Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/041—Carbon nanotubes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/04—Thermoplastic elastomer

Definitions

• the present invention relates to resin compositions, pellets, and molded products.
• Polycarbonate resin has excellent mechanical strength, electrical properties, transparency, etc., and is widely used as an engineering plastic in various fields such as electrical and electronic equipment fields and automobile fields.
• ABS resin Polymer alloy with acrylonitrile-butadiene-styrene resin (hereinafter also referred to as ABS resin) Because it has improved moldability compared to ABS resin, and has improved impact resistance and heat resistance compared to ABS resin alone, it is used as a material that has both strength, heat resistance, and moldability, including the automobile field, electrical and electronic equipment field, etc. Widely used in various fields.
• a molded article having excellent impact resistance and hardness can be obtained from the resin composition described in Patent Document 1.
• transparency may be required.
• the present invention aims to solve these problems, and is capable of providing a molded product that has excellent impact resistance and hardness, and also has excellent transparency.
• the purpose is to provide resin compositions, pellets, and molded products.
• the above-mentioned problems were solved by blending a predetermined elastomer into a polycarbonate resin such as bisphenol C-type polycarbonate resin. Specifically, the above problem was solved by the following means. ⁇ 1> In 100% by mass of the resin composition, (A) 80 to 99% by mass of polycarbonate resin; (B) 1 to 20% by mass of an elastomer containing styrene units in a proportion of 50% by mass or more of all structural units; A resin composition in which the polycarbonate resin (A) contains a structural unit represented by formula (1) in a proportion of 8 mol% or more of all structural units.
• R 1 represents a methyl group
• R 2 represents a hydrogen atom or a methyl group
• X 1 represents any of the following formulas
• R 3 and R 4 each independently represent a hydrogen atom or a methyl group
• Z combines with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent. represents a group.
• R 2 in the structural unit represented by formula (1) is a hydrogen atom
• X 1 is represented by -C(R 3 )(R 4 )- in ⁇ 1> or ⁇ 2>
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, further comprising a colorant.
• ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the colorant is 0.001 to 5 parts by mass based on 100 parts by mass of the polycarbonate resin (A). .
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the elastomer (B) contains high impact polystyrene.
• ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the elastomer (B) contains high impact polystyrene containing styrene units in a proportion of 85% by mass or more of all structural units.
• the polycarbonate resin (A) contains units represented by formula (1) in a proportion of less than 50 mol% of the total structural units, R 2 in the structural unit represented by formula (1) is a hydrogen atom, X 1 is represented by -C(R 3 R 4 )-, Furthermore, it contains a coloring agent, The content of the colorant is 0.001 to 5 parts by mass based on 100 parts by mass of the polycarbonate resin (A), The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the elastomer (B) contains high impact polystyrene.
• the polycarbonate resin (A) contains units represented by formula (1) in a proportion of less than 50 mol% of the total structural units, R 2 in the structural unit represented by formula (1) is a hydrogen atom, X 1 is represented by -C(R 3 R 4 )-, Furthermore, it contains a coloring agent, The content of the colorant is 0.001 to 5 parts by mass based on 100 parts by mass of the polycarbonate resin (A),
• ⁇ 10> A pellet of the resin composition according to any one of ⁇ 1> to ⁇ 9>.
• ⁇ 11> A molded article molded from the resin composition according to any one of ⁇ 1> to ⁇ 9>.
• ⁇ 12> A molded article molded from the pellet described in ⁇ 10>.
• ADVANTAGE OF THE INVENTION it is possible to provide a resin composition, pellets, and a molded product that can provide a molded product with excellent impact resistance and hardness, and also excellent transparency. Became.
• this embodiment a mode for carrying out the present invention (hereinafter simply referred to as “this embodiment”) will be described in detail.
• the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.
• " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
• various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated.
• the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography) unless otherwise specified. If the measurement methods, etc. explained in the standards shown in this specification differ from year to year, unless otherwise stated, they shall be based on the standards as of January 1, 2022.
• the resin composition of the present embodiment includes (A) 80 to 99 mass % of a polycarbonate resin and (B) an elastomer 1 to 1 containing styrene units in a proportion of 50 mass % or more of the total constituent units in 100 mass % of the resin composition. 20% by mass, and the polycarbonate resin (A) is characterized in that it contains the structural unit represented by formula (1) in a proportion of 8 mol% or more of the total structural units.
• R 1 represents a methyl group
• R 2 represents a hydrogen atom or a methyl group
• X 1 represents any of the following formulas
• R 3 and R 4 each independently represent a hydrogen atom or a methyl group
• Z combines with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and which may have a substituent. represents a group.
• a resin composition can be obtained which can provide a molded article having excellent impact resistance and hardness, and also excellent transparency. That is, polycarbonate resins containing the structural unit represented by formula (1) such as bisphenol C type polycarbonate resin in a proportion of 8 mol% or more of the total structural units (hereinafter simply referred to as "the structural unit represented by formula (1)")
• the structural unit represented by formula (1) A molded article with excellent hardness can be obtained by using a polycarbonate resin containing Furthermore, when an elastomer is blended with a polycarbonate resin containing the structural unit represented by formula (1), the impact resistance of the resulting molded product is improved.
• the resin composition of this embodiment includes (A) a polycarbonate resin.
• the polycarbonate resin (A) contains the structural unit represented by formula (1) in a proportion of 8 mol% or more of the total structural units.
• a molded article with excellent transparency and hardness can be obtained.
• Formula (1) (In formula (1), R 1 represents a methyl group, R 2 represents a hydrogen atom or a methyl group, X 1 represents any of the following formulas, R 3 and R 4 each independently represent a hydrogen atom or a methyl group, and Z combines with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent. represents a group. )
• R 2 is preferably a hydrogen atom.
• X 1 is In this case, at least one of R 3 and R 4 is preferably a methyl group, and more preferably both are methyl groups. Also, X 1 is In the case of , Z is bonded to carbon C bonded to two phenyl groups in the above formula (1) to form a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms; Examples of the alicyclic hydrocarbon group include cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group.
• Examples of the alicyclic hydrocarbon having a substituent formed by bonding Z to C include methyl substituted products, ethyl substituted products, and the like of the above-mentioned alicyclic hydrocarbon group.
• Examples of substituted compounds include those having a methyl substituent or an ethyl substituent.
• a cyclohexylidene group, a methyl substituted product of a cyclohexylidene group (preferably a 3,3,5-trimethyl substituted product), and a cyclododecylidene group are preferred.
• X 1 preferably has the following structure.
• a preferred specific example of the structural unit represented by the above formula (1) is 2,2-bis(3-methyl-4-hydroxyphenyl)propane, that is, a structural unit composed of bisphenol C (carbonate structural unit). It is.
• the polycarbonate resin may contain only one type of structural unit represented by formula (1), or may contain two or more types of structural units.
• the polycarbonate resin containing the structural unit represented by formula (1) may further contain the structural unit represented by formula (2).
• "containing the structural unit represented by formula (2)” means that the polycarbonate resin contained in the resin composition of this embodiment contains the structural unit represented by formula (1) and formula (2).
• it may also be a blend of a polycarbonate resin containing a structural unit represented by formula (1) and a polycarbonate resin containing a structural unit represented by formula (2). It's a good idea. By including the structural unit represented by formula (2), the heat resistance of the obtained molded product tends to be further improved.
• X 2 represents one of the following formulas
• R 3 and R 4 each independently represent a hydrogen atom or a methyl group
• Z combines with C to form an alicyclic hydrocarbon having 6 to 12 carbon atoms and optionally having a substituent. represents a group.
• X 2 is In this case, at least one of R 3 and R 4 is preferably a methyl group, and more preferably both are methyl groups. Also, X 2 is In the case of , Z bonds with carbon C bonded to two phenyl groups in the above formula (2) to form a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms, but Examples of the alicyclic hydrocarbon group include cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclododecylidene group.
• cycloalkylidene groups such as a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, and a cyclodode
• substituted compounds include those having a methyl substituent or an ethyl substituent.
• a cyclohexylidene group, a methyl substituted product of a cyclohexylidene group (preferably a 3,3,5-trimethyl substituted product), and a cyclododecylidene group are preferred.
• X 2 preferably has the following structure.
• the polycarbonate resin may contain only one type of structural unit represented by formula (2), or may contain two or more types.
• the polycarbonate resin may contain other structural units other than the structural unit represented by formula (1) and the structural unit represented by formula (2).
• other structural units include the following structural units derived from dihydroxy compounds.
• the proportion of the structural unit represented by formula (1) is 8 mol% or more, preferably 10 mol% or more, among all the structural units, It is more preferably 12 mol% or more, even more preferably 14 mol% or more, and depending on the use etc., 35 mol% or more, 40 mol% or more, 50 mol% or more, 70 mol% or more, 75 mol%. % or more.
• the amount By setting the amount to be equal to or more than the lower limit, the transparency of the obtained molded product tends to be further improved, and the surface hardness of the molded product tends to be increased.
• the proportion of the structural unit represented by the formula (1) may be 100 mol%, preferably 95 mol% or less, and 80 mol% depending on the purpose etc. Below, it may be 70 mol% or less, 50 mol% or less, less than 50 mol%, 40 mol% or less, 30 mol% or less, 26 mol% or less, or 20 mol% or less.
• the content is less than or equal to the upper limit, the impact resistance of the molded product obtained tends to be further improved, and the heat resistance of the molded product also tends to be improved. Furthermore, weather resistance tends to be improved by keeping it below the above-mentioned upper limit.
• the total of the structural units represented by the above formula (1) and the structural units represented by the formula (2) should account for 90% by mass or more of all the structural units excluding the terminal groups. is preferred, more preferably 95% by mass or more, and still more preferably 99% by mass or more.
• the upper limit of the total amount is 100% by mass or less.
• the polycarbonate resin used in this embodiment preferably has the following form.
• (A1) Polycarbonate resin containing the structural unit represented by formula (1) (A2) Polycarbonate resin containing the structural unit represented by formula (1) and polycarbonate resin containing the structural unit represented by formula (2) A blend of (A3) a polycarbonate resin containing the structural unit represented by formula (1) and a structural unit represented by formula (2); (A4) a polycarbonate resin containing the structural unit represented by formula (1); Blend product (A5) of polycarbonate resin containing the structural unit represented by formula (1) and the structural unit represented by formula (2) A polycarbonate resin containing the structural unit represented by formula (2) and the formula (1) ) A blend of a polycarbonate resin containing a structural unit represented by formula (2) and a polycarbonate resin containing a structural unit represented by formula (1) A blend of a polycarbonate resin containing a structural unit represented by formula (1) and a polycarbonate resin containing a structural unit represented by formula (2) (A7) In the above (A1) to (A6) , polycarbonate resin (A
• the lower limit of the viscosity average molecular weight (Mv) of the polycarbonate resin (A) used in this embodiment is preferably 5,000 or more, more preferably 8,000 or more, and 10,000 or more. is more preferable, and even more preferably 12,000 or more.
• the upper limit value of Mv is preferably 32,000 or less, more preferably 30,000 or less, even more preferably 29,000 or less, and even more preferably 27,000 or less. .
• the resin composition contains two or more types of (A) polycarbonate resins, it is the sum of the values obtained by multiplying the viscosity average molecular weight of each polycarbonate resin by the mass fraction.
• the viscosity average molecular weight of the polycarbonate resin containing the structural unit represented by formula (1) is preferably 20,000 to 30,000, more preferably 20,000 to 28,000.
• the viscosity average molecular weight of the polycarbonate resin containing the structural unit represented by formula (2) is preferably 12,000 to 28,000, more preferably 18,000 to 27,000.
• the polycarbonate resin (A) used in this embodiment has a pencil hardness of 3B to 3B as measured according to ISO 15184.
• An example is 2H, and 2B to 2H are preferred.
• Pencil hardness is measured according to the method described in Examples below.
• the pencil hardness of the polycarbonate resin containing the structural unit represented by formula (1) is preferably H to 2H
• the pencil hardness of the polycarbonate resin containing the structural unit represented by formula (2) is preferably , 2B to HB. Pencil hardness is measured according to the description in Examples below.
• the method for producing the polycarbonate resin used in this embodiment is not particularly limited, but for example, paragraphs 0027 to 0043 of JP 2014-065901 and the description of Examples can be referred to, and the contents thereof are incorporated herein. .
• the content of the polycarbonate resin (A) in the resin composition of the present embodiment is 80% by mass or more, preferably 82% by mass or more, and 84% by mass or more based on 100% by mass of the resin composition. is more preferable, more preferably 86% by mass or more, even more preferably 88% by mass or more. By setting it to the above lower limit or more, the heat resistance of the obtained molded product tends to be better. Further, the content of the polycarbonate resin (A) in the resin composition of the present embodiment is 99% by mass or less, preferably 98% by mass or less, and 97% by mass or less based on 100% by mass of the resin composition. There may be.
• the resin composition of the present embodiment includes (B) an elastomer containing styrene units in a proportion of 50% by mass or more of all structural units (hereinafter sometimes simply referred to as "(B) elastomer").
• (B) elastomer By using an elastomer with a high proportion of styrene units, it is possible to maintain the impact resistance of the resulting molded product as well as the high transparency inherent to the polycarbonate resin containing the structural unit represented by formula (1). .
• the proportion of styrene units in the elastomer (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more of the total structural units. It is more preferably at least 80% by mass, even more preferably at least 85% by mass, and it is preferably at most 99% by mass, and at most 98% by mass. It is more preferably at most 96% by mass, even more preferably at most 94% by mass, even more preferably at most 92% by mass.
• the impact resistance of the obtained molded product tends to be further improved.
• the amount to be equal to or more than the lower limit the transparency of the obtained molded product tends to be further improved.
• the elastomer (B) in this embodiment preferably includes high impact polystyrene (HIPS, high impact polystyrene).
• HIPS is a polymer in which a rubber-like polymer made of butadiene rubber or the like is dispersed in particles in a matrix made of an aromatic vinyl polymer such as polystyrene.
• HIPS can be obtained, for example, by dissolving a rubbery polymer in a mixed solution of an aromatic vinyl monomer and an inert solvent and stirring the mixture to perform bulk polymerization, suspension polymerization, solution polymerization, or the like.
• HIPS is, for example, a mixture in which a separately obtained aromatic vinyl polymer is mixed with a polymer obtained by dissolving a rubbery polymer in a mixed solution of an aromatic vinyl monomer and an inert solvent.
• the high-impact polystyrene preferably contains styrene units in a proportion of 85% by mass or more of all structural units.
• the transparency of the resulting resin composition can be further improved.
• a coloring agent into such a highly transparent resin composition, the color tone of the coloring agent can be appropriately expressed.
• jet blackness can be further improved by incorporating a black colorant.
• high-impact polystyrene which has a high proportion of styrene, has good impact resistance even though it is an elastomer with a small rubber component due to its good compatibility with polycarbonate resin containing the structural unit represented by formula (1). sex can be achieved.
• the mass average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) at 135°C using trichlorobenzene as a solvent is not particularly limited. Preferably it is 100,000 or more, more preferably 150,000 or more. Further, the average particle diameter of the rubbery polymer is not particularly limited, but generally 0.4 to 6.0 ⁇ m is suitable.
• the content of the elastomer (B) in the resin composition of the present embodiment is 1% by mass or more, preferably 2% by mass or more, and preferably 3% by mass or more based on 100% by mass of the resin composition. More preferred. When the content is equal to or more than the lower limit, the impact resistance of the obtained molded product tends to be further improved. Further, the content of the elastomer (B) in the resin composition of the present embodiment is 20% by mass or less, preferably 18% by mass or less, and 16% by mass or less based on 100% by mass of the resin composition. It is more preferably 14% by mass or less, even more preferably 12% by mass or less. When the content is below the upper limit, the appearance defects of the obtained molded product tend to be further improved.
• the resin composition of this embodiment may contain only one type of elastomer (B), or may contain two or more types of elastomer. When two or more types are included, it is preferable that the total amount falls within the above range.
• One form of the resin composition of the present embodiment can be configured to substantially not contain any elastomer other than HIPS. "Substantially free” means that the content of elastomers other than HIPS among the elastomers (B) contained in the resin composition is less than 10% by mass, and less than 5% by mass of the content of the elastomers (B). It is preferably present, more preferably less than 3% by mass, even more preferably less than 1% by mass.
• the resin composition of this embodiment may contain an ultraviolet absorber.
• Preferred examples of the UV absorber include benzotriazole UV absorbers, benzoxazine UV absorbers, triazine UV absorbers, and malonic acid ester UV absorbers, with benzotriazole UV absorbers being preferred.
• benzotriazole ultraviolet absorbers examples include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H- Benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-( 3,5-di-tert-octyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3- lauryl-5-methyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3- tert-butyl-5-methyl-2-
• the content of the ultraviolet absorber when the ultraviolet absorber is included, is preferably 0.01 to 1 part by weight based on 100 parts by weight of the polycarbonate resin (A).
• the content of the ultraviolet absorber is more preferably 0.03 to 0.7 parts by mass, and even more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the polycarbonate resin (A).
• the resin composition of this embodiment may contain only one type of ultraviolet absorber, or may contain two or more types of ultraviolet absorbers. When two or more types are included, it is preferable that the total amount falls within the above range.
• the resin composition of this embodiment may contain a stabilizer.
• stabilizers include heat stabilizers and antioxidants.
• a phosphorus stabilizer is preferably used. Any known phosphorus stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; Phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; examples include organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds; is particularly preferred.
• a hindered phenol stabilizer is preferably used as the antioxidant.
• Specific examples of hindered phenol stabilizers include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl) )-4-hydroxyphenyl]methyl]phosphate, 3,3',3',5,5'
• hindered phenol stabilizers examples include, for example, “Irganox (registered trademark) 1010” and “Irganox 1076” manufactured by BASF, "ADEK STAB AO-50” and “ADEK STAB AO-50” manufactured by ADEKA. AO-60'', etc.
• the content of the stabilizer in the resin composition of the present embodiment is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass, based on 100 parts by mass of the polycarbonate resin (A).
• the amount is usually 1 part by weight or less, preferably 0.5 part by weight or less, more preferably 0.3 part by weight or less.
• the resin composition of this embodiment may contain a colorant.
• the coloring agent may be a pigment or a dye, with dyes being preferred.
• the coloring agent may be a chromatic coloring agent or an achromatic coloring agent.
• inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, Bengara, chromium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chromic acid pigments such as yellow lead and molybdate orange; Examples include Russian pigments.
• organic pigments and/or organic dyes include phthalocyanine dyes and pigments such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes and pigments such as nickel azo yellow; methine dyes and pigments, pyrazolone dyes and pigments, thioindigo dyes and perinone.
• examples include condensed polycyclic dyes and pigments such as perylene-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, and quinophthalone-based dyes and pigments; anthraquinone-based, heterocyclic-based, and methyl-based dyes and pigments.
• the colorant contains a black dye.
• the content of the colorant in the resin composition of the present embodiment is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and more preferably 0.005 parts by mass or more, based on 100 parts by mass of the polycarbonate resin (A).
• the amount is usually 5 parts by weight or less, preferably 3 parts by weight or less, and more preferably 1 part by weight or less.
• the resin composition of this embodiment may contain a mold release agent.
• mold release agents include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. , ketone wax, light amide, etc., and aliphatic carboxylic acids, salts of aliphatic carboxylic acids, and esters of aliphatic carboxylic acids and alcohols are preferred.
• the descriptions in paragraphs 0055 to 0061 of JP 2018-095706A can be referred to, and the contents thereof are incorporated herein.
• the content thereof is preferably 0.05 to 3% by mass, and preferably 0.1 to 0.8% by mass in the resin composition. is more preferable, and even more preferably 0.1 to 0.6% by mass.
• the resin composition of this embodiment may contain only one type of mold release agent, or may contain two or more types of mold release agents. When two or more types are included, it is preferable that the total amount falls within the above range.
• the resin composition of the present embodiment contains other components other than the above, as necessary, as long as desired physical properties are not significantly impaired. You may do so.
• other components include other thermoplastic resins and various resin additives.
• resin additives include antistatic agents, flame retardants, flame retardant aids, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like.
• one type of resin additive may be contained, or two or more types may be contained in any combination and ratio.
• the resin composition of this embodiment has a small haze.
• the resin composition of this embodiment preferably has a haze of 70% or less, more preferably 50% or less, when molded into a flat test piece with a thickness of 48%. % or less, even more preferably 35% or less, even more preferably 30% or less, and even more preferably 20% or less. It is practical for the lower limit of the haze to exceed 0%, and even if it is 1% or more, the required performance is sufficiently satisfied.
• the haze described above is measured according to the description in the examples below.
• the resin composition of this embodiment also preferably has high hardness.
• the resin composition of this embodiment preferably has a pencil hardness of HB or higher when molded into a flat test piece with a thickness of 2 mm.
• the upper limit is not particularly determined, even if it is 4H or less, the required performance is sufficiently satisfied.
• the above-mentioned pencil hardness is measured according to the description in the examples below.
• the resin composition of this embodiment also preferably has excellent impact resistance.
• the notched Charpy impact strength is preferably 4 kJ/m 2 or more, and 5 kJ/m 2 It is more preferably at least 9 kJ/m 2 , even more preferably at least 10 kJ/m 2 .
• the practical upper limit of the Charpy impact strength is, for example, 50 kJ/m 2 or less.
• ⁇ Method for manufacturing resin composition> There are no restrictions on the method for manufacturing the resin composition of this embodiment, and any known method for manufacturing a polycarbonate resin composition can be widely adopted, and (A) a polycarbonate resin, (B) an elastomer, and others blended as necessary.
• the ingredients are mixed in advance using various mixers such as a tumbler or Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader.
• a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader.
• the melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.
• the resin composition of this embodiment is pellets. Further, the above-mentioned resin composition (for example, pellets) is molded into a molded article by various molding methods. That is, the molded article of this embodiment is molded from the resin composition or pellets of this embodiment.
• the shape of the molded product is not particularly limited and can be selected as appropriate depending on the use and purpose of the molded product, such as film, rod, cylindrical, annular, circular, elliptical, and polygonal shapes. , irregularly shaped products, hollow products, frame-shaped, box-shaped, panel-shaped products, etc. Among these, panel-shaped ones are preferred, and the thickness is, for example, about 1 mm to 5 mm.
• the method for molding the molded product is not particularly limited, and conventionally known molding methods can be employed, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, Gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding , pressure molding method, etc.
• the resin composition of this embodiment is suitable for molded articles obtained by injection molding, injection compression molding, and extrusion molding.
• the resin composition of this embodiment is not limited to molded articles obtained using these.
• the molded product of this embodiment is suitably used for parts such as electrical and electronic equipment, OA equipment, personal digital assistants, mechanical parts, home appliances, vehicle parts, various containers, and lighting equipment. Among these, it is particularly suitable for display parts, mobile information terminal parts, household electrical appliances, or indoor furniture.
• reaction solution was stirred and incubated at 220° C. for 30 minutes under a nitrogen gas atmosphere.
• pressure inside the reactor was reduced to 100 Torr over 40 minutes at the same temperature, and the reaction was further carried out for 100 minutes to distill out phenol.
• the temperature inside the reactor was raised to 284° C. over 60 minutes, and the pressure was reduced to 3 Torr, to distill out phenol corresponding to almost the entire theoretical amount of distillation.
• the pressure inside the reactor was maintained at less than 1 Torr at the same temperature, and the reaction was continued for an additional 60 minutes to complete the polycondensation reaction.
• the stirring rotational speed of the stirrer was 38 rotations/min
• the temperature of the reaction liquid immediately before the end of the reaction was 289° C.
• the stirring power was 1.00 kW.
• the reaction liquid in a molten state is sent to a twin-screw extruder, and butyl p-toluenesulfonate in a molar amount four times that of cesium carbonate is supplied from the first supply port of the twin-screw extruder.
• the reaction solution was extruded into a strand through a die of a twin-screw extruder and cut with a cutter to obtain pellets of polycarbonate resin A1.
• reaction solution was stirred and incubated at 220° C. for 30 minutes under a nitrogen gas atmosphere.
• pressure inside the reactor was reduced to 100 Torr over 40 minutes at the same temperature, and the reaction was further carried out for 100 minutes to distill out phenol.
• the temperature inside the reactor was raised to 284° C. over 60 minutes, and the pressure was reduced to 3 Torr, to distill out phenol corresponding to almost the entire theoretical amount of distillation.
• the pressure inside the reactor was maintained at less than 1 Torr at the same temperature, and the reaction was continued for an additional 60 minutes to complete the polycondensation reaction.
• the stirring rotational speed of the stirrer was 38 rotations/min
• the temperature of the reaction liquid immediately before the end of the reaction was 289° C.
• the stirring power was 0.60 kW.
• the reaction liquid in a molten state is sent to a twin-screw extruder, and butyl p-toluenesulfonate in a molar amount four times that of cesium carbonate is supplied from the first supply port of the twin-screw extruder.
• the reaction solution was extruded into a strand through a die of a twin-screw extruder and cut with a cutter to obtain pellets of polycarbonate resin A2.
• the pencil hardness of the polycarbonate resin and resin composition was determined by molding the polycarbonate resin into a 2 mm thick flat test piece, and measuring the pencil hardness using a pencil hardness tester at a load of 750 g in accordance with ISO 15184. Specifically, after drying polycarbonate resin pellets at 100°C for 5 hours, they were molded using an injection molding machine (“ ⁇ -2000i-150B” manufactured by Fanuc Corporation) at a cylinder temperature of 260°C and a mold temperature of 70°C.
• a flat test piece (150 mm x 100 mm x 2 mm thick) was prepared under conditions of a screw rotation speed of 100 rpm and an injection speed of 30 mm/sec.
• the pencil hardness of this flat test piece was measured using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) under a load of 750 g in accordance with ISO 15184.
• the mixture was fed into the extruder from the barrel upstream of the extruder at a set cylinder temperature of 260° C., a screw rotation speed of 180 rpm, and a discharge rate of 25 kg/hr, and was melt-kneaded to obtain resin composition pellets.
• ⁇ Haze> The haze was measured at 23° C. using a flat test piece molded to a thickness of 2 mm according to JIS K-7105. Specifically, after drying the resin composition pellets obtained above at 100° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.), the cylinder temperature was set at 280° C. A flat test piece (90 mm x 50 mm x 2 mm thick) was injection molded at a mold temperature of 80° C., a screw rotation speed of 100 rpm, and an injection speed of 100 mm/s. Regarding the flat test piece obtained above, the HAZE at 23° C. was measured using a haze meter according to JIS K-7105. As the haze meter, an NDH-2000 type haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd. was used. The unit of haze is expressed in %.
• the Charpy impact strength was measured in accordance with ISO 179 for unnotched Charpy impact strength and notched Charpy impact strength for a product molded into a 3 mm thick ISO test piece. Specifically, the pellets obtained above were dried at 100°C for 5 hours, and then molded using an injection molding machine (J85AD manufactured by Japan Steel Works) at a cylinder temperature of 280°C and a mold temperature of 80°C. A 3 mm thick ISO specimen was injection molded under the following conditions. Unnotched Charpy impact strength and notched Charpy impact strength were measured according to ISO179.
• ⁇ Comprehensive evaluation> Based on the evaluation of haze, pencil hardness, and notched Charpy impact strength, scores for each example and comparative example were calculated and evaluated as follows.
• the resin composition of this embodiment can provide molded products with excellent impact resistance and hardness, as well as excellent transparency (Examples 1-1 to 1) -12).
• Examples 1-1 to 1) -12 On the other hand, when the elastomer was not included (Comparative Examples 1-1 and 1-2), the impact resistance was poor. Furthermore, even if the material contained an elastomer, the haze increased when the styrene content was low (Comparative Examples 1-3 to 1-7).
• the mixture was fed into the extruder from the barrel upstream of the extruder at a set cylinder temperature of 260° C., a screw rotation speed of 180 rpm, and a discharge rate of 25 kg/hr, and was melt-kneaded to obtain resin composition pellets.
• Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-7 are those of Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-7, respectively. It was almost equivalent.

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• 2023
  • 2023-08-15 WO PCT/JP2023/029489 patent/WO2024038853A1/ja not_active Ceased
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