JP2021109922A - Resin composition and molding thereof - Google Patents

Abstract

To provide a resin composition that has excellent properties such as transparency, surface hardness and impact resistance and contains polycarbonate resin, acrylic resin and an impact resistance modifier.SOLUTION: A resin composition contains a polycarbonate resin containing a specific spiro ring structure and a polycarbonate resin derived from an aliphatic diol having a specific ether group, as well as an acrylic resin and an impact resistance modifier with a refractive index range of 1.485 or more and 1.495 or less.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing a polycarbonate resin, an acrylic resin and an impact resistance modifier.

Conventionally, methacrylic resin, polycarbonate resin (hereinafter, may be referred to as PC) and the like are known as transparent resins, and electric / electronic parts, optical parts, automobile parts, machine parts, etc. in the form of molded products, films, sheets, etc. It is used in a wide range of fields such as.

Methacrylic acid resins such as polymethylmethacrylate (hereinafter sometimes referred to as PMMA) have high transparency and hard surface hardness (pencil hardness H to 3H), and are often used as optical materials for lenses and optical fibers. .. However, since the glass transition temperature is as low as about 100 ° C. and the heat resistance is inferior, the use in the field of having heat resistance is limited. Further, there is a problem that the impact resistance is low.

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. Among these applications, those used outdoors are required to have high weather resistance, but in general, the weather resistance of polycarbonate resin is not superior to that of other transparent materials such as acrylic resin, and it becomes yellow due to outdoor exposure. Weirdness and devitrification occur. In addition, the surface is very soft (pencil hardness 4B to 2B), and there is a problem that it is easily scratched.

It is known that the mixture of PC and PMMA is essentially incompatible and produces an opaque material. For example, Patent Document 1 shows that the mixture of PC and PMMA is opaque and the physical characteristics of both polymers are not expressed.

A resin composition with an acrylic resin using a polycarbonate resin having a special structure has been reported (Patent Document 2), and excellent transparency, weather resistance and surface hardness have been achieved. However, according to the studies by the present inventors, it has been found that the resin composition described in Patent Document 2 has a problem in impact resistance, and particularly exhibits brittle fracture like an acrylic resin in a surface impact test. It was issued. Further, it has been found that the resin composition described in Patent Document 2 has a problem in chemical resistance. Therefore, among the compositions of the polycarbonate resin and the acrylic resin, a composition having good transparency, surface hardness, impact resistance, etc. has not been reported so far.

U.S. Pat. No. 431003 Japanese Unexamined Patent Publication No. 2015-232091

An object of the present invention is to provide a resin composition containing a polycarbonate resin, an acrylic resin, and an impact resistance modifier having excellent properties of transparency, surface hardness, and impact resistance.

As a result of intensive studies, the present inventors have applied an acrylic resin and a specific range of refractive index to a polycarbonate resin containing a specific spiro ring structure and a polycarbonate resin derived from an aliphatic diol having a specific ether group. It has been clarified that a resin composition having excellent transparency, surface hardness and impact resistance can be obtained by containing the impact-resistant modifier, and the present invention has been completed.
That is, according to the present invention, the subject of the invention is achieved by the following.

1. 1. The repeating unit is from the unit (a) represented by the following formula (1), the unit (b) represented by the following formula (2), and the carbonate unit (c) other than the unit (a) and the unit (b). The polycarbonate resin (A) containing 5 to 85 mol% of the unit (a), 15 to 95 mol% of the unit (b), and 0 to 80 mol% of the unit (c) among all the repeating units, the repeating unit is as follows. The unit (a) represented by the formula (1), the unit (b) represented by the following formula (2), and the carbonate unit (c) other than the unit (a) and the unit (b) are all repeated. The total of the polycarbonate resin (B) containing less than 5 mol% of the unit (a), 30 to 100 mol% of the unit (b), and 0 to 70 mol% of the unit (c), and the acrylic resin (C). A resin composition containing 5 to 60 parts by weight of the impact-resistant modifier (D) with respect to 100 parts by weight, and the refractive index of the impact-resistant modifier (D) is 1.485 or more and 1.495 or less. A resin composition characterized by being.

(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 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 carbonate unit (c) is a carbonate unit derived from at least one compound selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound and an aromatic dihydroxy compound.

3. 3. The resin composition according to item 1 or 2 above, wherein the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is 10:90 to 90:10.

4. The resin composition according to any one of the above items 1 to 3, wherein the total weight ratio of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) is 30:70 to 99: 1.

5. The resin composition according to any one of the above items 1 to 4, wherein the acrylic resin (C) contains 40 to 100 mol% of a repeating unit derived from methyl methacrylate.

6. The resin composition according to any one of the above items 1 to 5, wherein the haze of the test piece having a thickness of 6.2 mm is 30% or less.

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

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

The present invention is an impact-resistant modifier having a refractive index in a specific range in a composition of a polycarbonate resin containing a specific spiro ring structure, a polycarbonate resin derived from an aliphatic diol having a specific ether group, and an acrylic resin. By containing the above, it has become possible to provide a resin composition having excellent properties of transparency, surface hardness and impact resistance. Therefore, the industrial effect it produces is exceptional.

Hereinafter, the present invention will be described in detail.

(Polycarbonate resin (A))
The polycarbonate resin (A) used in the resin composition of the present invention has a repeating unit represented by the following formula (1), a unit (a), a unit (b) represented by the following formula (2), and a unit. It consists of a carbonate unit (c) other than the unit (a) and the unit (b), and the unit (a) is 5 to 85 mol%, the unit (b) is 15 to 95 mol%, and the unit (c) is included in all the repeating units. It is a polycarbonate resin containing 0 to 80 mol%.

(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 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 (a) represented by the above formula (1) is derived from a diol having a specific 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 (A) used in the resin composition of the present invention contains 5 to 85 mol% of the unit (a) represented by the above formula (1) as a repeating unit in the total repeating unit, and 10 to 80 mol%. It is preferably contained, more preferably 15 to 70 mol%, further preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%. When the unit (a) is within the above range, the resin composition does not become cloudy due to phase separation during extrusion or molding in the resin composition with the acrylic resin, and crystallizes during the polymerization of the polycarbonate resin. It is preferable because it is easy to polymerize without any problem.

The unit (b) represented by the above formula (2) is derived from an aliphatic diol having a specific ether group. Examples of such an aliphatic diol include units (b-1), (b-2) and (b-3) represented by the following formulas having a stereoisomeric relationship.

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 (b-1), (b-2) and (b-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 polycarbonate resin (A) used in the resin composition of the present invention contains 15 to 95 mol% of the repeating unit (b) represented by the above formula (2) in all the repeating units, and 20 to 90 mol%. It is preferably contained, more preferably 30 to 85 mol%, further preferably 40 to 80 mol%, and particularly preferably 50 to 80 mol%. When the unit (b) is within the above range, a resin composition having an excellent balance of transparency, surface hardness and impact resistance can be obtained.

The polycarbonate resin (A) used in the resin composition of the present invention can contain a carbonate unit (c) other than the unit (a) and the unit (b).

The carbonate unit (c) is preferably a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound and an aromatic dihydroxy compound. The carbonate unit (c) is a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound in terms of surface hardness and weather resistance. Is preferable.

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-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2-methyl-1,4-cyclohexanediol, and 1,2-cyclohexane. Cyclohexanedimethanol such as dimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, norbornandimethanol such as 2,3-norbornandimethanol, 2,5-norbornandimethanol, tricyclode Examples thereof include candimethanol, pentacyclopentadecanedimethanol, 1,3-adamantandiol, 2,2-adamantandiol, decalindimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and cyclohexane. Dimethanols 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.

In the polycarbonate resin (A) used in the resin composition of the present invention, the repeating unit contains the carbonate unit (c) in an amount of 0 to 80 mol%, preferably 1 to 60 mol%, and preferably 2 to 40 mol%. It is more preferably contained in mol%, further preferably contained in an amount of 3 to 20 mol%, and particularly preferably contained in an amount of 4 to 10 mol%. When the unit (c) is within the above range, a resin composition having an excellent balance of transparency, surface hardness and impact resistance can be obtained.

(Polycarbonate resin (B))
The polycarbonate resin (B) used in the resin composition of the present invention has a repeating unit represented by the following formula (1), a unit (a), a unit (b) represented by the following formula (2), and a unit. It consists of a carbonate unit (c) other than the unit (a) and the unit (b), and among all the repeating units, the unit (a) is less than 5 mol%, the unit (b) is 30 to 100 mol%, and the unit (c) is. It is a polycarbonate resin containing 0 to 70 mol%.

(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 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 (a) represented by the above formula (1) is derived from a diol having a specific spiro ring structure. Examples of the diol compound having such a spiro ring structure include the same compounds as those described above.

In the polycarbonate resin (A) used in the resin composition of the present invention, the repeating unit represented by the above formula (1) is less than 5 mol% in all repeating units, and 3 mol% or less. It is preferably 1 mol% or less, and it is particularly preferable that the unit (a) is not substantially contained.

The unit (b) represented by the above formula (2) is derived from an aliphatic diol having a specific ether group. Examples of such an aliphatic diol include the same compounds as those described above.

The polycarbonate resin (B) used in the resin composition of the present invention contains 30 to 100 mol% of the unit (b) represented by the above formula (2) as a repeating unit in the total repeating unit, and 50 to 99 mol%. It is preferably contained, more preferably 60 to 98 mol%, further preferably 70 to 97 mol%, and particularly preferably 80 to 96 mol%. When the unit (b) is within the above range, a resin composition having an excellent balance of transparency, surface hardness and impact resistance can be obtained.

The polycarbonate resin (B) used in the resin composition of the present invention can contain a carbonate unit (c) other than the unit (a) and the unit (b).

The carbonate unit (c) is preferably a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound and an aromatic dihydroxy compound. The carbonate unit (c) is a carbonate unit (c) derived from at least one compound selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound in terms of surface hardness and weather resistance. Is preferable.

Examples of the aliphatic diol compound, the alicyclic diol compound and the aromatic dihydroxy compound include the same compounds as those described above.

In the polycarbonate resin (B) used in the resin composition of the present invention, the repeating unit contains the carbonate unit (c) in an amount of 0 to 70 mol%, preferably 1 to 50 mol%, and preferably 2 to 40 mol%. It is more preferably contained in mol%, further preferably contained in an amount of 3 to 30 mol%, and particularly preferably contained in an amount of 4 to 20 mol%. When the unit (c) is within the above range, a resin composition having an excellent balance of transparency, surface hardness and impact resistance can be obtained.

(Manufacturing method of polycarbonate resin)
The polycarbonate resin of the polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention reacts a carbonate precursor such as a carbonic acid diester with a reaction means known per se for producing a normal polycarbonate resin, for example, a diol component. Manufactured by the method. 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 of distilling off the produced alcohol or phenol by stirring a predetermined ratio of the diol component with the carbonic acid diester while heating it in an inert gas atmosphere. 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. Specifically, diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate and the like are exemplified. Of these, diphenyl carbonate is particularly preferable. The amount of 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, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides and the like of alkali metals and alkaline earth metals are 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, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and diacetic acid. Examples 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 such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like, or basic salts 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 tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

As esters of sulfonic acid, methyl benzenesulfonic acid, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonic acid, phenylbenzenesulfonic acid, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluenesulfonate, phenyl paratoluenesulfonate 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 mol 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 viscosities (η SP} ) of the polycarbonate resin (A) and the polycarbonate resin (B) used in the resin composition of the present invention are 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 of 0.7 g of 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.

(Acrylic resin (C))
As the acrylic resin (C) used in the resin composition of the present invention, an acrylic resin as a thermoplastic resin is used. Examples of the monomer used for the acrylic resin include the following compounds. For example, methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( Meta) 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, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofur Frill (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acroyloxyethyl succinate, 2- (meth) acroyloxyethyl maleate, 2-(meth) phthalate Meta) Acroyloxyethyl, 2- (meth) aclioil oxyethyl, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) Examples thereof include 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 polymerized alone or may be used by polymerizing two or more kinds. Among them, it is preferable to contain methyl methacrylate and / or methyl acrylate. In particular, the monomer component preferably contains 40 to 100 mol% of methyl methacrylate, more preferably 50 to 100 mol%, and even more preferably 60 to 99 mol%. When the ratio of methyl methacrylate as the monomer component is within the above range, the heat-resistant decomposition property is excellent, molding defects such as silver are less likely to occur during molding, and the thermal deformation temperature is good. Further, other monomers that can be polymerized with these acrylic monomers, such as polyolefin monomers and vinyl monomers, may be used in combination.

The molecular weight of the acrylic resin is not particularly limited, but if the weight average molecular weight is in the range of 30,000 or more and 300,000 or less, appearance defects such as flow unevenness may occur when molding as a composition. It is possible to provide a composition having excellent mechanical properties and heat resistance.

The acrylic resin used in the resin composition of the present invention preferably has a specific viscosity in the range of 0.12 to 0.55. If the specific viscosity is less than 0.12, the molded product may become brittle. When the specific viscosity is higher than 0.55, the melt viscosity of the resin becomes high and the moldability may be inferior.

(Impact resistant modifier (D))
The resin composition of the present invention contains an impact-resistant modifier (D). The impact resistance modifier is preferably a core-shell type polymer composed of a core which is a rubber-like polymer and a shell obtained by graft-polymerizing the rubber-like polymer. By using the core-shell type polymer, the dispersibility in polycarbonate is improved, and high impact strength tends to be obtained.

The average particle size of the impact-resistant modifier is preferably 10 to 500 nm. It is more preferably 30 to 300 nm, still more preferably 50 to 200 nm, and most preferably 50 to 180 nm. If the average particle size is less than 10 nm, sufficient impact strength tends not to be obtained. On the other hand, when the average particle size exceeds 500 nm, the transparency of the obtained resin composition tends to decrease. The average particle size is measured in the latex state of the rubber-like polymer and the graft copolymer. The volume average particle size was measured using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. as a measuring device.

The rubber-like polymer corresponding to the core of the impact-resistant modifier is a rubber-like polymer of a vinyl-based monomer, or a polymer of a diene-based monomer and a vinyl-based monomer, and is a vinyl-based single. The fact that the polymer is at least one selected from a (meth) acrylic acid monomer and a (meth) acrylic acid alkyl ester monomer can achieve both transparency and impact resistance of the resin composition of the present invention. Further, it is preferable from the viewpoint of raw material cost.

The (meth) acrylic acid monomer is an acrylic acid monomer, a methacrylic acid monomer, or a mixture thereof. The (meth) acrylic acid alkyl ester monomer is an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, or a mixture thereof.

Specific examples of the diene-based monomer include 1,3-butadiene. Specific examples of the (meth) acrylic acid monomer and the (meth) acrylic acid alkyl ester monomer include acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. , Ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate. Examples of the polymer obtained from such a monomer include a butadiene-acrylic acid ester copolymer and the like.

The glass transition temperature (Tg) of the rubber-like polymer is preferably 0 ° C. or lower from the viewpoint of improving impact resistance. It is more preferably −20 ° C. or lower, and even more preferably −40 ° C. or lower.

The shell portion of the impact-resistant modifier is at least one vinyl-based monomer. The shell portion can be formed by graft polymerization with at least one vinyl-based monomer.

Examples of the vinyl-based monomer include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acids and unsaturated carboxylic acid esters. Among aromatic vinyl compounds, styrene, α-methylstyrene and the like are preferable, among vinyl cyanide compounds, acrylonitrile, methacrylonitrile and the like are preferable, and among unsaturated carboxylic acids and unsaturated carboxylic acid esters, acrylic Acids, methacrylic acids, acrylic acid esters having alkyl esters having 1 to 12 carbon atoms, methacrylic acid esters and the like are preferable. Since the dispersibility in the polycarbonate resin is excellent and the transparency of the obtained resin composition is excellent, the vinyl-based monomer used for graft polymerization is an unsaturated carboxylic acid ester, or an unsaturated carboxylic acid ester and an aromatic vinyl. It is preferably a mixture of compounds.

Further, the impact-resistant modifier includes one or more reactive groups selected from an epoxy group, a hydroxy group, a carboxy group, an alkoxy group, an isocyanato group, an acid anhydride group, and a acidified group in the graft portion. Can be introduced. As a result, the dispersibility and impact resistance may be improved as compared with the case where a rubber graft copolymer containing no reactive group is used.

The refractive index of the impact-resistant modifier used in the present invention is 1.485 or more and 1.495 or less, preferably 1.487 or more and 1.494 or less, and more preferably 1.490 or more and 1.493 or less. Is. When the refractive index of the impact-resistant modifier is within the above range, the resin composition is excellent in transparency and impact resistance.

As a method for producing the impact-resistant modifier, any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization may be adopted, but emulsion polymerization, that is, emulsion graft polymerization is preferable. Specifically, latex is added to a reaction vessel equipped with a stirrer, a vinyl monomer, a polymerization initiator, and water are further added, a chain transfer agent and a redox agent are added as necessary, and the mixture is heated and stirred. good.

The types of the polymerization initiator, chain transfer agent, and oxidation-reducing agent used here are not particularly limited, and known ones can be used. Further, the method of adding each raw material to the reaction vessel is not particularly limited, and the batch addition before the start of polymerization or the partial addition may be performed. Further, the graft polymerization is carried out in one stage or two or more stages, and the monomer composition of each stage may be the same or different, and even if the monomers are added all at once, they are continuously added. Alternatively, or a combination of these may be used.

When the emulsion polymerization method is adopted, a known polymerization initiator, that is, a pyrolysis-type polymerization initiator such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate should be used. Can be done. In addition, organic peroxides such as t-butylperoxyisopropyl carbonate, paramentanhydroperoxide, cumenehydroperoxide, dicumyl peroxide, t-butylhydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide. Oxides or peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate and other inorganic peroxides, and optionally sodium formaldehyde sulfoxylate, reducing agents such as glucose, and optionally iron sulfate ( Use as a redox-type polymerization initiator in combination with a transition metal salt such as II), a chelating agent such as disodium ethylenediamine tetraacetate if necessary, and a phosphorus-based flame retardant such as sodium pyrophosphate if necessary. You can also.

When the redox-type polymerization initiator system is used, the polymerization can be carried out even at a low temperature at which the peroxide is substantially not thermally decomposed, so that the polymerization temperature can be set in a wide range, which is preferable. Of these, it is preferable to use an aromatic ring-containing peroxide such as cumene hydroperoxide or dicumyl peroxide as a redox-type polymerization initiator. The amount of the polymerization initiator used and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when the redox-type polymerization initiator is used can be used within a known range.

When synthesizing an impact-resistant modifier by emulsification polymerization, the polymerization emulsifier includes alkali metal salts of higher fatty acids such as disproportionate logonic acid, oleic acid, and stearic acid, alkali metal salts of phosphoric acid compounds, and further. Can use conventionally known polymerization emulsifiers such as sulfonic acid and alkali metal salts of sulfuric acid compounds.

When an impact-resistant modifier is obtained by emulsion polymerization, for example, the impact modifier latex and an acid such as hydrochloric acid, or divalent or higher valent or higher such as calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride, calcium acetate, etc. After solidifying by mixing a metal salt, the impact-resistant modifier can be separated from the aqueous medium by heat treatment, dehydration, washing, and drying according to a known method (also referred to as a solidification method). Alternatively, an alcohol such as methanol, ethanol or propanol, or a water-soluble organic solvent such as acetone is added to the latex to precipitate an impact-resistant modifier, which is separated from the solvent by centrifugation or filtration, and then dried and isolated. You can also do it. As another method, the impact-resistant modifier component in the latex is extracted into the organic solvent layer by adding a slightly water-soluble organic solvent such as methyl ethyl ketone to the latex containing the impact-resistant modifier used in the present invention, and organic. Examples thereof include a method in which the solvent layer is separated and then mixed with water or the like to precipitate the impact-resistant modifier component. Further, the latex can be directly powdered by a spray drying method.

In the present invention, a resin composition in which a shock-resistant modifier is previously contained in an acrylic resin may be contained in a polycarbonate resin. Specific examples of the acrylic resin containing the impact resistance modifier are not particularly limited, and examples thereof include the following.

For example, Mitsubishi Chemical, trade name Acrypet IRK304, IRL309, VRL40, Kuraray, trade name Parapet GR00100, GR04970, GR-H60, Daicel Evonik, trade name PLEXIGLAS AG100, zk6HF, Asahi Kasei, product. Names such as Delpet SR8350 and SR8500 can be mentioned.

(Method for manufacturing a resin composition containing a polycarbonate resin, an acrylic resin and an impact resistance modifier)
The resin composition of the present invention preferably blends a polycarbonate resin (A), a polycarbonate resin (B), an acrylic resin (C), and an impact-resistant modifier (D) in a molten state. As a method of blending in a molten state, an extruder is generally used, and the molten resin is kneaded and pelletized at a molten resin temperature of 200 to 320 ° C., preferably 220 to 300 ° C., more preferably 230 to 290 ° C. As a result, pellets of a resin composition in which both resins are uniformly blended 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 polycarbonate resin (B) is preferably mixed in the range of 10:90 to 90:10. It is more preferably in the range of 15:85 to 85:15, further preferably in the range of 20:80 to 80:20, particularly preferably in the range of 25:75 to 75:25, and most preferably in the range of 30: It is in the range of 70 to 70:30. Within the above range, a resin composition having excellent surface hardness and impact resistance can be obtained.

The weight ratio of the polycarbonate resin and the acrylic resin, which is the sum of the polycarbonate resin (A) and the polycarbonate resin (B), is preferably mixed in the range of 30:70 to 99: 1. It is more preferably in the range of 50:50 to 95: 5, more preferably in the range of 60:40 to 90:10, particularly preferably in the range of 70:30 to 88:12, and most preferably in the range of 75 :. It is in the range of 25 to 85:15. Within the above range, a resin composition having excellent surface hardness and impact resistance can be obtained.

The impact-resistant modifier is mixed in the range of 5 to 60 parts by weight with respect to a total of 100 parts by weight of the polycarbonate resin and the acrylic resin. It is preferably in the range of 7 to 50 parts by weight, more preferably in the range of 8 to 40 parts by weight, further preferably in the range of 9 to 30 parts by weight, and particularly preferably in the range of 10 to 25 parts by weight. .. Within the above range, a resin composition having excellent transparency, surface hardness, and impact resistance can be obtained.

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

(Heat stabilizer)
The resin composition used in 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 pentaerythritol 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, dicyclohexylpentaerythritol diphosfite, and more preferably, distearylpentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) penta. Ellisritol diphosphite can be mentioned.

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 phosphenyl 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, monodecyl diphenyl 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.

Examples of the phosphate compound 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, and so on. 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 used in the present invention contains a hindered phenol-based heat stabilizer or a sulfur-based heat stabilizer as a heat stabilizer for the purpose of suppressing a decrease in molecular weight and deterioration of hue during extrusion / molding. It can also be added in combination with a phosphorus-based heat 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 used in 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 release agents include higher fatty acid esters of monohydric 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 monohydric or polyhydric 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 behenic 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 used in 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 used in 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 a complex. These light stabilizers may be used alone or in combination of two or more. The content of the light stabilizer is preferably 0.001 to 1 part by weight based on 100 parts by weight of the resin composition. More preferably, it is 0.01 to 0.5 parts by weight.

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

Epoxide-based stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allylglycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxidecyclohexylmethyl-3', 4'-epoxidecyclohexylcarboxylate. , 3,4-Epoxide-6-Methylcyclohexylmethyl-3', 4'-Epoxide-6'-Methylcyclohexylcarboxylate, 2,3-Epoxidecyclohexylmethyl-3', 4'-Epoxidecyclohexylcarboxylate, 4- (3,4-Epoxide-5-Methylcyclohexyl) Butyl-3', 4'-Epoxide Cyclohexylcarboxylate, 3,4-Epoxide Cyclohexylethylene Oxide, Cyclohexylmethyl-3,4-Epoxide Cyclohexylcarboxylate, 3,4-Epoxide -6-Methylcyclohexylmethyl-6'-methylsilohexylcarboxylate, 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-epoxide cyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxide cyclohexylcarboxylate, N-butyl-2 , 2-Dimethyl-3,4-Epoxide Cyclohexylcarboxylate, Cyclohexyl-2-methyl-3,4-Epoxide Cyclohexylcarboxylate, N-Butyl-2-isopropyl-3,4-Epoxide-5-Methylcyclohexylcarboxylate, Octadecyl-3,4-epoxide cyclohexylcarboxylate, 2-ethylhexyl-3', 4'-epoxide cyclohexylcarboxylate, 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 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the resin composition. It is desirable to mix in a range.

(Bluing agent)
The resin composition used in the present invention may contain a bluing agent in order 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.

One of these brewing agents may be used alone, or two or more thereof may be used in combination. 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 used in 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 incineration disposal or thermal recycling is performed. It is more suitable as a flame retardant in the molded product of the present invention.

When the flame retardant is blended, the range is preferably 0.05 to 50 parts by weight per 100 parts by weight of the resin composition. If it is less than 0.05 parts by weight, sufficient flame retardancy is not exhibited, and if it exceeds 50 parts by weight, the strength and heat resistance of the molded product are impaired.

(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, a casting method, and the like, an optical lens, an optical disk, an optical film, a placel substrate, and the like. It can be used as a molded product such as an optical card, a liquid crystal panel, a head lamp lens, a light guide plate, a diffuser plate, a protective film, an OPC binder, a front plate, a housing, a tray, a water tank, a lighting cover, a signboard, and a resin window. In particular, it can be used as a member requiring high surface hardness such as a front plate, a housing, a tray, a water tank, a lighting cover, a signboard, and a resin window.

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

(transparency)
In the resin composition of the present invention, the haze of the molded piece having a thickness of 2 mm is preferably 30% or less, more preferably 25% or less, further preferably 20% or less, and further preferably 15% or less. Especially preferable. When the haze is within the above range, the range of use as an optical member is not limited, which is preferable.

(Impact strength)
It resin composition of the present invention is preferably Charpy notched impact strength measured according to ISO179 is 15 kJ / ^{m 2} or more, and more preferably 18 kJ / ^{m 2} or more, 20 kJ / ^{m 2} or more Is even more preferable. The notched Charpy impact strength is 100 kJ / m ² or less, which has a sufficient function.

The resin composition of the present invention uses a high-speed puncture impact tester "Hydroshot HTM-P10" (manufactured by Shimadzu Corporation) at a punching test speed of 7 m / sec in a 23 ° C environment carried out in accordance with JIS K7211-2. It is preferable that the fracture form of the test piece in the punching test is ductile fracture.

(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.

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]

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

4. Notched Charpy Impact Strength The ISO bending test piece obtained by the following method was measured for notched Charpy impact strength according to ISO 179.

5. High-speed surface impact test Using a flat plate with a length of 45 mm, a width of 50 mm, and a thickness of 2 mmt obtained under the same conditions as the following method, a high-speed puncture impact tester "Hydroshot HTM-P10" (Shimadzu) according to JIS K7211-2. A punching test was carried out at a punching test speed of 7 mm / sec in an environment of 23 ° C., and the fracture form was visually confirmed.

6. Pencil hardness Based on JIS K5400, draw a line with a pencil under a load of 750 g while maintaining an angle of 45 degrees with respect to the surface of the molded product in a thermostatic chamber with an atmospheric temperature of 23 ° C, and visually check the surface condition. evaluated.

[Polycarbonate resin (A)]
PC-1 (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 / 1,9-nonanediol (hereinafter referred to as ND) = 72/21/7 (mol%), specific viscosity 0.396
PC-2 (Example):
Structural unit derived from ISS / structural unit derived from SPG / structural unit derived from ND = 58/38/4 (mol%), specific viscosity 0.425
[Polycarbonate resin (B)]
PC-3 (Example)
Structural unit derived from ISS / Structural unit derived from ND = 96/4 (mol%) decanol terminal-modified resin, specific viscosity 0.366
[Acrylic resin (C)]
C-1: Acrypet VH001 manufactured by Mitsubishi Chemical Corporation (acrylic resin obtained by copolymerizing 95 mol% of methyl methacrylate and 5 mol% of methyl acrylate)
[Impact-resistant modifier composite acrylic resin (C + D)]
C + D: Mitsubishi Chemical Corporation Acrypet VRL40 (refractive index of impact-resistant modifier: 1.492)
[Impact-resistant modifier (D)]
D-1: Kaneka M-230 manufactured by Kaneka Corporation (refractive index: 1.492)
D-2: Mitsubishi Chemical's Metabrene W-377 (refractive index: 1.492)

[Example 1]
<Manufacturing of polycarbonate resin>
(Manufacturing of Polycarbonate Resin (A))
Isosorbide (hereinafter abbreviated as ISS) 364 parts, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane (hereinafter abbreviated as SPG) ) 221 parts, 1,9-nonanediol (hereinafter abbreviated as ND) 39 parts, diphenyl carbonate (hereinafter abbreviated as DPC) 750 parts, and tetramethylammonium hydroxide 0.8 × ^10-2 parts as a catalyst and barium stearate. 0.6 × 10 ^-4 parts were heated to 200 ° C. in a nitrogen atmosphere to melt them. 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 (PC-1).

(Manufacturing of Polycarbonate Resin (B))
478 parts of isosorbide (hereinafter abbreviated as ISS), 33.5 parts of 1,9-nonanediol (hereinafter abbreviated as ND), 27.6 parts of decanol, 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and barium stearate as a catalyst. 0.0025 parts were heated to 120 ° C. under a nitrogen atmosphere to melt them. Then, the liquid was sent to the reaction vessel, the heat medium temperature of the capacitor was adjusted to 40 ° C., the resin internal temperature was adjusted to 170 ° C., and the degree of decompression was adjusted to 13.4 kPa over 30 minutes. Then, the degree of decompression was adjusted to 3.4 kPa over 20 minutes and kept at that temperature for 10 minutes. Further, the degree of decompression was adjusted to 0.9 kPa over 30 minutes, the internal temperature of the resin was adjusted to 180 ° C., and the temperature was maintained at that temperature for 10 minutes, then the degree of vacuum was set to 0.2 kPa, and the resin temperature was changed from 180 ° C. to 225 ° C. for 30 minutes. After reaching the specified viscosity, the mixture was discharged from the bottom of the reaction vessel under nitrogen pressure, cooled in a water tank, and cut with a pelletizer to obtain pellets (PC-3).

<Manufacturing of resin composition>
Polycarbonate resin PC-1, Polycarbonate resin PC-3, Acrylic resin C + D: Acrypet VRL40 (impact-resistant modifier composite acrylic resin) manufactured by Mitsubishi Chemical Co., Ltd. is used and mixed so that the weight ratio is 40:30. After that, it was supplied to the extruder. For extrusion, a vent type twin-screw extruder [Kobe Steel Co., Ltd. KTX-30] with a diameter of 30 mmφ is used, and pellets are obtained by melt-kneading at a screw rotation speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum degree of 3 kPa. rice field. The extrusion temperature was 250 ° C. from the supply port to the die portion. A part of the obtained pellets is dried at 90 ° C. for 6 hours or more in a hot air circulation type dryer, and then a test piece for evaluation is used at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine. (ISO bending test piece (ISO178, ISO179, ISO75-1 and ISO75-2 compliant), three-stage plate (1 mmt, 2 mmt, 3 mmt)) was molded. The evaluation results are shown in Table 1.

[Example 2]
<Manufacturing of resin composition>
Extruded with the blend weight ratio set to PC-1: PC-3: C + D = 20: 50: 30, the same operation as in Example 1 was carried out, and the same evaluation was performed. The results are shown in Table 1.

[Example 3]
<Manufacturing of resin composition>
Extruded with the blend weight ratio set to PC-1: PC-3: C-1: D-1 = 40: 30: 15: 15, the same operation as in Example 1 was performed, and the same evaluation was performed. .. The results are shown in Table 1.

[Example 4]
<Manufacturing of resin composition>
Extruded with the blend weight ratio set to PC-1: PC-3: C-1: D-2 = 40: 30: 15: 15, the same operation as in Example 1 was performed, and the same evaluation was performed. .. The results are shown in Table 1.

[Example 5]
(Manufacturing of Polycarbonate Resin (A))
Pellets were obtained in exactly the same manner as in Example 1 except that 294 parts of ISS, 400 parts of SPG, 22 parts of ND, and 750 parts of DPC were used as raw materials (PC-2).
<Manufacturing of resin composition>
Extruded with the blend weight ratio set to PC-2: PC-3: C + D = 20: 50: 30, the same operation as in Example 1 was carried out, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 1]
<Manufacturing of resin composition>
Extruded with the blend weight ratio set to PC-3: C + D = 70: 30, the same operation as in Example 1 was carried out, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 2]
<Manufacturing of resin composition>
Extruded with the blend weight ratio set to PC-1: C + D = 70: 30, the same operation as in Example 1 was carried out, and the same evaluation was performed. The results are shown in Table 1.

The resin composition of the present invention includes an optical lens, an optical disk, an optical film, a placel substrate, an optical card, a liquid crystal panel, a head lamp lens, a light guide plate, a diffuser plate, a protective film, an OPC binder, a front plate, a housing, a tray, and a water tank. It is useful as a member for lighting covers, signboards, resin windows, etc.

Claims (8)

The repeating unit is from the unit (a) represented by the following formula (1), the unit (b) represented by the following formula (2), and the carbonate unit (c) other than the unit (a) and the unit (b). The polycarbonate resin (A) containing 5 to 85 mol% of the unit (a), 15 to 95 mol% of the unit (b), and 0 to 80 mol% of the unit (c) among all the repeating units, the repeating unit is as follows. The unit (a) represented by the formula (1), the unit (b) represented by the following formula (2), and the carbonate unit (c) other than the unit (a) and the unit (b) are all repeated. The total of the polycarbonate resin (B) containing less than 5 mol% of the unit (a), 30 to 100 mol% of the unit (b), and 0 to 70 mol% of the unit (c), and the acrylic resin (C). A resin composition containing 5 to 60 parts by weight of the impact-resistant modifier (D) with respect to 100 parts by weight, and the refractive index of the impact-resistant modifier (D) is 1.485 or more and 1.495 or less. A resin composition characterized by being.

(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 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 carbonate unit (c) is a carbonate unit derived from at least one compound selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound and an aromatic dihydroxy compound. The resin composition according to claim 1 or 2, wherein the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is 10:90 to 90:10. The resin composition according to any one of claims 1 to 3, wherein the total weight ratio of the polycarbonate resin (A) and the polycarbonate resin (B) to the acrylic resin (C) is 30:70 to 99: 1. The resin composition according to any one of claims 1 to 4, wherein the acrylic resin (C) contains 40 to 100 mol% of a repeating unit derived from methyl methacrylate. The resin composition according to any one of claims 1 to 5, wherein the haze of the 2 mm-thick test piece is 30% or less. A molded product obtained by injection molding the resin composition according to any one of claims 1 to 6. A film or sheet formed from the resin composition according to any one of claims 1 to 6.