present invention, an elastic polymer can be used as an impact modifier. Examples of the elastic polymer include natural rubber or a rubber component having a glass transition temperature of 10°C or lower, and aromatic vinyl. Examples include graft copolymers in which one or more monomers selected from vinyl cyanide, acrylic esters, methacrylic esters, and vinyl compounds copolymerizable with these are copolymerized. 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 injection molding method, compression molding method, injection compression molding method, melt film forming method, casting method, etc., and can be used as a member for electrical and electronic applications, vehicle interior and exterior applications, etc. It can be used as a molded product.

[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 the Examples below. From the viewpoint of mechanical strength, the tensile failure strain (%) of the resin composition of the present embodiment is preferably as high as possible, preferably 15% or more, and more preferably 20% or more.

[Fracture toughness]
The fracture toughness of the resin composition of the present invention is the area value of the stress strain curve measured at 23°C in accordance with JIS K7127. Specifically, it is a value measured by the method described in Examples below. From the viewpoint of mechanical strength, the fracture toughness (MJ/m ³ ) of the resin composition of the present embodiment is preferably as high as possible, 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. It is preferable that the water absorption rate is 2.0% or less, since dimensional changes and warpage due to water absorption can be reduced in the molded product.

[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 composition film)
3. Tensile Breaking Strain The obtained film was subjected to a tensile test at a speed of 10 mm/min using a tensile testing machine manufactured by A&D Co., Ltd., and the elongation rate at breakage was defined as the tensile breaking strain.
4. Fracture toughness The obtained film was subjected to a tensile test at a speed of 10 mm/min using 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 The obtained film was dried at 80° C. for 12 hours, then immersed in water at 25° C. for 240 hours, and the weight increase was measured, and the water absorption was determined using the following formula.
Water absorption rate (%) = {(Resin weight after water absorption - Resin weight before water absorption) / Resin weight before water absorption} x 100

[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 = 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 ISS, specific viscosity 0.312

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

PC6 (Example):
Structural unit derived from bisphenol A (hereinafter referred to as 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-methyl methacrylate copolymer]
EMMA: Acrift WK307 manufactured by Sumitomo Chemical Co., Ltd. (weight ratio: ethylene/methyl methacrylate = 75/25)

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

[Example 1]
<Production of polycarbonate resin>
354 parts of ISS, 316 parts of SPG, 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 0.8 x 10 ^-2 parts of tetramethylammonium hydroxide and 0.6 x 10 ^-4 parts of barium stearate as catalysts 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 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.

<Preparation of kneaded composition film>
PC1 and EMMA were mixed at a weight ratio of 80:20 using a laboplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd. at a kneading temperature of 250°C, a kneading time of 7 minutes, a kneading rotation speed of 100 rpm, and under nitrogen conditions. went. Thereafter, a film with a thickness of 0.3 mm was produced using a hot press machine at a press temperature of 250° C. and a press time of 5 minutes. Various evaluations of the obtained films are listed in Table 1.

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

[Comparative example 1]
Except for using 455 parts of ISS, 105 parts of SPG, and 750 parts of DPC as raw materials, the same operation as in Example 1 was performed, and the same evaluation was performed (PC3). The results are listed in Table 1.

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

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

[Comparative example 4]
Except for using LDPE instead of EMMA, the operation was exactly the same as in Example 2, and the same evaluation was performed. The results are listed in Table 1.

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

[Comparative example 6]
The same operations as in Example 1 were performed, except that a film was produced using only PC1, and the same evaluation was performed. The results are listed in Table 1.

[Comparative Example 7]
The same operation as in Example 1 was performed, except that a film was produced using only PC2, and the same evaluation was performed. The results are listed in Table 1.

[Comparative example 8]
The same operations as in Example 1 were performed, except that a film was produced using only PC3, and the same evaluation was performed. The results are listed in Table 1.

[Comparative Example 9]
The same operations as in Example 1 were performed, except that a film was produced using only PC4, and the same evaluation was performed. The results are listed in Table 1.

[Comparative Example 10]
<Production of polycarbonate resin>
101 parts of ISS, 843 parts of SPG, 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 0.8 x 10 ^-2 parts of tetramethylammonium hydroxide and 0.6 x 10 ^-4 parts of barium stearate as catalysts 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 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. The resin crystallized and whitened at the stage of high vacuum, and subsequent evaluation was not possible (PC5).

[Example 3]
Except for using 553 parts of BPA, 316 parts of SPG, 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 11]
Except for using LDPE instead of EMMA, the operation was exactly the same as in Example 3, and the same evaluation was performed. The results are listed in Table 1.

[Comparative example 12]
Except for using 711 parts of BPA, 105 parts of SPG, and 750 parts of DPC as raw materials, the operation was exactly the same as in Example 3, and the same evaluation was performed (PC7). The results are listed in Table 1.

[Comparative Example 13]
The same operation as in Comparative Example 12 was performed, except that LDPE was used instead of EMMA, and the same evaluation was performed. The results are listed in Table 1.

[Comparative example 14]
The same operations as in Example 3 were performed, except that a film was produced using only PC6, and the same evaluation was performed. The results are listed in Table 1.

[Comparative Example 15]
The same operation as in Example 3 was performed, except that a film was produced using only PC7, and the same evaluation was performed. The results are listed 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 (6)

A polycarbonate resin (A) containing 15 to 75 mol% of repeating units represented by the following formula (a-1) out of all repeating units;
Copolymer (B) having a structural unit derived from ethylene and a structural unit derived from a methyl methacrylate monomer
Contains
The content of the structural unit derived from the methyl methacrylate monomer contained in the copolymer (B) is 10 to 50% by weight,
A resin composition in which the weight ratio of polycarbonate resin (A) and copolymer (B) is 50:50 to 99:1 .
(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 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 polycarbonate resin (A) contains a unit represented by the following formula (a-2).
The resin composition according to claim 1 or 2 , comprising a polycarbonate resin (A) having a specific viscosity of 0.15 to 1.5 as measured in a methylene chloride solution at 20°C. The resin composition according to any one of claims 1 to 3 , having a saturated water absorption rate of 2.0% by weight or less. A molded article obtained by injection molding the resin composition according to any one of claims 1 to 4 . A film or sheet formed from the resin composition according to any one of claims 1 to 4 .