JP7343404B2 - Resin compositions and molded products thereof - Google Patents

Description

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

Conventionally, transparent resins such as methacrylic resin and polycarbonate resin (hereinafter sometimes referred to as PC) have been used to produce electrical and electronic parts, optical parts, automobile parts, and mechanical parts in the form of molded products, films, and sheets. It is used in a wide range of fields such as

Methacrylic acid resins such as polymethyl methacrylate (hereinafter sometimes referred to as PMMA) have high transparency and hard surface hardness (pencil hardness H to 3H), and are often used as optical materials such as lenses and optical fibers. . However, its glass transition temperature is as low as about 100° C. and its heat resistance is poor, so its use in heat-resistant fields is limited. Furthermore, there is a problem of low impact resistance.

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

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

A resin composition using a polycarbonate resin having a special structure and an acrylic resin has been reported (Patent Document 2), and excellent transparency, weather resistance, and surface hardness have been achieved. However, according to the studies of the present inventors, the resin composition described in Patent Document 2 has a problem with impact resistance, and in particular, it has been found that it shows brittle fracture like acrylic resin in a surface impact test. Served. Furthermore, it has been found that the resin composition described in Patent Document 2 has a problem with chemical resistance. Therefore, no composition of polycarbonate resin and acrylic resin with good transparency, surface hardness, impact resistance, etc. has been reported so far.

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

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

As a result of extensive research, the present inventors have found that a polycarbonate resin containing a specific spiro ring structure and a polycarbonate resin derived from an aliphatic diol having a specific ether group are combined with an acrylic resin and a refractive index within a specific range. The present inventors have discovered that by containing an impact modifier having the following properties, a resin composition can be obtained that has excellent properties in transparency, surface hardness, and impact resistance, and has completed the present invention.
That is, according to the present invention, the objects of the invention are achieved as follows.

1. A repeating unit consisting of a unit (a) represented by the following formula (1), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). Polycarbonate resin (A) containing 5 to 85 mol% of units (a), 15 to 95 mol% of units (b), and 0 to 80 mol% of units (c) among all repeating units, the repeating units are as follows. Consisting of a unit (a) represented by formula (1), a unit (b) represented by formula (2) below, and a carbonate unit (c) other than unit (a) and unit (b), all repeats A total of polycarbonate resin (B) containing less than 5 mol% of unit (a), 30 to 100 mol% of unit (b), and 0 to 70 mol% of unit (c), and acrylic resin (C) in the unit. A resin composition containing 5 to 60 parts by weight of an impact modifier (D) per 100 parts by weight, wherein the impact modifier (D) has a refractive index of 1.485 or more and 1.495 or less. A resin composition characterized by:

(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 is a branched or straight-chain alkyl group having 1 to 20 carbon atoms, or a substituent. represents a cycloalkyl group having 6 to 20 carbon atoms, and m is 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. The resin composition according to item 1 or 2 above, wherein the weight ratio of polycarbonate resin (A) and polycarbonate resin (B) is 10:90 to 90:10.

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

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

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

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

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

The present invention applies an impact modifier having a refractive index in a specific range to 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 following, it has become possible to provide a resin composition having excellent properties in transparency, surface hardness, and impact resistance. Therefore, its industrial effects are exceptional.

The present invention will be explained in detail below.

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

(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 is a branched or straight-chain alkyl group having 1 to 20 carbon atoms, or a substituent. represents a cycloalkyl group having 6 to 20 carbon atoms, and m is an integer of 0 to 10.)

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

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

These are ether diols derived from carbohydrates, substances that can also be obtained from biomass in the natural world, and are one of the so-called renewable resources. Repeating units (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 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 polycarbonate resin (A) used in the resin composition of the present invention contains 15 to 95 mol% of the unit (b) whose repeating units are represented by the above formula (2), and 20 to 90 mol% of the total repeating units. It is preferably contained in an amount of 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 80 mol%. When the unit (b) is within the above range, a resin composition with 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 aliphatic diol compounds, alicyclic diol compounds, and aromatic dihydroxy compounds. Further, the carbonate unit (c) is a carbonate unit (c) derived from at least one compound selected from the group consisting of aliphatic diol compounds and alicyclic diol compounds in terms of surface hardness and weather resistance. is preferred.

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 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 repeating units of the polycarbonate resin (A) used in the resin composition of the present invention include carbonate units (c) in an amount of 0 to 80 mol%, preferably 1 to 60 mol%, and preferably 2 to 40 mol% of all repeating units. It is more preferable to contain it in mol%, even more preferably in a range of 3 to 20 mol%, and particularly preferably in a range of 4 to 10 mol%. When the unit (c) is within the above range, a resin composition with 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 (a) represented by the following formula (1), a unit (b) represented by the following formula (2), and a unit Consisting of (a) and a carbonate unit (c) other than unit (b), the unit (a) is less than 5 mol%, the unit (b) is 30 to 100 mol%, and the unit (c) is less than 5 mol% of all repeating units. 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 is a branched or straight-chain alkyl group having 1 to 20 carbon atoms, or a substituent. represents a cycloalkyl group having 6 to 20 carbon atoms, and m is an integer of 0 to 10.)

The unit (a) represented by 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 those similar to the above-mentioned compounds.

In the polycarbonate resin (A) used in the resin composition of the present invention, the unit (a) whose repeating unit is represented by the above formula (1) is less than 5 mol% of all repeating units, and 3 mol% or less is It is preferably 1 mol % or less, more preferably 1 mol % or less, and particularly preferably substantially free of the unit (a).

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

The polycarbonate resin (B) used in the resin composition of the present invention contains 30 to 100 mol% of the unit (b) whose repeating units are represented by the above formula (2), and 50 to 99 mol% of the total repeating units. It is preferably contained in an amount of 60 to 98 mol%, even more preferably 70 to 97 mol%, and particularly preferably 80 to 96 mol%. When the unit (b) is within the above range, a resin composition with 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 aliphatic diol compounds, alicyclic diol compounds, and aromatic dihydroxy compounds. Further, the carbonate unit (c) is a carbonate unit (c) derived from at least one compound selected from the group consisting of aliphatic diol compounds and alicyclic diol compounds in terms of surface hardness and weather resistance. is preferred.

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

The repeating units of the polycarbonate resin (B) used in the resin composition of the present invention include carbonate units (c) in an amount of 0 to 70 mol%, preferably 1 to 50 mol%, and preferably 2 to 40 mol% of all repeating units. It is more preferable to contain it in mol%, even more preferably in a range of 3 to 30 mol%, and particularly preferably in a range of 4 to 20 mol%. When the unit (c) is within the above range, a resin composition with an excellent balance of transparency, surface hardness and impact resistance can be obtained.

(Production method of polycarbonate resin)
The polycarbonate resins of the polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention can be prepared by reaction methods known per se for producing ordinary polycarbonate resins, for example, by reacting a diol component with a carbonate precursor such as a carbonic acid diester. manufactured by the method. Next, basic means for these manufacturing methods will be briefly explained.

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

Examples of the carbonic diester used in the transesterification reaction include esters of optionally substituted aryl groups and aralkyl groups having 6 to 12 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-cresyl carbonate. Among them, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the dihydroxy compound in total.

In the melt polymerization method, a polymerization catalyst can be used to speed up the polymerization rate, and examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, etc. of alkali metals and alkaline earth metals are preferably used. They can be used alone or in combination.

Alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples include dilithium oxyhydrogen, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, and lithium salt of phenol.

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

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

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

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

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

In addition, as esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl para-toluenesulfonate, ethyl para-toluenesulfonate, butyl para-toluenesulfonate, Octyl para-toluenesulfonate, phenyl para-toluenesulfonate, etc. are preferably used. Among them, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

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

(Specific viscosity: _ηSP )
The specific viscosity (η _SP ) of the polycarbonate resin (A) and polycarbonate resin (B) used in the resin composition of the present invention is preferably 0.2 to 1.5. When the specific viscosity is in the range of 0.2 to 1.5, the strength and moldability of the molded product will be good. It is more preferably 0.25 to 1.2, still more preferably 0.3 to 1.0, particularly preferably 0.3 to 0.5.

The specific viscosity in the present invention is determined from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
Note that specific viscosity can be measured, for example, in the following manner. First, polycarbonate resin is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble content is collected by filtration through Celite.The solution is removed and thoroughly dried to obtain a solid of the methylene chloride soluble content. The specific viscosity at 20° C. of a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride is determined using an Ostwald viscometer.

(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 monomers used in acrylic resins 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 ( meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, glycidyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate ) acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofur Furyl (meth)acrylate, acrylic (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(phthalate) meth) acroyloxyethyl, 2-(meth)acryoyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth) Examples 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 used by polymerizing alone, or two or more types may be polymerized and used. Among these, it is preferable to include methyl methacrylate and/or methyl acrylate. 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 proportion of methyl methacrylate as a monomer component is within the above range, it has excellent heat decomposition resistance, is less likely to cause molding defects such as silver during molding, and has a good heat distortion temperature. Further, other monomers that can be polymerized with these acrylic monomers, such as polyolefin monomers, vinyl monomers, etc., may be used in combination.

The molecular weight of the acrylic resin is not particularly limited, but if the weight average molecular weight is in the range of 30,000 or more and 300,000 or less, appearance defects such as uneven flow may occur when molding the composition. However, it is possible to provide a composition with 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 moldability may be poor.

(Impact modifier (D))
The resin composition of the present invention contains an impact modifier (D). The impact modifier is preferably a core-shell type polymer consisting of a core which is a rubbery polymer and a shell obtained by graft polymerization to the rubbery polymer. By using a core-shell type polymer, the dispersibility in polycarbonate becomes good, and high impact strength tends to be obtained.

The average particle diameter of the impact modifier is preferably 10 to 500 nm. The wavelength is more preferably 30 to 300 nm, even more preferably 50 to 200 nm, and most preferably 50 to 180 nm. When the average particle diameter is less than 10 nm, sufficient impact strength tends to be insufficient. On the other hand, when the average particle diameter exceeds 500 nm, the transparency of the resulting resin composition tends to decrease. Note that the average particle diameter is measured in the latex state of the rubbery polymer and graft copolymer. The volume average particle diameter was measured using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. as a measuring device.

The rubbery polymer corresponding to the core of the impact modifier is a rubbery polymer of vinyl monomers, or a polymer of diene monomers and vinyl monomers. The transparency and impact strength of the resin composition of the present invention can be achieved by the polymer being at least one selected from (meth)acrylic acid monomers and (meth)acrylic acid alkyl ester monomers; Furthermore, it is preferable from the viewpoint of raw material cost.

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

A specific example of the diene monomer is 1,3-butadiene. Specific examples of (meth)acrylic acid monomers and (meth)acrylic acid alkyl ester monomers include acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. , ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, and glycidyl methacrylate. Examples of polymers obtained from such monomers include butadiene-acrylic acid ester copolymers.

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

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

Examples of the vinyl monomer include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acids, and unsaturated carboxylic acid esters. Among aromatic vinyl compounds, styrene, α-methylstyrene, etc. are preferable, among cyanide vinyl compounds, acrylonitrile, methacrylonitrile, etc. are preferable, and among unsaturated carboxylic acids and unsaturated carboxylic acid esters, acrylic Preferred are acids, methacrylic acid, acrylic esters and methacrylic esters having alkyl esters having 1 to 12 carbon atoms. Unsaturated carboxylic acid esters, or unsaturated carboxylic acid esters and aromatic vinyl are preferred as vinyl monomers used in graft polymerization because of their excellent dispersibility in polycarbonate resins and the excellent transparency of the resin compositions obtained. Preferably it is a mixture of compounds.

Furthermore, the impact modifier may have one or more reactive groups selected from epoxy groups, hydroxy groups, carboxy groups, alkoxy groups, isocyanate groups, acid anhydride groups, and acid chloride groups in the grafting part. can be introduced. As a result, dispersibility and impact resistance may be improved compared to when a rubber graft copolymer containing no reactive groups is used.

The refractive index of the impact 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. It is. When the refractive index of the impact modifier is within the above range, the resin composition has excellent transparency and impact resistance.

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

The types of polymerization initiator, chain transfer agent, and redox agent used here are not particularly limited, and known ones can be used. Furthermore, there is no particular restriction on the method of adding each raw material to the reaction vessel, and addition may be carried out in batches or in portions before the start of polymerization. In addition, graft polymerization is carried out in one stage or in two or more stages, and the monomer composition in each stage may be the same or different, and even if the monomers are added all at once, they can be added continuously. or a combination of these.

When employing the emulsion polymerization method, use a known polymerization initiator, that is, a thermal decomposition type polymerization initiator such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate, etc. I can do it. In addition, organic peroxides such as t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide are also available. peroxides such as oxides or inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, and optionally reducing agents such as sodium formaldehyde sulfoxylate, 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 ethylenediaminetetraacetate, and a phosphorus flame retardant such as sodium pyrophosphate as necessary. You can also do it.

When a redox type polymerization initiator system is used, polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and therefore the polymerization temperature can be set within a wide range, which is preferable. Among these, aromatic ring-containing peroxides such as cumene hydroperoxide and dicumyl peroxide are preferably used as the redox polymerization initiator. The amount of the polymerization initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox type polymerization initiator is used, can be used within known ranges.

When synthesizing impact modifiers by emulsion polymerization, polymerization emulsifiers include alkali metal salts of higher fatty acids such as disproportionated rosin acid, oleic acid, and stearic acid, or alkali metal salts of phosphoric acid compounds. Conventionally known polymeric emulsifiers such as alkali metal salts of sulfonic acids and sulfuric acid compounds can be used.

When an impact modifier is obtained by emulsion polymerization, for example, the latex of the impact modifier and an acid such as hydrochloric acid, or a divalent or higher valent agent such as calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride, calcium acetate, etc. After coagulating by mixing metal salts, the impact modifier can be separated from the aqueous medium by heat treatment, dehydration, washing, and drying according to known methods (also referred to as coagulation method). Alternatively, an alcohol such as methanol, ethanol, or propanol, or a water-soluble organic solvent such as acetone is added to the latex to precipitate the impact modifier, and the impact modifier is separated from the solvent by centrifugation or filtration, and then dried and isolated. You can also. Another method is to add a slightly water-soluble organic solvent such as methyl ethyl ketone to the latex containing the impact modifier used in the present invention, and extract the impact modifier component in the latex into the organic solvent layer. Examples include a method of separating the solvent layer and then mixing it with water or the like to precipitate the impact modifier component. Alternatively, the latex can be directly pulverized by spray drying.

In addition, in the present invention, a resin composition may be used in which an impact modifier is previously contained in an acrylic resin and is contained in a polycarbonate resin. Specific examples of the acrylic resin containing an impact modifier include, but are not particularly limited to, the following.

For example, manufactured by Mitsubishi Chemical Corporation, product name Acrypet IRK304, IRL309, VRL40, manufactured by Kuraray Co., Ltd., product name Parapet GR00100, GR04970, GR-H60, manufactured by Daicel Evonik, product name PLEXIGLAS AG100, zk6HF, manufactured by Asahi Kasei Co., Ltd. Examples include Delpet SR8350 and SR8500.

(Method for producing a resin composition containing a polycarbonate resin, an acrylic resin, and an impact modifier)
The resin composition of the present invention is preferably a blend of a polycarbonate resin (A), a polycarbonate resin (B), an acrylic resin (C), and an impact modifier (D) in a molten state. As a method for blending in a molten state, an extruder is generally used, and the molten resin is kneaded and pelletized at a temperature of 200 to 320°C, preferably 220 to 300°C, more preferably 230 to 290°C. Thereby, pellets of the resin composition in which both resins are uniformly blended are obtained. The structure of the extruder, the structure of the screw, etc. are not particularly limited. If the temperature of the molten resin in the extruder exceeds 320°C, the resin may be colored or thermally decomposed. On the other hand, if the resin temperature is below 200°C, the resin viscosity may be too high and the extruder may be overloaded.

(weight ratio)
The weight ratio of the polycarbonate resin (A) and polycarbonate resin (B) is preferably in the range of 10:90 to 90:10. More preferably the range is 15:85 to 85:15, still more preferably the range is 20:80 to 80:20, particularly preferably the range is 25:75 to 75:25, most preferably 30: It is in the range of 70 to 70:30. By setting it within the above range, a resin composition with excellent surface hardness and impact resistance can be obtained.

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

The impact modifier is mixed in an amount of 5 to 60 parts by weight based on a total of 100 parts by weight of the polycarbonate resin and 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, still more preferably in the range of 9 to 30 parts by weight, and particularly preferably in the range of 10 to 25 parts by weight. . By setting it as the said range, a resin composition excellent in transparency, surface hardness, and impact resistance can be obtained.

(Additive)
The resin composition used in the present invention may include heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, and antibacterial agents, depending on the purpose and necessity. , ultraviolet absorbers, mold release agents, colorants, and other additives may be added.

(thermal stabilizer)
The resin composition used in the present invention particularly preferably contains a heat stabilizer in order to suppress molecular weight reduction and hue deterioration during extrusion and molding. Examples of the heat stabilizer include phosphorus-based heat stabilizers, phenol-based heat stabilizers, and sulfur-based heat stabilizers, and one type of these can be used alone or two or more types can be used in combination. It is preferable to incorporate a phosphite compound as the phosphorus stabilizer. Examples of the phosphite compound include pentaerythritol type phosphite compounds, phosphite compounds that react with dihydric phenols and have a cyclic structure, and phosphite compounds having other structures.

Specifically, the above pentaerythritol type phosphite compounds include, for example, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6 -di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples include bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and among them, distearylpentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are preferred. Erythritol diphosphite is mentioned.

Examples of the phosphite compound having a cyclic structure that reacts with the above dihydric phenols include 2,2'-methylenebis(4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) ) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6- tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) ) phosphite, 2,2'-methylene-bis-(4,6-di-t-butylphenyl)octyl phosphite, 6-tert-butyl-4-[3-[(2,4,8,10) Examples include -tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol.

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

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

Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferred.

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

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

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

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

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

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

Among these, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, pentaerythrityl-tetrakis {3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate}, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a'-(mesitylene-2,4,6-triyl) Tri-p-cresol, 2,2-thiodiethylenebis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, and the like are preferred.

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

The hindered phenol heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and even more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin composition. Part is mixed.

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

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

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

When a phosphite-based heat stabilizer, a phenol-based heat stabilizer, and a sulfur-based heat stabilizer are used together, the total amount of these is preferably 0.001 to 1 part by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the resin composition. It is blended in an amount of .01 to 0.3 parts by weight.

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

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

The higher fatty acid ester is preferably a partial or total ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of such partial or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, and behenic acid. Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenylbiphene -t, sorbitan monostearate, 2-ethylhexyl stearate and the like.

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

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

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

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

Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, and 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole. '-Hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3', 5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-bis (α,α'-dimethylbenzyl)phenylbenzotriazole, 2-[2'-hydroxy-3'-(3'',4'',5'',6''-tetraphthalimidomethyl)-5'-methylphenyl]benzotriazole , 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], methyl-3-[3 Benzotriazole ultraviolet absorbers typified by a condensate of -tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate and polyethylene glycol can be mentioned.

The proportion of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, and even more preferably 0.2 to 0.5 parts by weight based on 100 parts by weight of the resin composition. It is.

(light stabilizer)
The resin composition used in the present invention can contain a light stabilizer. Containing a light stabilizer has the advantage of good weather resistance and making it difficult for molded products to crack.

Examples of light stabilizers include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, didecanoic acid bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, 2,4- bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-2-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, Methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, Bis(2,2,6,6- Tetramethyl-4-piperidyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4 -benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) ) diphenylmethane-p,p'-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)benzene-1,3-disulfonate, bis(2,2,6,6-tetramethyl Hindered amines such as -4-piperidyl) phenyl phosphite, nickel such as nickel bis(octylphenyl sulfide, nickel complex -3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyl dithiocarbamate, etc.) Examples include complexes. These light stabilizers may be used alone or in combination of two or more. The content of the light stabilizer is preferably 0.001 to 1 part by weight based on 100 parts by weight of the resin composition. More preferably, it is 0.01 to 0.5 parts by weight.

(Epoxy stabilizer)
In order to improve hydrolyzability, an epoxy compound can be blended into the resin composition used in the present invention within a range that does not impair the purpose of the present invention.

Epoxy stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl carboxylate , 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl)butyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy -6-Methylcyclohexylmethyl-6'-methylsilohexylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxy dicyclo Pentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3, 5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2 , 2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, Octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3',4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3',4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl -3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate and the like. Bisphenol A diglycidyl ether is preferred from the viewpoint of compatibility.

Such an epoxy stabilizer is used in an amount of 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight, and 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 within a range.

(Bluing agent)
The resin composition used in the present invention may contain a bluing agent in order to cancel out the yellow tint of the lens due to the polymer or ultraviolet absorber. As the bluing agent, any one used for polycarbonate can be used without any particular problem. Generally, anthraquinone dyes are preferred because they are easily available.

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

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

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

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

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

(Molding)
The resin composition of the present invention can be molded and processed by any method such as an injection molding method, a compression molding method, an injection compression molding method, a melt film forming method, a casting method, etc., and can be used to produce optical lenses, optical discs, optical films, plastic cell substrates, etc. It can be used as molded products such as optical cards, liquid crystal panels, headlamp lenses, light guide plates, diffusion plates, protective films, OPC binders, front plates, casings, trays, water tanks, lighting covers, signboards, and resin windows. In particular, it can be used as members that require high surface hardness, such as front panels, housings, trays, water tanks, lighting covers, signboards, and resin windows.

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

(transparency)
The resin composition of the present invention preferably has a haze of 2 mm thick molded pieces of 30% or less, more preferably 25% or less, even more preferably 20% or less, and 15% or less. Particularly preferred. It is preferable that the haze is within the above range because the range of use as an optical member is not limited.

(Impact strength)
The resin composition of the present invention preferably has a notched Charpy impact strength of 15 kJ/m ² or more, more preferably 18 kJ/m ² or more, and 20 kJ/m ² or more as measured in accordance with ISO179. is even more preferable. Note that the notched Charpy impact strength is 100 kJ/m ² or less and has sufficient functionality.

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

(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.

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]

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

4. Notched Charpy Impact Strength The notched Charpy impact strength of the ISO bending test piece obtained by the method described below was measured in accordance with ISO 179.

5. High-speed surface impact test Using a flat plate measuring 45 mm long x 50 mm wide x 2 mm thick obtained under the same conditions as the method below, a high-speed puncture impact tester "Hydroshot HTM-P10" (Shimadzu) was used in accordance with JIS K7211-2. A punching test was conducted at a punching 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 on the surface of the molded product in a constant temperature room with an ambient temperature of 23 degrees C while holding a pencil at a 45 degree angle and applying a load of 750 g, and visually check the surface condition. evaluated.

[Polycarbonate resin (A)]
PC-1 (Example):
Structural unit derived from isosorbide (hereinafter referred to as ISS)/3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter referred to as SPG) Structural unit derived from / Structural unit derived from 1,9-nonanediol (hereinafter referred to as ND) = 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-terminated modified resin, specific viscosity 0.366
[Acrylic resin (C)]
C-1: Acrypet VH001 manufactured by Mitsubishi Chemical (acrylic resin copolymerized with 95 mol% methyl methacrylate and 5 mol% methyl acrylate)
[Impact modifier composite acrylic resin (C+D)]
C+D: Acrypet VRL40 manufactured by Mitsubishi Chemical Corporation (refractive index of impact modifier: 1.492)
[Impact modifier (D)]
D-1: Kane Ace M-230 manufactured by Kaneka (Refractive index: 1.492)
D-2: Metablane W-377 manufactured by Mitsubishi Chemical Corporation (refractive index: 1.492)

[Example 1]
<Production of polycarbonate resin>
(Manufacture of polycarbonate resin (A))
364 parts of isosorbide (hereinafter abbreviated as ISS), 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter abbreviated as SPG) ), 39 parts of 1,9-nonanediol (hereinafter abbreviated as ND), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 0.8×10 ^-2 parts of tetramethylammonium hydroxide and barium stearate as a catalyst. 0.6×10 ⁻⁴ parts were heated to 200° C. under a nitrogen atmosphere to melt them. Thereafter, the temperature was raised to 220° C. over 30 minutes, and the degree of pressure reduction was adjusted to 20.0 kPa. Thereafter, the temperature was raised to 240° C. and the degree of pressure reduction was adjusted to 10 kPa over a further 30 minutes. After holding at that temperature for 10 minutes, the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. After the reaction was completed, nitrogen was discharged from the bottom of the reaction tank under pressure, and while cooling in a water tank, the mixture was cut with a pelletizer to obtain pellets (PC-1).

(Manufacture 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 part was heated to 120° C. under a nitrogen atmosphere to melt it. Thereafter, the liquid was sent to the reaction tank, the temperature of the heat medium of the condenser was adjusted to 40°C, the internal temperature of the resin was adjusted to 170°C, and the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. Thereafter, the degree of vacuum was adjusted to 3.4 kPa over 20 minutes, and maintained at that temperature for 10 minutes. The degree of vacuum was increased to 0.9 kPa over another 30 minutes, the resin internal temperature was adjusted to 180°C, and after holding at that temperature for 10 minutes, the degree of vacuum was increased to 0.2 kPa, and the resin temperature was increased from 180°C to 225°C for 30 minutes. After reaching the specified viscosity, it was discharged from the bottom of the reaction tank under nitrogen pressure, and while cooling in a water tank, it was cut with a pelletizer to obtain pellets (PC-3).

<Manufacture of resin composition>
Polycarbonate resin PC-1, polycarbonate resin PC-3, acrylic resin C+D: Using Mitsubishi Chemical's Acrypet VRL40 (impact modifier composite acrylic resin), they were mixed at a weight ratio of 40:30:30. After that, it was fed to the extruder. For extrusion, a vented twin-screw extruder [Kobe Steel, Ltd. KTX-30] with a diameter of 30 mm was used, and the pellets were melted and kneaded at a screw rotation speed of 150 rpm, a discharge rate of 20 kg/h, and a vent vacuum of 3 kPa. Ta. Note that the extrusion temperature was 250° C. from the supply port to the die portion. After drying a part of the obtained pellets in a hot air circulation dryer at 90°C for 6 hours or more, test pieces were prepared using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 60°C. (ISO bending test piece (according to ISO178, ISO179, ISO75-1 and ISO75-2), 3-stage plate (1 mmt, 2mmt, 3mmt)) was molded. The evaluation results are shown in Table 1.

[Example 2]
<Manufacture of resin composition>
Except for extruding at a blend weight ratio of PC-1:PC-3:C+D=20:50:30, the operation was exactly the same as in Example 1, and the same evaluation was performed. The results are listed in Table 1.

[Example 3]
<Manufacture of resin composition>
Except for extruding at a blend weight ratio of 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 listed in Table 1.

[Example 4]
<Manufacture of resin composition>
Except for extruding at a blend weight ratio of 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 listed in Table 1.

[Example 5]
(Manufacture of polycarbonate resin (A))
Pellets were obtained by performing exactly the same operation 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).
<Manufacture of resin composition>
Except for extruding at a blend weight ratio of PC-2:PC-3:C+D=20:50:30, 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 1]
<Manufacture of resin composition>
Except for extruding at a blend weight ratio of PC-3:C+D=70:30, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are listed in Table 1.

[Comparative example 2]
<Manufacture of resin composition>
Except for extruding at a blend weight ratio of PC-1:C+D=70:30, the operation was exactly the same as in Example 1, and the same evaluation was performed. The results are listed in Table 1.

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

Claims (8)

A repeating unit consisting of a unit (a) represented by the following formula (1), a unit (b) represented by the following formula (2), and a carbonate unit (c) other than the unit (a) and the unit (b). Polycarbonate resin (A) containing 5 to 85 mol% of units (a), 15 to 95 mol% of units (b), and 0 to 80 mol% of units (c) among all repeating units, the repeating units are as follows. Consisting of a unit (a) represented by formula (1), a unit (b) represented by formula (2) below, and a carbonate unit (c) other than unit (a) and unit (b), all repeats A total of polycarbonate resin (B) containing less than 5 mol% of unit (a), 30 to 100 mol% of unit (b), and 0 to 70 mol% of unit (c), and acrylic resin (C) in the unit. A resin composition containing 5 to 60 parts by weight of an impact modifier (D) per 100 parts by weight, wherein the impact modifier (D) has a refractive index of 1.485 or more and 1.495 or less. A resin composition characterized by:

(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 is a branched or straight-chain alkyl group having 1 to 20 carbon atoms, or a substituent. represents a cycloalkyl group having 6 to 20 carbon atoms, and m is an integer of 0 to 10.)

2. 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) and the polycarbonate resin (B) is 10:90 to 90:10. The resin composition according to any one of claims 1 to 3, wherein the weight ratio of the total of polycarbonate resin (A) and polycarbonate resin (B) to 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 repeating units derived from methyl methacrylate. The resin composition according to any one of claims 1 to 5, wherein the haze of a 2 mm thick test piece is 30% or less. A molded article obtained by injection molding the resin composition according to any one of claims 1 to 6. A film or sheet formed from the resin composition according to any one of claims 1 to 6.