JP7582837B2 - Resin composition and molded article thereof - Google Patents

Description

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

Conventionally, methacrylic resins and polycarbonate resins (hereinafter sometimes referred to as PC) are known as transparent resins, and they are used in a wide range of fields such as electrical and electronic components, optical components, automotive components, and mechanical components in the form of molded products, films, and sheets.

Methacrylic acid resins such as polymethyl methacrylate (hereinafter sometimes referred to as PMMA) have high transparency and high surface hardness (pencil hardness H to 3H), and are widely used as optical materials such as lenses and optical fibers. However, their glass transition temperature is low at around 100°C, and their heat resistance is poor, limiting their use in fields requiring heat resistance. Another problem is that they have low impact resistance.

Polycarbonate resin made from bisphenol A is widely used in vehicles and building materials due to its excellent heat resistance, impact resistance, flame retardancy and transparency. Among these applications, high weather resistance is required, especially for outdoor use, but the weather resistance of polycarbonate resin is generally not as good as other transparent materials such as acrylic resin, and yellowing and devitrification occur when exposed to the outdoors. In addition, the surface is very soft (pencil hardness 4B to 2B) and is easily scratched.

It is known that blends of PC and PMMA are essentially incompatible and produce opaque materials. For example, Patent Document 1 shows that blends of PC and PMMA are opaque and do not exhibit the physical properties of both polymers.

A resin composition using a polycarbonate resin with a special structure and an acrylic resin has been reported (Patent Document 2), which has achieved excellent transparency, weather resistance, and surface hardness. However, according to the inventors' investigations, the resin composition described in Patent Document 2 has issues with impact resistance.

In addition, polycarbonate resin and acrylic resin are easily charged, and there is a problem that dust easily adheres to the surface of the molded product due to static electricity. One method of dealing with this static electricity is to add hydrophilic polyamide-based polymers such as polyetheresteramide and polyetheramide to impart antistatic properties (Patent Document 3). However, when these hydrophilic polyamide-based polymers are added to polycarbonate resin or acrylic resin, there is a problem that transparency is significantly reduced.

Therefore, no compositions of polycarbonate resin and acrylic resin that have good transparency, surface hardness, impact resistance, and antistatic properties have been reported to date.

U.S. Pat. No. 4,319,003 JP 2015-232091 A JP 2002-129026 A

The object of the present invention is to provide a resin composition containing a polycarbonate resin, an acrylic resin, an impact modifier and an antistatic agent, which has excellent properties such as transparency, surface hardness, impact resistance and antistatic properties.

Means for Solving the Problems The present inventors have conducted extensive research and have discovered that by incorporating an acrylic resin, an impact modifier having a refractive index within a specific range, and a block polymer having a specific structure into a polycarbonate resin containing a specific spiro ring structure, a resin composition having excellent properties such as transparency, surface hardness, impact resistance, and antistatic properties can be obtained, thereby completing the present invention.
That is, according to the present invention, the object of the invention is achieved as follows.

1. A resin composition comprising 100 parts by weight of a polycarbonate resin (A) containing 5 to 85 mol % of carbonate structural units (a) represented by the following formula (1) out of 100 mol % of all carbonate structural units, and an acrylic resin (B), 5 to 60 parts by weight of an impact modifier (C) having a refractive index of 1.485 to 1.495, and 1 to 20 parts by weight of a block polymer (D) having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, R represents a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and m represents an integer from 0 to 10.)

2. The resin composition according to the preceding paragraph 1, wherein the polycarbonate resin (A) is composed of a carbonate structural unit (a) represented by the formula (1) and another carbonate structural unit (b), and the carbonate structural unit (b) is a carbonate structural unit (b) 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 the polycarbonate resin (A) to the acrylic resin (B) is 30:70 to 99:1.
4. The resin composition according to any one of items 1 to 3 above, wherein the acrylic resin (B) contains 40 to 100 mol % of structural units derived from methyl methacrylate.
5. The resin composition according to any one of items 1 to 4, wherein a haze of a 5.2 mm thick test piece is 20 or less.
6. The resin composition according to any one of items 1 to 5 above, which has a Charpy notched impact strength measured in accordance with ISO 179 of 10 kJ/m2 or ^more .
7. The resin composition according to any one of items 1 to 6 above, which has a pencil hardness of B or more as measured in accordance with JIS K-5600.
8. The resin composition according to any one of items 1 to 7 above, wherein the surface resistivity of the molded product is 1×10 ¹⁵ (Ω/□) or less.
9. A molded article obtained by molding the resin composition according to any one of items 1 to 8 above.
10. A film or sheet formed from the resin composition according to any one of items 1 to 8 above.

The present invention makes it possible to provide a resin composition that has excellent properties such as transparency, surface hardness, impact resistance, and antistatic properties by incorporating an impact modifier having a specific range of refractive index and a block polymer having a specific structure into a resin component of a polycarbonate resin containing a specific spiro ring structure and an acrylic resin. Therefore, the industrial effects achieved are exceptional.

The present invention will be described in detail below.
(Polycarbonate resin (A))
The polycarbonate resin used in the resin composition of the present invention is a polycarbonate resin containing 5 to 85 mol % of carbonate structural units (a) represented by the following formula (1) relative to 100 mol % of all carbonate structural units.

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, R represents a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and m represents an integer from 0 to 10.)

The carbonate structural unit (a) represented by the above formula (1) is derived from a diol having a spiro ring structure. Examples of diol compounds having such a spiro ring structure include alicyclic diol compounds such as 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, and 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane.

Preferably, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane is used.

The polycarbonate resin used in the resin composition of the present invention contains 5 to 85 mol %, preferably 10 to 80 mol %, more preferably 15 to 75 mol %, and even more preferably 20 to 70 mol % of the carbonate structural unit (a) represented by the above formula (1) out of 100 mol % of all carbonate structural units. When the carbonate structural unit (a) is within the above range, the resin composition does not become cloudy due to phase separation during extrusion or molding of the resin composition with the acrylic resin, and polymerization is easy without crystallization during polymerization of the polycarbonate resin, which is preferable.

The polycarbonate resin used in the resin composition of the present invention contains the carbonate structural unit (a) represented by the above formula (1), and is used as a copolymer with another carbonate structural unit (b).

The carbonate structural unit (b) is preferably a carbonate structural unit (b) 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. In addition, from the standpoint of surface hardness and weather resistance, the carbonate structural unit (b) is preferably a carbonate structural unit (b) derived from at least one compound selected from the group consisting of an aliphatic diol compound and an alicyclic diol compound.

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, and 2,2-diethyl-1,3-propanediol. , 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc., and 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; cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; norbornane dimethanols such as 2,3-norbornane dimethanol and 2,5-norbornane dimethanol; tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalin dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and isosorbide; and cyclohexanedimethanols and isosorbide 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, with bisphenol A being preferred.

The carbonate structural unit (b) is contained in an amount of 15 to 95 mol %, preferably 20 to 90 mol %, more preferably 25 to 85 mol %, and even more preferably 30 to 80 mol %, of the total carbonate structural units (100 mol %). When the carbonate structural unit (b) is within the above range, a resin composition having an excellent balance of transparency, surface hardness, impact resistance, and antistatic properties can be obtained.

(Production method of polycarbonate resin (A))
The polycarbonate resin used in the resin composition of the present invention is produced by a reaction means known per se for producing ordinary polycarbonate resins, for example, a method of reacting a diol component with a carbonate precursor such as a carbonic acid diester. The basic means for these production methods will now be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by heating and stirring a specified ratio of diol components with a carbonic acid diester in an inert gas atmosphere, and distilling off the resulting alcohol or phenols. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenols, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenols. If necessary, a terminal terminator, antioxidant, etc. may also be added.

The carbonic acid diester used in the transesterification reaction may be an ester of an aryl group or an aralkyl group having 6 to 12 carbon atoms, which may be substituted. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 moles, more preferably 1.00 to 1.06 moles, per mole of the total of the dihydroxy compounds.

In addition, in the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. 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 or alkaline earth metals are preferably used, and these compounds can be used alone or in combination.

Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, 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, dilithium hydrogen phosphate, disodium phenylphosphate, disodium, dipotassium, dicesium, and dilithium salts of bisphenol A, and sodium, potassium, cesium, and lithium salts 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, barium diacetate, barium stearate, etc.

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. Other examples include tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Other examples include bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc. These compounds may be used alone or in combination of two or more.

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

A catalyst deactivator can also be added in the later stages of the reaction. Known catalyst deactivators are effectively used as catalyst deactivators, and among these, ammonium salts and phosphonium salts of sulfonic acid are preferred. Furthermore, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, and salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid are preferred.

As sulfonic acid esters, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, octyl paratoluenesulfonate, phenyl paratoluenesulfonate, etc. are preferably used. Among these, tetrabutylphosphonium dodecylbenzenesulfonate 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 moles per mole of the catalyst, more preferably 0.5 to 10 moles, and even more preferably 0.8 to 5 moles.

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

The specific viscosity referred to in the present invention is determined by dissolving 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
[ _t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls]
The specific viscosity can be measured, for example, as follows: First, polycarbonate resin is dissolved in methylene chloride in an amount 20 to 30 times its weight, and the soluble matter is collected by filtration through Celite. The solution is then removed and the mixture is thoroughly dried to obtain a solid that is soluble in methylene chloride. 0.7 g of the solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined using an Ostwald viscometer.

(Acrylic resin (B))
The acrylic resin used in the resin composition of the present invention is an acrylic resin as a thermoplastic resin. The following compounds can be mentioned as monomers used in the acrylic resin. 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, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Examples of the acrylate include acrylate, acrylic (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acroyloxyethyl succinate, 2-(meth)acroyloxyethyl maleate, 2-(meth)acroyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, and cyclododecyl acrylate.

These may be polymerized alone or in combination of two or more. Among these, it is preferable to contain methyl methacrylate and/or methyl acrylate. In particular, it is preferable to contain 40 to 100 mol% of methyl methacrylate as a monomer component, 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, the resin has excellent thermal decomposition resistance, is less likely to cause molding defects such as silver during molding, and has a good heat distortion temperature. In addition, 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 as long as the weight average molecular weight is in the range of 30,000 or more and 300,000 or less, a composition with excellent mechanical properties and heat resistance can be provided without causing poor appearance such as uneven flow when molded into a composition.

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. If the specific viscosity is higher than 0.55, the melt viscosity of the resin may increase, resulting in poor moldability.

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

The average particle size of the impact modifier (C) is preferably 10 to 500 nm. More preferably, it is 30 to 300 nm, even 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, if the average particle size exceeds 500 nm, the transparency of the resulting 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 a MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. as a measuring device.

The rubbery polymer corresponding to the core of the impact modifier (C) is a rubbery polymer of a vinyl monomer, or a polymer of a diene monomer and a vinyl monomer, and the vinyl monomer is at least one selected from a (meth)acrylic acid monomer and a (meth)acrylic acid alkyl ester monomer, which is preferable from the viewpoint of achieving both transparency and impact strength of the resin composition of the present invention, and also from the viewpoint of raw material costs.

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 a 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, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, and glycidyl methacrylate. Polymers obtained from such monomers include, for example, butadiene-acrylic acid ester copolymers.

From the viewpoint of improving impact resistance, it is preferable that the glass transition temperature (Tg) of the rubber-like polymer is 0°C or lower. It is more preferable that it is -20°C or lower, and even more preferable that it is -40°C or lower.

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

Examples of vinyl monomers include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acids, and unsaturated carboxylic acid esters. Among aromatic vinyl compounds, styrene and α-methylstyrene are preferred, among vinyl cyanide compounds, acrylonitrile and methacrylonitrile are preferred, and among unsaturated carboxylic acids and unsaturated carboxylic acid esters, acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters having alkyl esters with 1 to 12 carbon atoms are preferred. Since they have excellent dispersibility in polycarbonate resins and the resulting resin composition has excellent transparency, it is preferred that the vinyl monomer used in the graft polymerization is an unsaturated carboxylic acid ester, or a mixture of an unsaturated carboxylic acid ester and an aromatic vinyl compound.

Furthermore, one or more reactive groups selected from epoxy groups, hydroxy groups, carboxy groups, alkoxy groups, isocyanate groups, acid anhydride groups, and acid chloride groups can be introduced into the graft portion of the impact modifier (C). This can improve dispersibility and impact resistance compared to the use of a rubber graft copolymer that does not contain reactive groups.

The refractive index of the impact modifier (C) 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. When the refractive index of the impact modifier (C) is within the above range, the transparency and impact resistance of the resin composition are excellent.

The impact modifier (C) may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but emulsion polymerization, i.e., emulsion graft polymerization, is preferred. Specifically, latex is added to a reaction vessel equipped with a stirrer, followed by addition of a vinyl monomer, a polymerization initiator, and water, and optionally a chain transfer agent and an oxidation-reduction agent, followed by heating and stirring.

The types of polymerization initiator, chain transfer agent, and redox agent used here are not particularly limited, and known ones can be used. The method of adding each raw material to a reaction vessel is also not particularly limited, and they may be added all at once before the start of polymerization, or may be added in portions. The graft polymerization is carried out in one or more stages, and the monomer composition in each stage may be the same or different. The monomers may be added all at once, continuously, or in a combination of these.

When the emulsion polymerization method is employed, known polymerization initiators, i.e., thermal decomposition type polymerization initiators such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate, can be used. In addition, redox type polymerization initiators can be used in combination with organic peroxides such as t-butylperoxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide, or inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, as well as reducing agents such as sodium formaldehyde sulfoxylate and glucose, transition metal salts such as iron (II) sulfate, chelating agents such as disodium ethylenediaminetetraacetate, and phosphorus-based flame retardants such as sodium pyrophosphate.

When a redox type polymerization initiator system is used, the polymerization can be carried out even at a low temperature where the peroxide does not substantially decompose thermally, and therefore the polymerization temperature can be set within a wide range, which is preferable. Among them, it is preferable to use an aromatic ring-containing peroxide such as cumene hydroperoxide or dicumyl peroxide as the 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 a redox type polymerization initiator is used, can be within the known range.

When synthesizing the impact resistance modifier (C) by emulsion polymerization, the polymerization emulsifier that can be used may be any of the conventionally known polymerization emulsifiers, such as 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, and further alkali metal salts of sulfonic acid and sulfuric acid compounds.

When the impact modifier (C) is obtained by emulsion polymerization, for example, the latex of the impact modifier (C) is mixed with an acid such as hydrochloric acid or a divalent or higher metal salt such as calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride, or calcium acetate to coagulate, and then the mixture is heat-treated, dehydrated, washed, and dried according to a known method to separate the impact modifier from the aqueous medium (also called the coagulation method). Alternatively, the impact modifier can be precipitated by adding a water-soluble organic solvent such as an alcohol such as methanol, ethanol, or propanol, or acetone to the latex, and then separated from the solvent by centrifugation or filtration, and then dried and isolated. As another method, a method can be mentioned in which a slightly water-soluble organic solvent such as methyl ethyl ketone is added to the latex containing the impact modifier used in the present invention to extract the impact modifier component in the latex into the organic solvent layer, and after separating the organic solvent layer, the impact modifier component is precipitated by mixing with water or the like. The latex can also be directly powdered by a spray drying method.

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

For example, Mitsubishi Chemical Corporation's ACRYPET IRK304, IRL309, VRL40, Kuraray Co., Ltd.'s PARAPET GR00100, GR04970, GR-H60, Daicel-Evonik Co., Ltd.'s PLEXIGLAS AG100, zk6HF, Asahi Kasei Corporation's DELPET SR8350, SR8500, etc.

(Block polymer (D))
The resin composition of the present invention contains a block polymer (D) having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded.

The polyether chain functions as a hydrophilic segment, and the inclusion of the polyether chain provides antistatic performance. The weight average molecular weight of the polyether chain is preferably 1,000 to 15,000 from the viewpoint of heat resistance and reactivity with polyolefin chains. Such block polymers can be obtained, for example, by a method described in JP-A-2001-278985 and JP-A-2003-48990 in which polypropylene or polyethylene is acid-modified and reacted with polyalkylene glycol.

Since the block polymer (D) used in the present invention exhibits antistatic properties by being dispersed in a polycarbonate resin and an acrylic resin, it is generally preferred that the surface resistance of the block polymer (D) itself is as low as possible. The surface resistance of such a block polymer is generally 1×10 ¹⁰ to 1×10 ⁴ Ω, but the surface resistance of the block polymer (D) used in the present invention is preferably 1×10 ⁹ to 1×10 ⁴ Ω, and more preferably 1×10 ⁸ to 1×10 ⁴ Ω.

To further improve the antistatic properties, antistatic agents other than the block polymers described above may be used in combination, if necessary.

Other antistatic agents that can be used include surfactants [anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.], salts other than surfactant salts, and ionic liquids.

(Method for producing a resin composition containing a polycarbonate resin, an acrylic resin, an impact modifier and a block polymer)
The resin composition of the present invention is preferably prepared by blending a polycarbonate resin, an acrylic resin, an impact modifier, and an antistatic agent containing a block polymer in a molten state. As a method for blending in a molten state, an extruder is generally used, and the molten resin is kneaded at a temperature of 200 to 320°C, preferably 220 to 300°C, more preferably 230 to 290°C, and then pelletized. This provides pellets of a resin composition in which both resins are uniformly blended. The configuration of the extruder, the configuration of the screw, and the like are not particularly limited. If the molten resin temperature in the extruder exceeds 320°C, the resin may become discolored or may undergo thermal decomposition. On the other hand, if the resin temperature is below 200°C, the resin viscosity may be too high and the extruder may be overloaded.

(Weight ratio)
The weight ratio of the polycarbonate resin (A) and the acrylic resin (B) used in the present invention is preferably in the range of 30:70 to 99:1. More preferably, it is in the range of 35:65 to 95:5, even more preferably in the range of 40:60 to 93:7, particularly preferably in the range of 45:55 to 92:8, and most preferably in the range of 50:50 to 90:10. By keeping it in the above range, a resin composition excellent in surface hardness and impact resistance can be obtained.

The impact modifier (C) used in the present invention is blended in the range of 5 to 60 parts by weight per 100 parts by weight of the total of the polycarbonate resin and the acrylic resin. The range is preferably 7 to 55 parts by weight, more preferably 8 to 50 parts by weight, even more preferably 9 to 48 parts by weight, and particularly preferably 10 to 45 parts by weight. By using the above range, a resin composition with excellent transparency, surface hardness, and impact resistance can be obtained.

The block polymer (D) used in the present invention is blended in the range of 1 to 20 parts by weight per 100 parts by weight of the total of the polycarbonate resin and the acrylic resin. The range is preferably 2 to 19 parts by weight, more preferably 3 to 18 parts by weight, even more preferably 5 to 16 parts by weight, and particularly preferably 8 to 15 parts by weight. By adjusting the range to the above range, a resin composition excellent in transparency, surface hardness, impact resistance, and antistatic properties can be obtained.

(Additives)
The resin composition used in the present invention may contain additives such as a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, a surfactant, an antibacterial agent, an ultraviolet absorber, a release agent, and a colorant depending on the application and need.

(Heat stabilizer)
The resin composition used in the present invention preferably contains a heat stabilizer in order to suppress the molecular weight reduction and the deterioration of the color tone during extrusion and molding. Examples of the heat stabilizer include phosphorus-based heat stabilizers, phenol-based heat stabilizers, and sulfur-based heat stabilizers, and these can be used alone or in combination of two or more. It is preferable to blend a phosphite compound as the phosphorus-based 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 with other structures.

Specific examples of the pentaerythritol-type phosphite compounds include 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, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like. Among these, distearyl pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are preferred.

Examples of phosphite compounds that react with the above dihydric phenols to form a cyclic structure 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, Examples of such phosphite include 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylene-bis-(4,6-di-t-butylphenyl)octylphosphite, and 6-tert-butyl-4-[3-[(2,4,8,10)-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol.

Examples of the phosphite compounds having the above other structures include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl)phosphite, tris(di-i
so-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.

Examples of 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, diisopropyl phosphate, etc., and preferably triphenyl phosphate and trimethyl phosphate.

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

Examples of phosphonate compounds 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 diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are preferably used.

The above phosphorus-based heat stabilizers can be used alone or in combination of two or more kinds. 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 parts by weight, and even more preferably 0.01 to 0.3 parts by weight per 100 parts by weight of the resin composition.

The resin composition used in the present invention may contain a hindered phenol-based heat stabilizer or a sulfur-based heat stabilizer in combination with a phosphorus-based heat stabilizer to suppress a decrease in molecular weight or deterioration in color during extrusion and molding.

Examples of hindered phenol-based heat stabilizers include, but are not limited to, those that have an antioxidant function, such as 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-thiazole-bis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, tetrakis(methylene- ...) and tetrakis(methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate). diethylene bis{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 (e)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-triyl)tri-p-cresol, etc.

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}, etc. are preferred.

These hindered phenol-based heat stabilizers may be used alone or in combination of two or more.
The hindered phenol-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 even more preferably 0.01 to 0.3 part by weight, per 100 parts by weight of the resin composition.

Examples of sulfur-based heat stabilizers include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-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. Of 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 mixed in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight, and even more preferably 0.01 to 0.3 parts by weight per 100 parts by weight of the resin composition.

When using a combination of a phosphite-based heat stabilizer, a phenol-based heat stabilizer, and a sulfur-based heat stabilizer, the total amount of these is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.3 parts by weight, per 100 parts by weight of the resin composition.

(Release Agent)
The resin composition used in the present invention may contain a mold release agent in order to further improve releasability from a mold during melt molding, within the scope of the present invention.

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

As the higher fatty acid ester, partial or full esters of monohydric or polyhydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms are preferred. Examples of partial or full esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearate monosorbitate, stearyl stearate, behenic acid monoglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, etc.

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

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

These release agents may be used alone or in combination of two or more. The amount of such release agents 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 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, and cyanoacrylate-based ultraviolet absorbers, and among these, benzotriazole-based ultraviolet absorbers are preferred.

Benzotriazole-based ultraviolet absorbers include, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 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 Benzotriazole-based ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers are typified by 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], and methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate-polyethylene glycol condensate.

The proportion of such ultraviolet absorbers 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, per 100 parts by weight of the resin composition.

(Light stabilizer)
The resin composition used in the present invention may contain a light stabilizer. The inclusion of a light stabilizer has the advantages of being excellent in terms of weather resistance and making the molded product less susceptible to cracking.

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]butyl malonate, 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-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-4-piperidyl)phenylphosphat Examples of light stabilizers include hindered amines such as dimethylaminoethyl ester, nickel bis(octylphenyl sulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, and nickel complexes such as nickel dibutyldithiocarbamate. These light stabilizers may be used alone or in combination of two or more. The content of the light stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the resin composition.

(Epoxy stabilizer)
In order to improve hydrolysis resistance, the resin composition used in the present invention may contain an epoxy compound within the range not impairing the object 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'-methylcyclohexyl carboxylate, 2,3-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl carboxylate, 4-(3,4-epoxy-5-methylcyclohexyl)butyl-3',4'-epoxycyclohexyl carboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylcyclohexylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetrafluoroethylene glycol ... phenylethylene epoxide, octyl epoxythalate, 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-epoxycyclohexyl carboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexyl carboxylate, octadecyl-3,4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3',4'-epoxycyclohexyl carboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3',4'-epoxycyclohexyl carboxylate, 4,5-epoxy tetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxy tetrahydrophthalic anhydride, diethyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, etc. Bisphenol A diglycidyl ether is preferred in terms of compatibility, etc.

It is desirable to mix such epoxy stabilizers 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, per 100 parts by weight of the resin composition.

(Bluing agent)
The resin composition used in the present invention can be blended with a bluing agent to eliminate the yellow color of the lens due to the polymer or ultraviolet absorbing agent. As the bluing agent, any agent that is used for polycarbonate can be used without any problem. In general, anthraquinone dyes are easily available and are preferred.

Specific examples of bluing agents include Solvent Violet 13 (CA. No. (Color Index No.) 60725), Solvent Violet 31 (CA. No. 68210), Solvent Violet 33 (CA. No. 60725), Solvent Blue 94 (CA. No. 61500), Solvent Violet 36 (CA. No. 68210), Solvent Blue 97 (Bayer's "Macrolex Violet RR"), and Solvent Blue 45 (CA. No. 61110).

These bluing agents may be used alone or in combination of two or more. These bluing agents are preferably mixed 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 retardant)
The resin composition used in the present invention can also be blended with a flame retardant. Examples of the flame retardant include halogen-based flame retardants such as brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, and chlorinated polyethylene, phosphate-based flame retardants such as monophosphate compounds and phosphate oligomer compounds, organic phosphorus-based flame retardants other than phosphate-based flame retardants such as phosphinate compounds, phosphonate compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, organic metal salt-based flame retardants such as organic sulfonic acid alkali (earth) metal salts, boric acid metal salt-based flame retardants, and stannic acid metal salt-based flame retardants, as well as silicone-based flame retardants, ammonium polyphosphate-based flame retardants, and triazine-based flame retardants. In addition, flame retardant assistants (e.g., sodium antimonate, antimony trioxide, etc.) and drip prevention agents (polytetrafluoroethylene having fibril forming ability, etc.) may be blended and used in combination with the flame retardant.

Among the flame retardants mentioned above, compounds that do not contain chlorine or bromine atoms are more suitable as flame retardants for the molded article of the present invention, which is characterized by its reduced environmental impact, because they reduce factors that are considered undesirable when incinerating or thermally recycling the material.

When a flame retardant is added, the amount is preferably in the range of 0.05 to 50 parts by weight per 100 parts by weight of the resin composition. At 0.05 parts by weight or more, sufficient flame retardancy is likely to be achieved, and at 50 parts by weight or less, the strength and heat resistance of the molded product will be excellent.

(Molded products)
The resin composition of the present invention can be molded and processed into a molded product (including a sheet or a film) by any method such as injection molding, compression molding, injection compression molding, melt film forming, or casting, and can be used as a molded product such as an optical lens, an optical disk, an optical film, a plastic substrate, an optical card, a liquid crystal panel, a headlamp lens, a light guide plate, a diffusion plate, a protective film, an OPC binder, a front plate, a housing, a tray, a water tank, a lighting cover, a signboard, a plastic window, etc. 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, or a plastic window.

(Transparency)
The haze of a 2 mm thick molded piece of the resin composition of the present invention is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less. If the haze is within the above range, the range of use as an optical member is not limited, which is preferable.

(Impact Strength)
The resin composition of the present invention preferably has a notched Charpy impact strength of 10 kJ/ ^m2 or more, more preferably 11 kJ/m2 or ^more , even more preferably 12 kJ/m2 ^{or more} , and particularly preferably 13 kJ/m2 or ^more , measured in accordance with ISO 179. Note that a notched Charpy impact strength of 100 kJ/m2 or ^less provides sufficient functionality.

(Pencil hardness)
The resin composition of the present invention preferably has a pencil hardness of B or more. From the viewpoint of being more excellent in scratch resistance, it is more preferable that the pencil hardness is HB or more. A pencil hardness of 4H or less has sufficient function. The pencil hardness can be increased by increasing the weight ratio of the acrylic resin. In the present invention, the pencil hardness refers to a hardness at which no scratch marks are left when the resin composition of the present invention is rubbed with a pencil having a specific pencil hardness, and is defined as a hardness that satisfies the JIS standard.
It is preferable to use as an index the pencil hardness used in the surface hardness test of a coating film, which can be measured according to K-5600. The pencil hardness becomes softer in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B.

(Antistatic properties)
The resin composition of the present invention preferably has a surface resistivity of 1 x 10 ¹⁵ Ω/□ or less, more preferably 1 x 10 14 Ω/□ or less, and even more preferably 1 x 10 ¹³ Ω/□ or less, as measured using a high resistance resistivity meter MCP- ^HT450 manufactured by Mitsubishi Chemical Analytical Corporation at a measurement voltage of 1000 V.

(Surface Treatment)
Molded articles formed from the resin composition of the present invention can be subjected to various surface treatments. The surface treatment referred to here is a method for forming a new layer on the surface of a resin molded article, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc., and any commonly used method can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water-repellent/oil-repellent coat, ultraviolet absorbing coat, infrared absorbing coat, and metallizing (vapor deposition, etc.). Hard coat is a particularly preferred and necessary surface treatment.

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight." The resins and evaluation methods used in the examples 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: Measured using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate resin 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, and t is the number of seconds that the sample solution falls]

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 Industries Co., Ltd.

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

5. Pencil Hardness Based on JIS K-5600, a line was drawn on the surface of a molded article in a thermostatic chamber at an atmospheric temperature of 23° C. with a pencil held at a 45° angle and a load of 750 g applied, and the surface condition was visually evaluated.

6. Antistatic performance A flat plate of 45 mm length x 50 mm width x 2 mm thickness obtained under the same conditions as the method described below was conditioned for one week in an environment of 23°C and 50% humidity. After that, the surface resistivity (Ω/□) of the molded product was measured using a resistivity meter (high resistance resistivity meter MCP-HT450 manufactured by Mitsubishi Chemical Analyc Corporation) at a measurement voltage of 1000 V. The smaller the value, the better the antistatic performance.

[Polycarbonate resin (A)]
PC-1 (Example):
Structural units derived from isosorbide (hereinafter referred to as ISS)/structural units derived from 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter referred to as SPG)/structural units derived from 1,9-nonanediol (hereinafter referred to as ND)=72/21/7 (mol %), specific viscosity 0.396
PC-2 (Example):
Structural units derived from ISS/structural units derived from SPG/structural units derived from ND=58/38/4 (mol %), specific viscosity 0.425
PC-3 (Comparative Example)
Structural units derived from ISS/structural units derived from ND=88/12 (mol %), specific viscosity 0.366
PC-4 (Comparative Example)
Structural units derived from ISS/structural units derived from 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM)=70/30 (mol %), specific viscosity 0.378
PC-5 (Comparative Example)
Aromatic polycarbonate resin having structural units derived from bisphenol A, L-1225WP manufactured by Teijin Limited

[Acrylic resin (B)]
B-1 (Example): Acrypet VH001 manufactured by Mitsubishi Chemical Corporation (acrylic resin copolymerized with 95 mol % of methyl methacrylate and 5 mol % of methyl acrylate)
[Impact modifier composite acrylic resin (B+C)]
B+C (Example): Acrypet VRL40 manufactured by Mitsubishi Chemical Corporation (refractive index of impact modifier: 1.492)

[Impact Modifier (C)]
C-1 (Example): Kane Ace M-230 (refractive index: 1.492) manufactured by Kaneka Corporation
C-2 (Example): Mitsubishi Chemical Corporation's Metablen W-377 (refractive index: 1.492)
C-3 (Comparative Example): Mitsubishi Chemical Corporation's Metablen W-450A (refractive index: 1.472)

[Antistatic Agent (D)]
D-1 (Example): Block polymer having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded. PELECTRON PVL (surface resistance: 3×10 ⁶ Ω) manufactured by Sanyo Chemical Industries, Ltd.
D-2 (Example): Block polymer having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded. Pelestat 230 (Sanyo Chemical Industries, Ltd.) (Surface resistance: 5×10 ⁷ Ω)
D-3 (Example): Block polymer having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded. Pelestat 300 (Sanyo Chemical Industries, Ltd.) (Surface resistance: 1×10 ⁸ Ω)
D-4 (Comparative Example): Block polymer having a structure in which a polyamide block and a polyether block are ester-bonded. Pelestat NC6321 (Surface resistance: 1×10 ⁹ Ω) manufactured by Sanyo Chemical Industries, Ltd.

[Example 1]
<Production of polycarbonate resin>
364 parts of isosorbide (hereinafter abbreviated as ISS), 221 parts of 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 0.6×10 ⁻⁴ parts of barium stearate as catalysts were heated to 200° C. under a nitrogen atmosphere and melted. Thereafter, the temperature was raised to 220° C. over 30 minutes and the degree of vacuum was adjusted to 20.0 kPa. Thereafter, the temperature was raised to 240° C. over another 30 minutes and the degree of vacuum was adjusted to 10 kPa. After maintaining the temperature for 10 minutes, the degree of vacuum was reduced to 133 Pa or less over 1 hour. After the reaction was completed, the reaction mixture was discharged from the bottom of the reaction tank under nitrogen pressure, and while being cooled in a water tank, it was cut with a pelletizer to obtain pellets (PC-1).

<Production of Resin Composition>
Polycarbonate resin PC-1, impact modifier composite acrylic resin B+C, and block polymer D-1 were mixed in a weight ratio of 63:27:10 and then fed to an extruder. Extrusion was performed using a vented twin-screw extruder with a diameter of 30 mm [Kobe Steel KTX-30] at a screw rotation speed of 150 rpm, a discharge rate of 20 kg/h, and a vent vacuum of 3 kPa to obtain pellets. The extrusion temperature was 250°C from the feed port to the die. A portion of the obtained pellets was dried in a hot air circulation dryer at 90°C for 6 hours or more, and then molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 60°C into evaluation test pieces (ISO bending test pieces (compliant with ISO178, ISO179, ISO75-1 and ISO75-2), three-stage plates (1 mmt, 2 mmt, 3 mmt)) and a flat plate with dimensions of 45 mm length x 50 mm width x 2 mmt thickness. The evaluation results are shown in Table 1.

[Example 2]
<Production of Resin Composition>
Except for the fact that the blend weight ratio was PC-1:B+C:D-1=68:29:3, the same procedures and evaluations were carried out as in Example 1. The results are shown in Table 1.

[Example 3]
<Production of Resin Composition>
Except for the fact that the blend weight ratio was PC-1:B+C:D-1=60:25:15, the same procedures and evaluations were carried out as in Example 1. The results are shown in Table 1.

[Example 4]
<Production of Resin Composition>
Except for changing the type of block polymer D and extruding at PC-1:B+C:D-2=63:27:10, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 1.

[Example 5]
<Production of Resin Composition>
Except for changing the type of block polymer D and extruding at a ratio of PC-1:B+C:D-3=63:27:10, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 1.

[Example 6]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the types of acrylic resin B and impact modifier C were changed and the blend weight ratio was PC-1:B-1:C-1:D-1=63:13.5:13.5:10. The results are shown in Table 1.

[Example 7]
<Production of Resin Composition>
The types of acrylic resin B and impact modifier C were changed, and the blend weight ratio was PC-1:
Except for the fact that the extrusion ratio was B-1:C-2:D-1=63:13.5:13.5:10, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 1.

[Example 8]
<Production of polycarbonate resin>
Using 294 parts of ISS, 400 parts of SPG, 22 parts of ND and 750 parts of DPC as raw materials, the same procedure as in Example 1 was carried out to obtain pellets (PC-2).

<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the types of polycarbonate, acrylic resin B, and impact modifier C were changed and the blend weight ratio was PC-2:B-1:C-1:D-1=63:9:18:10. The results are shown in Table 1.

[Example 9]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the types of acrylic resin B and impact modifier C were changed and the blend weight ratio was PC-1:B-1:C-1:D-1=36:27:27:10. The results are shown in Table 1.

[Example 10]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the types of acrylic resin B and impact modifier C were changed and the blend weight ratio was PC-1:B-1:C-1:D-1=72:9:9:10. The results are shown in Table 1.

[Comparative Example 1]
<Production of Resin Composition>
Except for changing the type of block polymer D and setting the blend weight ratio PC-1:B+C:D-4=63:27:10, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 2.

[Comparative Example 2]
<Production of polycarbonate resin>
450 parts of isosorbide (hereinafter abbreviated as ISS), 67 parts of 1,9-nonanediol (hereinafter abbreviated as ND), 750 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 0.0033 parts of barium stearate as a catalyst were heated to 150°C under a nitrogen atmosphere and melted. Thereafter, the mixture was sent to a reaction vessel, and the heat transfer medium temperature of the condenser was adjusted to 40°C, the internal resin temperature was adjusted to 170°C, and the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the degree of vacuum was adjusted to 3.4 kPa over 20 minutes, and the temperature was maintained for 10 minutes. The degree of vacuum was further reduced to 0.9 kPa over 30 minutes, the internal temperature of the resin was adjusted to 220°C, and the temperature was maintained for 10 minutes. After that, the degree of vacuum was reduced to 0.2 kPa, and the resin temperature was increased from 220°C to 240°C over 30 minutes. After the resin reached a specified viscosity, the resin was discharged from the bottom of the reaction tank under nitrogen pressure, and while cooling in a water tank, the resin was cut with a pelletizer to obtain pellets (PC-3).

<Production of Resin Composition>
Except for changing the type of polycarbonate and setting the blend weight ratio PC-3:B+C:D-1=63:27:10, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 2.

[Comparative Example 3]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the types of polycarbonate, acrylic resin B, and impact modifier C were changed and the blend weight ratio was PC-3:B-1:C-1:D-1=63:13.5:13.5:10. The results are shown in Table 2.

[Comparative Example 4]
<Production of polycarbonate resin>
Pellets (PC-4) were obtained in the same manner as in Example 1, except that 354 parts of ISS, 150 parts of CHDM, and 750 parts of DPC were used as raw materials.

<Production of Resin Composition>
Except for changing the type of polycarbonate and setting the blend weight ratio PC-4:B+C:D-1=63:27:10, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 2.

[Comparative Example 5]
<Production of Resin Composition>
Except for changing the type of acrylic resin B, not using impact modifier C, and extruding at a blend weight ratio of PC-1:B-1:D-1=63:27:10, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 2.

[Comparative Example 6]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the types of acrylic resin B and impact modifier C were changed and the blend weight ratio was PC-1:B-1:C-3:D-1=63:13.5:13.5:10. The results are shown in Table 2.

[Comparative Example 7]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the type of polycarbonate was changed, the acrylic resin B and the impact modifier C were not used, and the blend weight ratio was PC-3:D-1 = 90:10. The results are shown in Table 2.

[Comparative Example 8]
<Production of Resin Composition>
Except for not using the acrylic resin B and the impact modifier C and extruding the blend weight ratio PC-1:D-1=90:10, the same operations as in Example 1 were carried out and the same evaluations were carried out. The results are shown in Table 2.

[Comparative Example 9]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the type of polycarbonate was changed, the acrylic resin B and the impact modifier C were not used, and the blend weight ratio was PC-4:D-1 = 90:10. The results are shown in Table 2.

[Comparative Example 10]
<Production of Resin Composition>
Polycarbonate resin PC-5 and block polymer D-1 were mixed at a weight ratio of 90:10 and then fed to an extruder. Extrusion was performed using a vented twin-screw extruder with a diameter of 30 mmφ [Kobe Steel Works, Ltd. KTX-30], with a screw rotation speed of 150 rpm, a discharge rate of 20 kg/h, and a vent vacuum of 3 kPa to obtain pellets by melt kneading. The extrusion temperature was 280°C from the feed port to the die. A part of the obtained pellets was dried in a hot air circulation dryer at 120°C for 6 hours or more, and then molded into evaluation test pieces (ISO bending test pieces (compliant with ISO178, ISO179, ISO75-1 and ISO75-2), three-stage plates (1 mmt, 2 mmt, 3 mmt)) and flat plates with a length of 45 mm, width of 50 mm, and thickness of 2 mmt using an injection molding machine at a cylinder temperature of 280°C and a mold temperature of 80°C. The evaluation results are shown in Table 2.

[Comparative Example 11]
<Production of Resin Composition>
Except for not using block polymer D and setting the blend weight ratio PC-1:B+C=70:30, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 2.

[Comparative Example 12]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the acrylic resin B was not used, the type of impact modifier C was changed, and the blend weight ratio was PC-1:C-1:D-1 = 63:27:10. The results are shown in Table 2.

[Comparative Example 13]
<Production of Resin Composition>
The same operations and evaluations were carried out as in Example 1, except that the types of acrylic resin B and impact modifier C were changed and the blend weight ratio was set to PC-1:B-1:C-1:D-1=45:9:36:10 and extruded. The results are shown in Table 2.

[Comparative Example 14]
<Production of Resin Composition>
Except for the fact that the blend weight ratio was PC-1:B+C:D-1=56:24:20, the same operations and evaluations were carried out as in Example 1. The results are shown in Table 2.

The resin composition of the present invention is useful as a material for optical lenses, optical disks, optical films, plastic cell substrates, optical cards, liquid crystal panels, headlamp lenses, light guide plates, diffusion plates, protective films, OPC binders, front panels, housings, trays, aquariums, lighting covers, signs, plastic windows, and the like.

Claims (10)

A polycarbonate resin comprising repeating units comprising a carbonate unit (a) represented by the following formula (1) and another carbonate unit (b), the carbonate unit (b) being 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 polycarbonate resin containing 5 to 85 mol % of the carbonate structural unit (a) represented by the following formula (1) and 15 to 95 mol % of the carbonate unit (b) in 100 mol % of all carbonate structural units: The resin composition contains 5 to 60 parts by weight of an impact modifier (C) having a refractive index of 1.485 or more and 1.495 or less, and 1 to 20 parts by weight of a block polymer (D) having a structure in which polyolefin blocks and polyether blocks are repeatedly and alternately bonded, relative to a total of 100 parts by weight of (A) and an acrylic resin (B) containing 40 to 100 mol % of repeating units derived from methyl methacrylate, and the weight ratio of the polycarbonate resin (A) to the acrylic resin (B) is 30:70 to 99:1 .
(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, R represents a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and m represents an integer of 0 to 10.) The polycarbonate resin (A) contains 10 to 80 mol% of the carbonate structural unit (a) represented by the formula (1) and 20 to 90 mol% of the carbonate unit (b) in 100 mol% of all carbonate structural units . The resin composition according to claim 1. 3. The resin composition according to claim 1, wherein the weight ratio of the polycarbonate resin (A) to the acrylic resin (B) is from 35:65 to 95:5 . 4. The resin composition according to claim 1, wherein the acrylic resin (B) contains 50 to 100 mol % of a structural unit derived from methyl methacrylate. The resin composition according to any one of claims 1 to 4, in which the haze of a 2 mm thick test piece is 20 or less. The resin composition according to any one of claims 1 to 5, having a notched Charpy impact strength measured in accordance with ISO 179 of 10 kJ / m2 or ^more . The resin composition according to any one of claims 1 to 6, which has a pencil hardness of B or more as measured according to JIS K-5600. The resin composition according to any one of claims 1 to 7, wherein the surface resistivity of the molded product is 1 x 10 ¹⁵ (Ω/□) or less. A molded article obtained by molding a resin composition according to any one of claims 1 to 8. A film or sheet formed from the resin composition according to any one of claims 1 to 8.