JP2005187639A - Transparency resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent resin composition having excellent optical properties such as low birefringence, high heat resistance, surface hardness, and excellent balance between rigidity and toughness.
SOLUTION: A maleimide / olefin copolymer having a specific structure and having a specific constituent and a number average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less, 50 to 99% by weight, acrylonitrile unit 21 A transparent resin composition comprising 1 to 50% by weight of an acrylonitrile / styrene copolymer containing ˜45% by weight.
[Selection figure] No selection figure.

Description

  The present invention relates to a transparent resin composition having excellent optical properties such as low birefringence, high heat resistance, surface hardness, and excellent balance between rigidity and toughness.

  Inorganic glass has been used as an optical material for a long time, but recently, a transparent resin excellent in moldability and light weight has been used as an optical material replacing glass. The plasticization of optical components reflects recent developments in information-related technologies using light, such as films and sheets for flat panel displays such as LCDs, light guide plates for backlights, optical disks, optical fibers, optical waveguides, etc. Actively studied in the field. Transparent resins are also widely used in fields other than optics, such as the electrical / electronic field, automobile field, medical field, food packaging field, and construction material field.

  Conventionally, glass has generally been used as a transparent material, but in recent years, polymer materials have come to be used in terms of productivity, weight reduction, cost, and the like. Examples of such transparent resins include polystyrene (hereinafter abbreviated as PS), polymethyl methacrylate (hereinafter abbreviated as PMMA), polycarbonate (hereinafter abbreviated as PC), nylon, and the like.

  On the other hand, an N-alkyl group-substituted maleimide / olefin copolymer (for example, see Patent Document 1), an N-alicyclic alkyl group-substituted maleimide / N-alkyl group-substituted maleimide / olefin copolymer (for example, see Patent Document 2). ), N-alkyl group-substituted maleimide / N-alkyl group-substituted maleimide / olefin copolymer (see, for example, Patent Document 3) has characteristics such as excellent transparency, heat resistance, and mechanical strength. It is disclosed. In addition, a resin composition comprising an N-alkyl group-substituted maleimide / olefin copolymer and an acrylonitrile / styrene copolymer has been proposed, and it is suitable for optical applications because of its excellent heat resistance and very low birefringence. (For example, refer to Patent Document 4).

JP-A-4-50213

Japanese Patent No. 2928828 Japanese Patent No. 2928826 Japanese Patent No. 3414083

  However, although PS, PMMA, and copolymers and resin compositions containing them are excellent in transparency, they have poor heat resistance and toughness, and therefore, usable applications are limited. PC exhibits relatively high heat resistance and excellent toughness, but birefringence is likely to occur, which may cause problems in optical applications, and has problems such as low surface hardness and easy damage. Nylon is excellent in heat resistance and toughness, but has problems such as high water absorption, low rigidity and low surface hardness.

  The N-substituted maleimide / olefin copolymers proposed in Patent Documents 1, 2, and 3 have high heat resistance and excellent balance between rigidity and toughness, but birefringence tends to occur slightly. In some optical applications where very small birefringence is required, there has been a problem. In addition, the resin composition proposed in Patent Document 4 has characteristics such as extremely low birefringence and excellent heat resistance, surface hardness, and rigidity, but has poor toughness. Problems remained in handling.

  The present inventors have a resin composition comprising an N-substituted maleimide / olefin copolymer and an acrylonitrile / styrene copolymer having a specific substituent, which has excellent optical properties such as low birefringence and high heat resistance. The present invention has been completed by finding that it has excellent properties and surface hardness, and is excellent in the balance between rigidity and toughness.

That is, in the present invention, the total amount of the unit represented by the following general formula (I) and the unit represented by the following general formula (III) is 40 to 60 mol% of the whole polymer, and the unit represented by the following general formula (II). Is 40 to 60 mol% of the whole polymer, the value of component (I) / (III) is 60/40 to 99/1 (molar ratio), and the number average molecular weight is 1 × 10 ³ or more and 5 × A transparent resin composition comprising 50 to 99% by weight of a maleimide / olefin copolymer resin of 10 ⁶ or less and 1 to 50% by weight of an acrylonitrile / styrene copolymer containing 21 to 45% by weight of an acrylonitrile unit. It is about.

（Ｒ１はメチル基、炭素数３〜１２のシクロアルキル基、フェニル基、アルキル置換フェニル基、ナフチル基から選ばれる少なくとも１種以上の有機基を示す。）

(R1 represents at least one organic group selected from a methyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, and a naphthyl group.)

（Ｒ２、Ｒ３は各々独立して水素又は炭素数１〜６のアルキル基を示す。）

(R2 and R3 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.)

（Ｒ４は炭素数２〜１８の直鎖状あるいは分岐状アルキル基、炭素数２〜１８の直鎖状あるいは分岐状エーテル基から選ばれる少なくとも１種以上の有機基を示す。）
以下、本発明について詳細に説明する。

(R4 represents at least one organic group selected from a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched ether group having 2 to 18 carbon atoms.)
Hereinafter, the present invention will be described in detail.

  Here, R1 of the unit represented by the general formula (I) is at least one organic group selected from a methyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, and a naphthyl group. If the unit has an organic group other than these, the resulting resin composition has poor heat resistance.

  Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. Examples of the alkyl-substituted phenyl group include a 2-methylphenyl group and 2-ethylphenyl group. Group, 2-n-propylphenyl group, 2-i-propylphenyl group, 2-n-butylphenyl group, 2-s-butylphenyl group, 2-t-butylphenyl group, 2-n-pentylphenyl group, 2-t-pentylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-di-n-propylphenyl group, 2,6-di-i-propylphenyl group, 2- Methyl-6-ethylphenyl group, 2-methyl-6-i-propylphenyl group, 2,4,6-trimethylphenyl group, 2,4-dimethylphenyl Can include groups such as, among which, in particular heat resistance, rigidity, preferably a methyl group since the transparent resin composition having excellent toughness.

  In addition, R2 and R3 of the unit represented by the general formula (II) are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and when the number of carbon atoms exceeds 6, the obtained transparent resin composition Heat resistance is inferior. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, A cyclohexyl group etc. can be mentioned, Among these, since it becomes a transparent resin composition excellent in especially heat resistance and toughness, a methyl group is preferable.

  R4 of the unit represented by the general formula (III) is at least one selected from a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched ether group having 2 to 18 carbon atoms. When the organic group is an organic group other than these, the toughness of the transparent resin composition is poor.

  Examples of the linear or branched alkyl group having 2 to 18 carbon atoms include an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. , Dodecyl group, lauryl group, stearyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, 1,2-dimethylpropyl group, 2-ethylhexyl group, i-amyl group, etc. Examples of the linear or branched ether group having 2 to 18 carbon atoms include 3-methoxypropyl group, 3-ethoxypropyl group, 3-propoxypropyl group, 3-i-propoxypropyl group, 3- Butoxypropyl group, 3-i-butoxypropyl group, 3-decyloxypropyl group, 3-lauroxypropyl group, 3-myristoxypropyl group, etc. Among the particularly heat resistance, n- butyl group from becoming transparent resin composition having excellent toughness, it is preferable that 3-ethoxypropyl group.

  Such maleimide / olefin copolymers include, for example, radicals of maleimides that derive units represented by general formulas (I) and (III) and olefins that derive units represented by general formula (II). It can be obtained by a copolymerization reaction.

  In this case, examples of the compound for deriving the unit represented by the general formula (I) include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like, and a transparent resin composition particularly excellent in heat resistance and rigidity. N-methylmaleimide is preferable because a product is obtained.

  Examples of the compound for deriving the unit represented by the general formula (II) include olefins such as isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, Of these, isobutene is preferable because it becomes a transparent resin composition excellent in heat resistance and toughness.

  Examples of the compound that derives the unit represented by the general formula (III) include N-ethylmaleimide, Nn-propylmaleimide, Nn-butylmaleimide, Nn-pentylmaleimide, and Nn-hexyl. Maleimide, N-laurylmaleimide, Ni-propyl maleimide, Ni-butyl maleimide, Ns-butyl maleimide, Nt-butyl maleimide, Ni-amyl maleimide, N-3-methoxypropyl maleimide, Examples thereof include maleimides such as N-3-ethoxypropylmaleimide, and among them, Nn-butylmaleimide and N-3-ethoxypropylmaleimide are preferable because a transparent resin composition excellent in heat resistance and toughness is obtained. .

  The value of component (I) / (III) constituting the maleimide / olefin copolymer used in the present invention is 60/40 to 99/1 (molar ratio), preferably 70/30 to 99/1 (molar ratio). When the value of (I) / (III) exceeds 99/1, the toughness of the transparent resin composition becomes poor, and when it is less than 60/40, the heat resistance of the transparent resin composition is poor. Become.

  Moreover, the total amount of the unit represented by the general formula (I) and the unit represented by the general formula (III) constituting the maleimide / olefin copolymer used in the present invention is in the range of 40 to 60 mol%, particularly The amount is preferably 45 to 55 mol% because it becomes a transparent resin composition having excellent heat resistance and rigidity. Here, when the total amount of the unit represented by the general formula (I) and the unit represented by the general formula (III) exceeds 60 mol%, the resulting transparent resin composition becomes brittle. On the other hand, when it is less than 40 mol%, the heat resistance of the transparent resin composition is lowered.

The maleimide / olefin copolymer used in the present invention has a number average molecular weight (Mn) of 1 × 10 ³ or more and 5 × 10 ⁶ or less, and is particularly excellent in the balance between toughness and moldability, and therefore 1 × 10 ⁴ or more. 5 × 10 ⁵ or less is preferable. When the number average molecular weight exceeds 5 × 10 ⁶ , the melt viscosity of the maleimide / olefin copolymer becomes too high, so that the fluidity of the resin composition becomes poor and the molding process becomes inferior. On the other hand, when the number average molecular weight is less than 1 × 10 ³ , the toughness of the transparent resin composition becomes poor. Here, the number average molecular weight in the present invention is a standard polystyrene conversion value obtained by gel permeation chromatography (GPC).

  The maleimide / olefin copolymer used in the present invention is particularly excellent in the balance of heat resistance, toughness, and rigidity. Therefore, N-methylmaleimide / Nn-butylmaleimide, isobutene copolymer, N- A methylmaleimide / N-3-ethoxypropylmaleimide / isobutene copolymer is preferred.

  Furthermore, the maleimide / olefin copolymer constituting the transparent resin composition used in the present invention contains units derived from other monomer components as long as the purpose of the present invention is not impaired. Such other monomer components may include, for example, styrene derivatives such as styrene and α-methylstyrene; methacrylic acid such as methacrylic acid, methyl methacrylate, and ethyl methacrylate or esters thereof; acrylic acid, acrylic acid Acrylic acid such as methyl and ethyl acrylate or esters thereof; vinyl esters such as vinyl acetate and vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propio vinyl ether, and butyl vinyl ether; maleic anhydride; acrylonitrile One or more compounds The recited, it is preferably not more than 5 mol% as its content.

  The maleimide / olefin copolymer used in the present invention is a compound derived from a unit represented by the general formula (I), a compound derived from a unit represented by the general formula (II), and the general formula (III). It can be obtained by polymerizing a compound for deriving a unit by a known method. As such a polymerization method, for example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a precipitation polymerization method, and an emulsion polymerization method can be obtained, and among them, a resin particularly excellent in transparency and color tone Since the composition can be obtained, it is preferably obtained by a precipitation polymerization method.

  As a polymerization initiator used in the polymerization reaction, for example, benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, organic peroxides such as t-butylperoxyacetate and t-butylperoxybenzoate; 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), 2, Examples thereof include azo initiators such as 2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, and 1,1′-azobis (cyclohexane-1-carbonitrile).

  Examples of the solvent used in the solution polymerization method and the precipitation polymerization method include aromatic solvents such as benzene, toluene, and xylene; alcohol solvents such as methanol, ethanol, propyl alcohol, and butyl alcohol; cyclohexane, dioxane, tetrahydrofuran, acetone, and methyl ethyl ketone. , Dimethylformamide, isopropyl acetate, a mixed solvent of an aromatic solvent and an alcohol solvent, and the like.

  Although the polymerization temperature in that case can be suitably set according to the decomposition temperature of a polymerization initiator, generally it is preferable to carry out in 40-150 degreeC.

Alternatively, the maleimide / olefin copolymer can also be obtained by post-imidizing the maleic anhydride / olefin copolymer with an amine compound.
Such a post-imidation reaction includes, for example, maleic anhydride / olefin copolymer in an alcohol solvent such as methanol, ethanol and propanol; an aromatic solvent such as benzene and toluene; an ester solvent such as ethyl acetate and isopropyl acetate; It is dissolved or dispersed in a solvent such as a mixed solvent of an aromatic solvent and an alcohol solvent, N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), dimethylformamide (hereinafter abbreviated as DMF), and amine. A method in which an amidation reaction and an imidation reaction are continuously carried out by reacting with a compound at a temperature of 50 to 250 ° C., an amide body is obtained by reacting with an amine compound, and then the amide body is heated for dehydration and cyclization. It can be produced by a method of imidization.

  Examples of amine compounds include, for example, methylamine, cyclopropylamine, cyclobutylamine, cyclohexylamine, adamantylamine, aniline, 2-methylphenylamine, 2-ethylphenylamine, 2-n-propylphenylamine, 2-i- Propylphenylamine, 2-n-butylphenylamine, 2-s-butylphenylamine, 2-t-butylphenylamine, 2-n-pentylphenylamine, 2-t-pentylphenylamine, 2,6-dimethylphenyl Amine, 2,6-diethylphenylamine, 2,6-di-n-propylphenylamine, 2,6-di-i-propylphenylamine, 2-methyl-6-ethylphenylamine, 2-methyl-6- i-propylphenylamine, 2,4,6-trimethylphenyl Min, 2,4-dimethylphenylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, dodecylamine, laurylamine, stearylamine, i-propylamine, i-butylamine, s-butylamine, t-butylamine, 1,2-dimethylpropylamine, 2-ethylhexylamine, i-amylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropyl Amine, 3-i-propoxypropylamine, 3-butoxypropylamine, 3-i-butoxypropylamine, 3-decyloxypropylamine, N-3-lauroxypropylamine, 3-myristoxypropylamine, etc. Can In particular, methylamine is preferable as the amine compound for deriving the unit represented by the general formula (I) because it is a transparent resin composition having an excellent balance of heat resistance, toughness, and rigidity. As the amine compound for deriving the unit shown, n-butylamine and 3-ethoxypropylamine are preferable.

  In the transparent resin composition of the present invention, an acrylonitrile / styrene copolymer is added for the purpose of improving moldability by increasing fluidity and reducing birefringence. The reason why the birefringence of a transparent resin composition comprising a maleimide / olefin copolymer and an acrylonitrile / styrene copolymer is small is that the maleimide / olefin copolymer has a positive birefringence, and an acrylonitrile / styrene copolymer. This is because they have negative birefringence and cancel each other's birefringence. Moreover, since the acrylonitrile / styrene copolymer having a specific composition of acrylonitrile content is compatible with the maleimide / olefin copolymer, the resin composition of the present invention has high transparency.

  The acrylonitrile / styrene copolymer used in the present invention is an acrylonitrile / styrene copolymer containing 21 to 45% by weight of acrylonitrile units. Here, when the acrylonitrile unit is less than 21% by weight or more than 45% by weight, the compatibility of the maleimide / olefin copolymer and the acrylonitrile / styrene copolymer is lowered, so that the resin composition becomes opaque. Also, heat resistance is reduced.

  The blending ratio of the maleimide / olefin copolymer and the acrylonitrile / styrene copolymer constituting the transparent resin composition of the present invention is 99 to 50 wt% of the maleimide / olefin copolymer and 1 to 50 of the acrylonitrile / styrene copolymer. 90% to 50% by weight of maleimide / olefin copolymer and 10% to acrylonitrile / styrene copolymer, because the resin composition has an excellent balance of weight%, particularly optical properties such as low birefringence, moldability, and heat resistance. A weight of 50 is preferred. When the maleimide / olefin copolymer is less than 50% by weight, the resulting transparent resin composition has poor heat resistance. When the maleimide / olefin copolymer exceeds 99% by weight, acrylonitrile / styrene copolymer is used. The effect of improving fluidity and reducing birefringence by adding a polymer is poor.

  The transparent resin composition of the present invention requires phenolic, phosphorus, sulfur and other antioxidants in order to suppress coloring, decomposition, cross-linking, etc. due to thermal history during production or molding. It may be contained accordingly. These antioxidants may be used alone or in combination. Although the detail is shown below, this invention is not restrict | limited to these at all.

  Examples of the phenolic antioxidant include pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), thiodiethylene-bis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionamide], diethyl [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] phosphate, 3,3 ′, 3 ′ ', 5,5', 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, ethyl Bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione 2,6-di-t-butyl-4- [4,6-bis (octylthio) -1,3,5-triazin-2-ylamino] phenol, 3,9-bis [2- {3- (3 -T-butyl-4-hydroxy-5-methylphenyl) Propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5 -Methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl acrylate, and 2, And 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate.

  Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorus Acid, tetrakis (2,4-di-t-butylphenyl) (1,1-biphenyl) -4,4'-diylbisphosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol di Phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,4-dicumylphenyl) pentaerythritol-diphosphite, tetrakis (2,4-t-butylphenyl) ) (1,1-biphenyl) -4,4′-diylbisphosphonite, di-t-butyl-m-cresyl-phosphonite, etc. It is.

  Examples of sulfur antioxidants include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropioate. And pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. It is done.

  Other antioxidants include, for example, an antioxidant having both a function as a phenol-based antioxidant and a function as a phosphorus-based antioxidant, as a phenol / phosphorus-based antioxidant, 6- [3- ( 3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxaphosphepine, vitamin Examples of the E-based antioxidant include 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol.

  Among the above antioxidants, it is preferable that the transparent resin composition contains a phenolic antioxidant and a phosphorus antioxidant because it is difficult to color. In that case, it is preferable to contain a phosphorus antioxidant in the ratio of 100-500 weight part with respect to 100 weight part of phenolic antioxidant, for example. Moreover, as content of antioxidant, it is 100-20000 ppm normally.

  In addition, when the transparent resin composition is used as an optical material, it is assumed that the transparent resin composition is irradiated with light such as visible light, ultraviolet light, and infrared light. Therefore, a hindered amine light stabilizer, an ultraviolet absorber, a light stabilizer, a near infrared absorber, and the like may be contained as necessary for the purpose of suppressing the thermal coloring and light degradation. Although the detail is shown below, this invention is not restrict | limited to these at all.

  As the hindered amine light stabilizer, those having a molecular weight of 1,000 or more are preferable because of excellent thermal coloring suppression effect. Furthermore, since content of a hindered amine light stabilizer is excellent in the thermal coloring prevention effect and the light stabilization effect, it is usually 100 to 15000 ppm.

  Examples of such a hindered amine light stabilizer include poly [(6-morpholino-s-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene. {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dibutylamine- 1,3,5-triazine-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) 1,6-hexamethylenediamine and N- (2,2,6,6- Tetramethyl-4-piperidyl) bu Polyamine condensate, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino ] -6-chloro-1,3,5-triazine condensate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine condensate and the like. .

  Examples of the ultraviolet absorber include conventionally known ultraviolet absorbers such as benzotriazole, benzophenone, triazine, benzoate, salicylic acid, acrylate, and metal complex. As content of a ultraviolet absorber, it is 500-100000 ppm normally.

  Examples of the ultraviolet absorber include compounds as disclosed in JP 2001-98163 A, specifically phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 4-t-octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl 3', 5'-di-t- Butyl-4′-hydroxybenzoate, octadecyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3 ′, 5′-di-t -Salicylate derivatives such as butyl-4'-hydroxybenzoate and mixtures thereof, 2,4-dihydroxyben Zophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxybenzophenone derivatives such as 2,2 ′, 4,4′-tetrahydroxybenzophenone and mixtures thereof, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5′-di -T-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzo Triazole, 2- (3-tert-butyl-2-hydroxy-5-methyl Enyl) -5-chlorobenzotriazole, 2- (3′-s-butyl-2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) Benzotriazole, 2- (3 ′, 5′-di-t-amyl-2′-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) Phenyl] -2H-benzotriazole, 2-[(3′-t-butyl-2′-hydroxyphenyl) -5 ′-(2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3 '-T-butyl-5'-{2- (2-ethylhexyloxy) carbonylethyl} -2'-hydroxyphenyl] -5-chlorobenzotriazole 2- [3′-t-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3′-t-butyl-2′-hydroxy- 5 ′-(2-methoxycarbonylethyl) phenyl] benzotriazole, 2- [3′-tert-butyl-2′-hydroxy-5- (2-octyloxycarbonylethyl) phenyl] benzotriazole, 2- [3 ′ -T-butyl-2'-hydroxy-5 '-{2- (2-ethylhexyloxy) carbonylethyl} phenyl] benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide) Methyl) -5-methylphenyl] benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzo Triazole, 2- (3′-dodecyl-2′-hydroxy-5′-methylphenyl) benzotriazole and 2- [3′-tert-butyl-2′-hydroxy-5 ′-(2-isooctyloxycarbonylethyl) ) Phenyl] benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2,2 ′ -Methylenebis [4-t-butyl-6- (2H-benzotriazol-2-yl) phenol], poly (3-11) (ethylene glycol) and 2- [3'-t-butyl-2'-hydroxy- Condensate with 5 ′-(2-methoxycarbonylethyl) phenyl] benzotriazole, poly (3-11) (ethylene glycol) and methyl 3- [3- ( H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate condensate, 2-ethylhexyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazole) -2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t-butyl-5- (5-chloro-2H-benzo Triazol-2-yl) -4-hydroxyphenyl] propionic acid, and 2- (4,6-diphenyl-1,3,5-triazine-2- Le) -5- [hexyl (oxy)] - phenol, and the like.

  Examples of near infrared absorbers include cyanine-based near infrared absorbers, pyrylium-based infrared absorbers, squarylium-based near-infrared absorbers; croconium-based infrared absorbers, azulenium-based near infrared absorbers, phthalocyanine-based near infrared absorbers, dithiol metals Examples thereof include complex near infrared absorbers, naphthoquinone near infrared absorbers, anthraquinone near infrared absorbers, indophenol near infrared absorbers, and azimuth near infrared absorbers.

  Moreover, the transparent resin composition of the present invention includes, in addition to the above-mentioned components, pigments, lubricants, antiblocking agents, antistatic agents, surfactants, polymer electrolytes, conductive complexes, inorganic fillers, dyes, plasticizers, Oil or the like may be contained as necessary, and other resins may be contained only when transparency is not impaired. Although the detail is shown below, this invention is not restrict | limited to these at all.

  Examples of the lubricant include aliphatic hydrocarbon lubricants such as liquid paraffin, natural paraffin and polyethylene wax; higher aliphatic alcohols and higher fatty acid lubricants such as cetyl alcohol, stearyl alcohol and stearic acid; stearamide, oleamide , Aliphatic amide type lubricants such as palmitic acid amide and methylene bisstearamide; metal soap type lubricants such as calcium stearate, zinc stearate, magnesium stearate and barium stearate; fatty acids such as butyl stearate and ethylene glycol stearate Ester-based lubricants; silicone oils and the like are mentioned, and the content of the lubricant is usually 1 to 10,000 ppm.

  Other resins include, for example, acrylonitrile / styrene copolymer-based impact-resistant resins such as ASA (acrylonitrile / styrene / acrylic rubber), ABS (acrylonitrile / butadiene / styrene), AES (acrylonitrile / EPDM or EPR / styrene), SAS ( Acrylonitrile / styrene copolymer graft polycarbonate resin (AS-g-PC), acrylonitrile / styrene copolymer grafted ethylene / glycidyl methacrylate copolymer, such as styrene / acrylonitrile / silicon) Combined resin (AS-g-EGMA), acrylonitrile / styrene copolymer grafted ethylene / ethyl acrylate copolymer resin (AS-g-EEA), acrylonitrile · Styrene copolymer grafted polyethylene resin (AS-g-LDPE), acrylonitrile-styrene copolymer grafted polypropylene resin (AS-g-PP), such as amorphous nylon.

  The method for producing the resin transparent resin composition of the present invention is not particularly limited as long as the components constituting the composition exhibit good dispersibility. For example, a single-screw extruder, a twin-screw extruder, Examples thereof include a method of mixing using a melt kneading apparatus such as a Brabender, roll, kneader, Banbury mixer, or a method of mixing the components constituting the transparent resin composition by dissolving or dispersing them in a solvent.

  The transparent resin composition of the present invention can be formed into a molded body by a conventionally known molding method, for example, injection molding, injection compression molding, gas assist method injection molding, extrusion molding, solution cast molding, multilayer extrusion molding, rotation Examples of the method include molding, hot press molding, blow molding, and the obtained molded body is subjected to surface treatment such as printing, painting, hard coating, antireflection coating, vacuum deposition, sputtering, and antiglare coating. You can also.

  The use of the transparent resin composition of the present invention is not particularly limited. For example, relays, burn-in sockets, connectors, sensor housings, variable resistors, polyvaricon cases, aeration bobbins, transistors in the electric / electronic equipment field, IC, LSI, LED and other sealing materials, IC card IC memory sealing materials, motors, capacitors, switches, sensors, and other sealing materials; Cameras, VTRs, projectors, and other imaging equipment fields, finder , Filters, prisms, Fresnel lenses, body materials, etc .; cards, disks, pickup lenses, etc. in the optical recording field such as CD players, DVD players, MD players, game machines, etc .; optical fibers, optical switches, optical connectors, etc. in the optical communication field; LCD, yes Light guide plate, light guide, Fresnel lens, retardation film, polarizing film protective film, prism sheet, reflector film, separator film, light in information equipment field such as EL, PDP, copier, printer, facsimile, touch panel, optical file Diffusion sheet, transparent electrode substrate, display surface protective film and sheet, anti-glare film, anti-reflection film, electromagnetic wave shielding film, ink tank, covers, body materials, etc .; meters, lamps, etc. in vehicles such as automobiles and trains, Lenses, sockets, fuse cases, instrument covers, etc .; eyeglass lenses, contact lenses, endoscope lenses, syringes, artificial dialysers, drug containers, dentures, ampoule cutter containers, etc. in the field of medical equipment; , Surveillance camera lenses, carports, terraces, lighting components, etc .; can be suitably used as lighting components, toys, sunglasses, stationery, cosmetic containers, fishing gear, food containers, drinking water containers, etc. in the daily necessities field .

  The composition obtained by the present invention is excellent in optical properties such as low birefringence, has high heat resistance and surface hardness, and is excellent in the balance between rigidity and toughness, so it is suitably used in applications such as the optical field. can do.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

  Various physical properties shown in the examples were measured by the following methods.

~ Number average molecular weight ~
It calculated | required as a standard polystyrene conversion value by the elution curve of the maleimide olefin copolymer measured using the gel permeation chromatography (GPC) (The Tosoh Corporation make, brand name HLC-802A).

~ Total light transmittance ~
The measurement was performed according to JIS K7105 (1981).

~ Deflection temperature under load ~
It measured based on JISK7191 (1996).

~ Scratch pencil hardness ~
It measured based on JISK5600-5-4 (1996).

~ Elongation at break ~
It measured based on JISK7161 (1994).

~ Bending elastic modulus ~
It measured based on JISK7171 (1994).

~ Birefringence ~
Using a fully automatic birefringence meter (trade name KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), measurement was performed under the condition of a measurement wavelength of 546 nm.

Synthesis example 1
A 5 L separable flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a cooling tube was charged with 500 g of maleic anhydride / isobutene copolymer (manufactured by Kuraray Co., Ltd., trade name Isoban 10) and 3000 g of NMP as a solvent, The maleic anhydride / isobutene copolymer was dissolved in NMP by stirring at room temperature. Then, after introducing 100 g of methylamine gas at room temperature, the mixture was heated to 80 ° C. and stirred for 1 hour to amidate the maleic anhydride unit and then cooled to room temperature. Subsequently, after 240 g of n-butylamine was introduced, the mixture was heated to 80 ° C. and stirred for 1 hour to amidate the remaining maleic anhydride units. Subsequently, after the temperature was raised to 205 ° C. and the mixture was stirred for 1 hour, an imidization reaction was performed, and then the mixture was cooled to room temperature and reprecipitated using isopropanol to recover the polymer.

From the elemental analysis, infrared absorption spectrum measurement (hereinafter abbreviated as IR measurement), ¹ H-NMR measurement and ¹³ C-NMR measurement, the polymer produced was N-methylmaleimide residue unit / Nn-butyl. It was confirmed to be an N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer in which maleimide residue unit / isobutene residue unit = 0.45 / 0.05 / 0.50 (molar ratio). The number average molecular weight of the produced polymer was 92,000.

Synthesis example 2
A 5 L separable flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a cooling tube was charged with 500 g of maleic anhydride / isobutene copolymer (manufactured by Kuraray Co., Ltd., trade name Isoban 10) and 3000 g of NMP as a solvent, The maleic anhydride / isobutene copolymer was dissolved in NMP by stirring at room temperature. Then, after introducing 100 g of methylamine gas at room temperature, the mixture was heated to 80 ° C. and stirred for 1 hour to amidate the maleic anhydride unit and then cooled to room temperature. Subsequently, after introducing 340 g of 3-ethoxypropylamine, the temperature was raised to 80 ° C. and stirred for 1 hour to amidate the remaining maleic anhydride unit. Subsequently, after the temperature was raised to 205 ° C. and the mixture was stirred for 1 hour, an imidization reaction was performed, and then the mixture was cooled to room temperature and reprecipitated using isopropanol to recover the polymer.

From the elemental analysis, IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement, the polymer produced was N-methylmaleimide residue unit / N-3-ethoxypropylmaleimide residue unit / isobutene residue unit = 0. It was confirmed that the N-methylmaleimide / N-3-ethoxypropylmaleimide / isobutene copolymer was 46 / 0.04 / 0.50 (molar ratio). Moreover, the number average molecular weight of the produced | generated polymer was 95000.

Synthesis example 3
A 5 L separable flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a cooling tube was charged with 500 g of maleic anhydride / isobutene copolymer (manufactured by Kuraray Co., Ltd., trade name Isoban 10) and 3000 g of NMP as a solvent, The maleic anhydride / isobutene copolymer was dissolved in NMP by stirring at room temperature. Next, 200 g of methylamine gas was introduced at room temperature, the temperature was raised to 80 ° C., and the mixture was stirred for 1 hour to amidate maleic anhydride units. Subsequently, after the temperature was raised to 205 ° C. and the mixture was stirred for 1 hour, an imidization reaction was performed, and then the mixture was cooled to room temperature and reprecipitated using isopropanol to recover the polymer.

From the elemental analysis, IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement, the polymer produced is N-methylmaleimide residue unit / isobutene residue unit = 0.50 / 0.50 (molar ratio). It was confirmed to be an N-methylmaleimide / isobutene copolymer. Moreover, the number average molecular weight of the produced | generated polymer was 90000.

Synthesis example 4
A 5 L separable flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a cooling tube was charged with 500 g of maleic anhydride / isobutene copolymer (manufactured by Kuraray Co., Ltd., trade name Isoban 10) and 3000 g of NMP as a solvent, The maleic anhydride / isobutene copolymer was dissolved in NMP by stirring at room temperature. Next, after introducing 50 g of methylamine gas at room temperature, the mixture was heated to 80 ° C. and stirred for 1 hour to amidate maleic anhydride units, and cooled to room temperature. Subsequently, after 240 g of n-butylamine was introduced, the mixture was heated to 80 ° C. and stirred for 1 hour to amidate the remaining maleic anhydride units. Subsequently, after the temperature was raised to 205 ° C. and the mixture was stirred for 1 hour, an imidization reaction was performed, and then the mixture was cooled to room temperature and reprecipitated using isopropanol to recover the polymer.

From the elemental analysis, IR measurement, ¹ H-NMR measurement and ¹³ C-NMR measurement, the polymer produced was N-methylmaleimide residue unit / Nn-butylmaleimide residue unit / isobutene residue unit = 0.20. It was confirmed to be an N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer having a ratio of /0.30/0.50 (molar ratio). Moreover, the number average molecular weight of the produced | generated polymer was 98000.

Examples 1-2 and Comparative Examples 1-3
Using a tumbler mixer, 80% by weight of the N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer obtained in Synthesis Example 1 and 20% by weight of an acrylonitrile / styrene copolymer having different acrylonitrile unit contents shown in Table 1 were used. After dry blending, it was subjected to a 30 mmφ twin-screw extruder (manufactured by Nippon Steel Works, trade name TEX30), extruded and pelletized to obtain a resin composition.

Next, the obtained resin composition pellets are subjected to an injection molding machine (trade name IS50EP, manufactured by Toshiba Machine Co., Ltd.), and injection molding is performed under the conditions of a nozzle temperature of 260 ° C., a mold temperature of 90 ° C., and an injection pressure of 1600 kg / cm ^2. A test piece was obtained. As a result of evaluating the transparency using this injection test piece, as shown in Table 1, a resin composition having excellent transparency was obtained when the acrylonitrile unit content was in the range of 21 to 45% by weight.

Example 3
90% by weight of the N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer obtained in Synthesis Example 1 and an acrylonitrile / styrene copolymer having an acrylonitrile unit content of 29% by weight (manufactured by Technopolymer Co., Ltd., product) After 10% by weight of Sanlex SAN-L) was dry blended with a tumbler mixer, it was subjected to a 30 mmφ twin screw extruder (product name: TEX30, manufactured by Nippon Steel Co., Ltd.), extruded and pelletized to obtain a transparent resin composition. .

Next, the obtained transparent resin composition pellets were subjected to an injection molding machine (trade name IS50EP, manufactured by Toshiba Machine Co., Ltd.) under the conditions of a nozzle part temperature of 260 ° C., a mold temperature of 80 ° C., and an injection pressure of 1600 kg / cm ² . A test piece was obtained by injection molding. Table 2 shows the results of physical properties measured using this injection test piece. The obtained transparent resin composition had low birefringence, high transparency, and excellent balance of heat resistance, rigidity, surface hardness, and toughness.

Example 4
Instead of the N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer obtained in Synthesis Example 1, the N-methylmaleimide / N-3-ethoxypropylmaleimide / isobutene copolymer obtained in Synthesis Example 2 was used. A transparent resin composition good for the same method as in Example 3 was obtained except that coalescence was used, and the evaluation was performed.

  The results are shown in Table 2. The obtained transparent resin composition had low birefringence, high transparency, and excellent balance of heat resistance, rigidity, surface hardness, and toughness.

Comparative Example 4
The N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer obtained in Synthesis Example 1 was subjected to a 30 mmφ twin-screw extruder (manufactured by Nippon Steel Works, Ltd., trade name: TEX30), extruded and pelletized.

Next, the obtained resin pellets were subjected to an injection molding machine (trade name IS50EP, manufactured by Toshiba Machine Co., Ltd.), and injection molded under the conditions of a nozzle part temperature of 260 ° C., a mold temperature of 85 ° C., and an injection pressure of 1600 kg / cm ^2. A specimen was obtained. Table 2 shows the results of physical properties measured using this injection test piece. Although the obtained resin had high transparency, the birefringence was slightly large.

Comparative Example 5
10% by weight of N-methylmaleimide / isobutene copolymer 90% by weight obtained by Synthesis Example 3 and acrylonitrile / styrene copolymer having 29% by weight of acrylonitrile unit (trade name, Sanrex SAN-L, manufactured by Technopolymer Co., Ltd.) % Was dry blended with a tumbler mixer, then subjected to a 30 mmφ twin screw extruder (manufactured by Nippon Steel Works, trade name: TEX30), extruded and pelletized to obtain a resin composition.

Next, the obtained resin composition pellets were subjected to an injection molding machine (trade name IS50EP, manufactured by Toshiba Machine Co., Ltd.), and injection molded under the conditions of a nozzle part temperature of 260 ° C., a mold temperature of 80 ° C., and an injection pressure of 1600 kg / cm ^2. A test piece was obtained. Table 2 shows the results of physical properties measured using this injection test piece. The obtained resin composition had low birefringence and high transparency, but had poor toughness.

Comparative Example 6
90% by weight of N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer and 29% by weight of acrylonitrile unit obtained by Synthesis Example 4 (trade name Sun, manufactured by Technopolymer Co., Ltd.) Rex SAN-L) 10% by weight was dry blended with a tumbler mixer, then subjected to a 30 mmφ twin-screw extruder (manufactured by Nippon Steel Works, trade name: TEX30), extruded and pelletized to obtain a resin composition.

Next, the obtained resin composition pellets were subjected to an injection molding machine (trade name IS50EP, manufactured by Toshiba Machine Co., Ltd.), and injection molded under the conditions of a nozzle part temperature of 260 ° C., a mold temperature of 80 ° C., and an injection pressure of 1600 kg / cm ^2. A test piece was obtained. Table 2 shows the results of physical properties measured using this injection test piece. The obtained resin composition had low birefringence and high transparency, but had poor heat resistance and rigidity.

Claims (2)

The total amount of the unit represented by the following general formula (I) and the unit represented by the following general formula (III) is 40 to 60 mol% of the whole polymer, and the unit represented by the following general formula (II) is 40 to 40% of the whole polymer. Maleimide having 60 mol%, a component (I) / (III) value of 60/40 to 99/1 (molar ratio), and a number average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less A transparent resin composition comprising 50 to 99% by weight of an olefin copolymer and 1 to 50% by weight of an acrylonitrile / styrene copolymer containing 21 to 45% by weight of acrylonitrile units.

(R1 represents at least one organic group selected from a methyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, and a naphthyl group.)

(R2 and R3 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.)

(R4 represents at least one organic group selected from a linear or branched alkyl group having 2 to 18 carbon atoms and a linear or branched ether group having 2 to 18 carbon atoms.) The maleimide / olefin copolymer is an N-methylmaleimide / Nn-butylmaleimide / isobutene copolymer or an N-methylmaleimide / N-3-ethoxypropylmaleimide / isobutene copolymer. Item 2. The transparent resin composition according to Item 1.