JP2006143758A - Transparent resin composition and transparent film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent resin composition which can be suitably used as an optical film or the like and is excellent in transparency, heat resistance, toughness and melt processability. <P>SOLUTION: The transparent resin composition comprises 40-98 wt% of an N-substituted maleimide-olefin copolymer having a specific structure and a number average molecular weight of from 1×10<SP>3</SP>to 5×10<SP>6</SP>, 40-1 wt% of a graft-modified 1,3-butadiene-styrene copolymer rubber prepared by grafting 1,3-butadiene-styrene copolymer rubber particles with a styrene-acrylonitrile copolymer, and 1-20 wt% of an acrylic plasticizer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transparent resin composition comprising an N-substituted maleimide / olefin copolymer, a graft-modified 1,3-butadiene / styrene copolymer rubber grafted with a styrene / acrylonitrile copolymer, and an acrylic plasticizer. Further, the present invention relates to a transparent film comprising the transparent resin composition, and in particular, a transparent resin composition excellent in transparency, heat resistance, toughness and melt processability, and a transparent film comprising the transparent resin composition. It is about.

  Inorganic glass has been used as an optical material for a long time, but in recent years, a transparent resin excellent in moldability and light weight has been used as an optical material replacing inorganic glass. The plasticization of optical components reflects the development of information-related technologies using light in recent years, such as fields for flat panel display films and sheets such as LCDs, light guide plates for backlights, optical disks, optical fibers, and optical waveguides. It is being actively studied. 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.

  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, it is disclosed that the N-substituted maleimide / olefin copolymer has characteristics such as transparency, low birefringence, heat resistance, and mechanical strength (see, for example, Patent Document 1). .

  Further, it is disclosed that a resin composition comprising an N-substituted maleimide / olefin copolymer and an elastomer has characteristics such as excellent transparency, heat resistance, toughness and the like (see, for example, Patent Document 2). ).

  Furthermore, a resin composition comprising an N-alkyl group-substituted maleimide / olefin copolymer and a styrene / acrylonitrile copolymer has been proposed, and it has excellent heat resistance and very low birefringence, and is therefore suitable for optical applications. (For example, refer to Patent Document 3).

  Further, a method for producing a succinimide resin composition in the presence of a styrene-based impact resistant resin such as ABS resin, AES resin, AAS resin, ACS resin or the like is disclosed (for example, see Patent Document 4).

Japanese Patent No. 3168466 Japanese Patent No. 3214003 Japanese Patent No. 3414083 Japanese Patent Laid-Open No. 2002-3528

  However, PS, PMMA, and copolymers and resin compositions containing them are excellent in transparency but have poor heat resistance and toughness. Further, 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 and resin compositions proposed in Patent Documents 1 and 3 have characteristics such as high transparency, excellent heat resistance, surface hardness, and rigidity, but poor toughness. Problems remain in handling properties during molding or after molding.

  The resin composition proposed in Patent Document 2 comprises an N-substituted maleimide / olefin copolymer and an elastomer having a refractive index difference of 0.01 or less with respect to the copolymer, and high transparency is obtained. However, there is no description about a method for improving the dispersion state of the elastomer in the N-substituted maleimide / olefin copolymer, and it is a problem that satisfactory transparency cannot always be obtained. .

  Patent Document 4 relates to a method for producing a succinimide resin composition having excellent quality with high production efficiency, and does not describe any method for improving the dispersion state of the styrene resin in the succinimide resin. However, it was a problem that satisfactory transparency could not always be obtained.

  Then, an object of this invention is to provide the transparent resin composition excellent in transparency, heat resistance, toughness, and melt processability.

  As a result of intensive studies on the above problems, the present inventors have found that a resin composition comprising an N-substituted maleimide / olefin copolymer, a graft-modified rubber having a specific molecular structure, and a plasticizer having a specific molecular structure is highly transparent. Have been found to be excellent in heat resistance, toughness, and melt processability, and have led to the completion of the present invention.

That is, the present invention comprises 40 to 60 mol% of units represented by the following general formula (I) and 60 to 40 mol% of units represented by the following general formula (II), and the number average molecular weight is 1 × 10 ³ or more and 5 × 10 ⁶ or less N-substituted maleimide / olefin copolymer 40-98% by weight, 1,3-butadiene / styrene copolymer rubber particles grafted with styrene / acrylonitrile copolymer grafted 1,3 The present invention relates to a transparent resin composition comprising 40 to 1% by weight of a butadiene / styrene copolymer rubber and 1 to 20% by weight of an acrylic plasticizer.

（ここで、Ｒ１は炭素数１〜６のアルキル基、炭素数３〜１２のシクロアルキル基から選ばれる少なくとも１種以上の有機基を示す。）

(Here, R1 represents at least one organic group selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms.)

（ここで、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。）
以下、本発明について詳細に説明する。

(Here, R2 and R3 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.)
Hereinafter, the present invention will be described in detail.

The N-substituted maleimide / olefin copolymer constituting the transparent resin composition of the present invention is composed of 40 to 60 mol% of the unit represented by the general formula (I) and 60 to 60 units represented by the general formula (II). It is a copolymer composed of 40 mol%, and is an N-substituted maleimide / olefin copolymer having a number average molecular weight of 1 × 10 ^{3 to} 5 × 10 ⁶ .

  R1 of the unit represented by the general formula (I) is at least one organic group selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms. When it is a unit to have, transparency when it is set as a resin composition will be inferior.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s- Examples thereof include a butyl group, a t-butyl group, and a 1,2-dimethylpropyl group. 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. In particular, R1 of the unit represented by the general formula (I) is preferably a methyl group or a cyclohexyl group because it becomes a transparent resin composition having an excellent balance between heat resistance and toughness.

  Moreover, 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 heat resistance when the resin composition is obtained. It becomes 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 and the like can be mentioned, and among them, a methyl group is preferable because it becomes a transparent resin composition having an excellent balance between heat resistance and toughness.

  Such an N-substituted maleimide / olefin copolymer is, for example, a radical copolymer of a maleimide that derives a unit represented by the general formula (I) and an olefin that derives a unit represented by the general formula (II). It can be obtained by a polymerization reaction.

  At that time, examples of maleimides for deriving the unit represented by the general formula (I) include N-methylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide and the like, and are particularly transparent with excellent balance of heat resistance and toughness. N-methylmaleimide and N-cyclohexylmaleimide are preferable because a conductive resin composition 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 is a transparent resin composition having an excellent balance between heat resistance and toughness.

  Further, the unit represented by the general formula (I) constituting the N-substituted maleimide / olefin copolymer used in the present invention is in the range of 40 to 60 mol%, and in particular, transparency excellent in balance between heat resistance and toughness. Since it becomes a resin composition, it is preferable that it is 45-55 mol%. Here, when the unit represented by the general formula (I) exceeds 60 mol%, the resulting resin composition becomes brittle. On the other hand, when it is less than 40 mol%, the heat resistance of the resin composition is lowered.

The N-substituted maleimide / olefin copolymer used in the present invention has a number average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less, and becomes a transparent resin composition particularly excellent in balance between toughness and melt processability. Therefore, it is preferably 1 × 10 ⁴ or more and 5 × 10 ⁵ or less. Here, when the number average molecular weight of the N-substituted maleimide / olefin copolymer exceeds 5 × 10 ⁶ , the melt viscosity of the N-substituted maleimide / olefin copolymer becomes too high, so that the fluidity of the resin composition is low. It becomes poor and the melt processability becomes inferior. On the other hand, when the number average molecular weight is less than 1 × 10 ³ , the toughness of the 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).

  Since the N-substituted maleimide / olefin copolymer used in the present invention is a transparent resin composition particularly excellent in the balance between heat resistance and toughness, N-methylmaleimide / isobutene copolymer, N-cyclohexylmaleimide -It is preferable that it is at least 1 or more types of N-substituted maleimide olefin copolymer chosen from an isobutene copolymer.

  Furthermore, the N-substituted maleimide / olefin copolymer used in the present invention may contain units derived from other monomer components as long as it does not impair the purpose of the present invention. Examples of such other monomer components include styrene derivatives such as styrene and α-methylstyrene; methacrylic acid such as methacrylic acid, methyl methacrylate, and ethyl methacrylate or esters thereof; acrylic acid, methyl acrylate, and ethyl acrylate. One or more selected from acrylic acid such as acrylic acid or the like; 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 Compounds and their inclusion It is preferably not more than 5 mol% as.

  The N-substituted maleimide / olefin copolymer used in the present invention polymerizes a compound derived from the unit represented by the general formula (I) and a compound derived from the unit represented by the general formula (II) by a known method. Can be obtained. As such a polymerization method, for example, it can be obtained by any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a precipitation polymerization method, and an emulsion polymerization method, and among them, transparency that is particularly excellent in transparency and color tone. The resin composition 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.

  The polymerization temperature at that time can be appropriately set according to the decomposition temperature of the polymerization initiator, and is generally preferably in the range of 40 to 150 ° C.

  Alternatively, the N-substituted maleimide / olefin copolymer can be obtained by post-imidizing the maleic anhydride / olefin copolymer with an amine compound as an alternative method.

  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; Amidation reaction and imide by dissolving or dispersing in a mixed solvent of an aromatic solvent and an alcohol solvent, a solvent such as N-methyl-2-pyrrolidone, dimethylformamide, and reacting with an amine compound at a temperature of 50 to 250 ° C. It can be produced by a method of continuously performing an oxidization reaction, a method of reacting with an amine compound to obtain an amide, and then heating and dehydrating and ring-closing the amide to perform imidization.

  Examples of amine compounds include methylamine, cyclopropylamine, cyclobutylamine, cyclohexylamine, adamantylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, i-propylamine, i- Examples include butylamine, s-butylamine, t-butylamine, and 1,2-dimethylpropylamine. Among them, since it becomes a transparent resin composition having an excellent balance of heat resistance and toughness, it is represented by the general formula (I). Methylamine and cyclohexylamine are preferred as the amine compound for deriving the unit.

  The graft-modified 1,3-butadiene / styrene copolymer rubber constituting the transparent resin composition of the present invention is obtained by graft polymerization of a styrene / acrylonitrile copolymer to 1,3-butadiene / styrene copolymer rubber particles. A graft copolymer rubber. The graft-modified 1,3-butadiene / styrene copolymer rubber and the N-substituted maleimide / olefin are obtained by graft polymerization of the styrene / acrylonitrile copolymer onto the 1,3-butadiene / styrene copolymer rubber particles. The compatibility of the copolymer is improved, and as a result, the dispersibility of the 1,3-butadiene / styrene copolymer rubber particles in the N-substituted maleimide / olefin copolymer is improved, and as a result The resin composition is excellent in transparency and toughness. In addition, when rubber particles are rubber particles other than 1,3-butadiene / styrene copolymer rubber particles, or 1,3-butadiene / styrene copolymer rubber which is not graft-modified with styrene / acrylonitrile copolymer When it is a particle, the obtained resin composition is inferior in toughness.

  Here, the 1,3-butadiene / styrene copolymer rubber particles constituting the graft-modified 1,3-butadiene / styrene copolymer rubber were more excellent in heat resistance and toughness when used as a transparent resin composition. Since it becomes a thing, it is more preferable that it is what was bridge | crosslinked partially. Further, the 1,3-butadiene / styrene copolymer rubber particles may be a copolymer of a polyfunctional vinyl monomer, that is, a monomer having a plurality of ethylenically unsaturated bonds. When the polyfunctional vinyl monomer is used, the rubber particles are easily crosslinked or grafted, and the toughness of the transparent resin composition is further improved.

  The average particle size of the 1,3-butadiene / styrene copolymer rubber particles is preferably in the range of 0.01 to 1 μm, particularly 0, because the resin composition is particularly excellent in transparency and toughness. The thickness is preferably in the range of 0.05 to 0.8 μm. In addition, since the resin composition is particularly excellent in transparency, the 1,3-butadiene / styrene copolymer having an absolute difference in refractive index of 0.02 or less with respect to the refractive index of the N-substituted maleimide / olefin copolymer. The rubber particles are preferably coalesced rubber particles, and particularly preferably 1,3-butadiene / styrene copolymer rubber particles of 0.01 or less.

  The ratio of 1,3-butadiene monomer residue unit and styrene monomer residue unit in the 1,3-butadiene / styrene copolymer rubber particles is arbitrary, and among them, the N-substituted maleimide / olefin 1,3-butadiene / styrene copolymer rubber particles having a smaller refractive index difference than the refractive index of the copolymer, and a resin composition having particularly high transparency and toughness. Monomer residue unit / styrene monomer residue unit = 95/5 to 70/30 (% by weight) is preferable.

  The graft-modified 1,3-butadiene / styrene copolymer rubber can be produced by a method known as a general method for producing a graft copolymer. For example, the above-mentioned 1,3-butadiene / styrene copolymer rubber particles, styrene monomer, acrylonitrile monomer, radical polymerization initiator, solvent, etc. are charged, emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk Examples of the polymerization method include emulsion polymerization. Among these polymerization methods, the emulsion polymerization method is preferable because the production of the graft copolymer is facilitated. Further, the graft-modified 1,3-butadiene / styrene copolymer rubber obtained at that time is styrene that is not bonded as a branch to the 1,3-butadiene / styrene copolymer rubber particles as long as the object of the present invention can be carried out. -An acrylonitrile copolymer may be mixed.

  The proportion of 1,3-butadiene / styrene copolymer rubber particles and styrene / acrylonitrile copolymer in the graft-modified 1,3-butadiene / styrene copolymer rubber is particularly high in transparency, heat resistance, toughness, and melt processability. Therefore, the 1,3-butadiene / styrene copolymer rubber particles are preferably 20 to 95% by weight and the styrene / acrylonitrile copolymer is preferably 5 to 80% by weight.

  Moreover, the ratio of the styrene monomer residue unit and the acrylonitrile monomer residue unit in the styrene / acrylonitrile copolymer is arbitrary, and among them, the N-substituted maleimide / olefin copolymer and the styrene / acrylonitrile copolymer Since the resin composition has excellent compatibility and particularly high transparency and toughness, the styrene monomer residue unit / acrylonitrile monomer residue unit = 60/40 to 85/15 (% by weight). Preferably there is.

  The transparent resin composition of the present invention contains an acrylic plasticizer. The acrylic plasticizer provides good dispersibility of the 1,3-butadiene / styrene copolymer rubber particles in the N-substituted maleimide / olefin copolymer, resulting in excellent transparency and toughness. It becomes what becomes a resin composition. The acrylic plasticizer softens the styrene / acrylonitrile copolymer in the 1,3-butadiene / styrene copolymer rubber, and as a result, becomes a transparent resin composition having excellent toughness. When a plasticizer other than an acrylic plasticizer is used as the plasticizer, the obtained resin composition may not easily achieve the effect of improving toughness, and the transparency may be lowered.

  As the acrylic plasticizer, those generally known as an acrylic plasticizer can be used, and for example, the acrylic plasticizer can be produced by a method described in WO01 / 083619. In addition, (trade name) ARUFON UP1061 (manufactured by Toa Gosei Co., Ltd.), (trade name) ARUFON UP1070 (manufactured by Toa Gosei Co., Ltd.), (trade name) ARUFON UP1080 (manufactured by Toa Gosei Co., Ltd.) and the like are obtained as commercial products. It is also possible. Among them, the acrylic plasticizer has excellent compatibility with the N-substituted maleimide / olefin copolymer, and more excellent transparency when used as a transparent resin composition. Alkyl ester polymer, methacrylic acid alkyl ester polymer, acrylic acid alkyl ester-maleimide compound copolymer, methacrylic acid alkyl ester-maleimide compound copolymer, acrylic acid alkyl ester-aromatic vinyl compound copolymer, alkyl methacrylate It is more preferable that it is at least one plasticizer selected from the group consisting of ester-aromatic vinyl copolymers, and since it becomes a resin composition excellent in transparency and toughness in particular, an alkyl acrylate polymer, Less selected from the group consisting of alkyl methacrylate polymers It is preferably also one or more plasticizers. In addition, the acrylic plasticizer in the present invention refers to an acrylic plasticizer and a methacrylic plasticizer as generally referred to as acrylic, and includes an acrylic acid alkyl ester polymer and a methacrylic acid alkyl ester. The polymer includes not only homopolymers of acrylic acid alkyl esters and methacrylic acid alkyl esters but also copolymers of acrylic acid alkyl esters and methacrylic acid esters.

  Examples of the alkyl acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, dodecyl acrylate, Examples include hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, and the like. These may be used alone or in combination of two or more. .

  Examples of the alkyl methacrylate ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, Examples include hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate, phenoxyethyl methacrylate, and the like. These may be used alone or in combination of two or more. .

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, dimethylstyrene, pt-butylstyrene, vinylnaphthalene, 2,4-dimethylstyrene, and methoxystyrene. , Styrene derivatives such as bromostyrene, fluorostyrene, hydroxystyrene, vinylxylene, aminostyrene, cyanostyrene, nitrostyrene, chloromethylstyrene, acetoxystyrene, p-dimethylaminomethylstyrene, vinylnaphthalene, and the like. Two or more kinds may be used.

  Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide, N-phenylmaleimide and the like, and these may be used alone or in combination of two or more.

In addition, the acrylic plasticizer has a toughness, transparency, melt processability, and a transparent resin composition having excellent volatility resistance and bleed-out resistance. Therefore, the weight average molecular weight is 5 × 10 ² or more. It is preferably 1 × 10 ⁴ or less, particularly preferably 8 × 10 ² or more and 8 × 10 ³ or less.

  The transparent resin composition of the present invention comprises 40 to 98% by weight of the N-substituted maleimide / olefin copolymer, 40 to 1% by weight of the graft-modified 1,3-butadiene / styrene copolymer rubber and the acrylic plastic. 1 to 20% by weight of the agent, and since it becomes a resin composition having an excellent balance of heat resistance, toughness and melt processability, the N-substituted maleimide / olefin copolymer 45 to 94% by weight, The graft-modified 1,3-butadiene / styrene copolymer rubber is preferably composed of 40 to 5% by weight and the acrylic plasticizer of 1 to 15% by weight. Here, when the N-substituted maleimide / olefin copolymer is less than 40% by weight, the heat resistance of the resin composition becomes poor, and when the N-substituted maleimide / olefin copolymer exceeds 98% by weight, the resin composition The toughness of things becomes poor. On the other hand, when the graft-modified 1,3-butadiene / styrene copolymer rubber exceeds 40% by weight, the heat resistance, transparency, and fluidity of the resin composition may be poor, and melt molding may be difficult. When the graft-modified 1,3-butadiene / styrene copolymer rubber is less than 1% by weight, the toughness of the resin composition becomes poor. Further, when the acrylic plasticizer is less than 1% by weight, the fluidity and toughness of the resin composition are insufficient, and when the acrylic plasticizer exceeds 20% by weight, the heat resistance of the resin composition is extremely poor. .

  Since the transparent resin composition of the present invention is particularly excellent in moldability, N-substituted maleimide / olefin copolymer, graft-modified 1,3-butadiene / styrene copolymer rubber, and acrylic It is preferable that 1 to 60 parts by weight of a styrene / acrylonitrile copolymer is blended with 100 parts by weight of the total amount of the plasticizer.

  The transparent resin composition of the present invention comprises the N-substituted maleimide / olefin copolymer, the graft-modified 1,3-butadiene / styrene copolymer rubber, the acrylic plasticizer, and optionally the styrene / The acrylonitrile copolymer can be produced by general mixing and kneading, and as the mixing and kneading apparatus at that time, for example, a single screw extruder, a twin screw extruder, a brabender, a roll, a kneader, Examples thereof include a melt kneading apparatus such as a Banbury mixer. Alternatively, a method may be used in which the respective components are dissolved or dispersed in a solvent and mixed. Furthermore, in the presence of at least one component, a method of producing another component from a raw material of the other component by a method such as modification or polymerization may be used.

  In addition, when the transparent resin composition of the present invention is used as an optical material, it is expected to be irradiated with light such as visible light, ultraviolet light, and infrared light. For the purpose of suppressing deterioration, the transparent resin composition of the present invention may contain, for example, a hindered amine light stabilizer, an ultraviolet absorber, a light stabilizer, a near-infrared absorber, and the like as necessary.

  Furthermore, the transparent resin composition of the present invention contains pigments, lubricants, antiblocking agents, antistatic agents, surfactants, polymer electrolytes, conductive complexes, inorganic fillers, dyes, oils, etc. in addition to the above-described components. You may contain as needed.

  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, multilayer extrusion molding, rotational molding, hot pressing. It can be formed into an injection-molded product, a film, a tube, a sheet, a pipe, a bottle or the like by a method such as molding, blow molding or foam molding.

  As a method for producing a transparent film comprising the transparent resin composition of the present invention, any method may be used, such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, a compression molding method, and the like. A publicly known method can be mentioned. Examples of the melt extrusion method include a T-die method and an inflation method. The transparent film thus obtained may be made into a transparent stretched film by a stretching method. Examples of a biaxial stretching method that can be employed include a tenter method and a tube method, and a uniaxial stretching method includes, for example, a water tank stretching method, Examples thereof include a radiation stretching method, a hot air heating method, a hot plate heating method, and a roll heating method.

  The thickness of the film is preferably 10 to 500 μm, and particularly preferably 20 to 200 μm because of excellent balance between mechanical properties and handling properties. Moreover, since this film becomes a thing excellent in transparency especially, it is preferable that the haze based on JISK7136 is 2% or less.

  The film may be coated with a thin film for the purpose of imparting functions such as gas barrier properties, scratch resistance and chemical resistance. That is, various thermoplastic resins; thermosetting resins having amino groups, imino groups, epoxy groups, silyl groups, etc .; radiation curable resins having acryloyl groups, methacryloyl groups, vinyl groups, etc .; Addition agent, wax, dispersant, pigment, solvent, dye, plasticizer, UV absorber, inorganic filler, etc., gravure roll coating method, Meyer bar coating method, reverse roll coating method, dip coating method, air knife coating method It can be applied by a method such as a calendar coating method, a squeeze coating method, a kiss coating method, a phanten coating method, a spray coating method, or a spin coating method. Furthermore, after coating, a cured thin film layer can be obtained by performing curing by irradiation with radiation or thermal curing by heating as necessary. In printing, a gravure method, an offset method, a flexo method, a silk screen method, or the like can be used. In addition, for the purpose of imparting gas sealability and the like, it may have a metal oxide layer mainly composed of aluminum, silicon, magnesium, zinc, etc., and the metal oxide layer may be formed by vacuum deposition, sputtering, ion It is preferably formed by a plating method, a plasma CVD method or the like.

  Furthermore, the film can be laminated with other films. As a method of laminating, any publicly known method may be used. For example, heat bonding methods such as heat sealing method, impulse sealing method, ultrasonic bonding method, high frequency bonding method; extrusion laminating method, hot melt laminating method, Examples of the laminating method include a dry laminating method, a wet laminating method, a solventless adhesive laminating method, a thermal laminating method, and a coextrusion method. As a film to be laminated, for example, polyester resin film, polyvinyl alcohol resin film, cellulose resin film, polyvinyl fluoride resin film, polyvinylidene chloride resin film, polyacrylonitrile resin film, nylon resin film, polyethylene resin film, polypropylene resin film, Examples thereof include an acetate resin film, a polyimide resin film, a polycarbonate resin film, and a polyacrylate resin film.

  Since the transparent resin composition of the present invention is excellent in transparency, heat resistance, toughness, etc., flat panel displays such as LCD, organic EL, PDP, touch panel, electronic paper, copying machines, printers, facsimiles, optical files, etc. It can be suitably used as an optical film used in the information equipment. Specific examples of the optical film include, for example, a retardation film, a polarizing film protective film, a reflector film, a separator film, a light diffusion film, a transparent electrode film substrate, a display surface protective film, an antiglare film, an antireflection film, and an electromagnetic wave shielding film. , Ultraviolet absorbing film, far infrared absorbing film, near infrared absorbing film and the like.

  Moreover, it can be used conveniently also in uses other than the said optical film, for example, the following uses can be mentioned.

  Recording field: electrostatic recording substrate, OHP, second original drawing, slide film, microfilm, X-ray film.

  Optical and magnetic memory field: Thermo-plastic recording, ferroelectric memory, magnetic tape, ID card, barcode.

  Antistatic field: Meter windows, television cathode ray tubes, clean room windows, semiconductor packaging materials, dust mask films for photomasks.

  Electromagnetic shielding field: measuring instruments, medical equipment, radiation detectors, IC components, CRT.

  Photoelectric conversion element field: solar cell window, optical amplifier, optical sensor.

  Heat ray reflection field: windows (architecture, automobiles, etc.), incandescent bulbs, cooking oven windows, furnace viewing windows, selective permeable membranes.

  Planar heating element field: defroster, aircraft, automobile, freezer, incubator, goggles, medical equipment, liquid crystal display.

  Electronic parts / circuit materials: Capacitors, resistors, thin film composite circuits, leadless LSI chip carrier mounting, dry film resists.

  Electrode field: Paper battery electrodes.

Light transmission filter field: UV cut filter, UV transmission filter, UV transmission visible light absorption filter, color separation filter, color temperature conversion filter, neutral density filter, contrast filter, wavelength calibration filter, interference filter, infrared transmission filter, infrared cut filter , Heat ray absorption filter, heat ray reflection filter Gas selective permeable membrane field: oxygen / nitrogen separation membrane, carbon dioxide separation membrane, hydrogen separation membrane.

  Electrical insulation field: Insulation adhesive tape, motor slot liner, transformer phase insulation, lead wire insulation, high voltage cable insulation coating.

  Polymer sensor field: optical sensor, infrared sensor, acoustic wave sensor, pressure sensor.

  Surface protection field: CRT, furniture, system kitchen, automobile interior and exterior, paint protection film.

  Sliding material field: Hopper / chute lining, belt conveyor sliding material, guide rail sliding material, paper feeding roller for copying machines, computer mouse.

  Porous film field: moisture permeable waterproof material, filter material for microfiltration membrane.

  Other fields: energization heat transfer, printer ribbon, electric cable shield, water leakage prevention film, battery separation film.

  Furthermore, it can be used suitably in applications other than the above films, for example, relays, burn-in sockets, connectors, sensor housings, variable resistors, polyvaricon cases, aeration bobbins used in electrical and electronic equipment; transistors, ICs , LSI, LED sealing materials, IC card IC memory sealing materials, motors, capacitors, switches, sensors and other sealing materials; cameras, VTRs, projectors and other imaging devices Viewfinders, filters, prisms, Fresnel lenses, body materials, etc .; cards, discs, pickup lenses, etc. used in optical recording equipment such as CD players, DVD players, MD players, game machines, etc .; Optical switch, optical connector, etc. Light guide plate, light guide, Fresnel lens, prism sheet, light diffusion sheet, transparent electrode sheet substrate, display surface used in information equipment such as LCD, organic EL, PDP, copying machine, printer, facsimile, touch panel, optical file Protective sheets, ink tanks, covers, body materials, etc .; meters, lamps, lenses, sockets, fuse cases, instrument covers, etc. used in vehicles such as automobiles, trains, etc .; glasses used in the medical equipment field Lenses, contact lenses, endoscope lenses, syringes, artificial dialysers, chemical containers, dentures, ampoule cutter containers, etc .; lighting windows, doors, surveillance camera lenses, carports, terraces, lighting components, etc. in the field of building materials; Used lighting parts, toys, sunglasses, stationery, cosmetic containers, fishing equipment, food Vessel, can be cited for drinking water container or the like.

  The transparent resin composition obtained by the present invention is excellent in transparency, heat resistance, toughness, and melt processability, and therefore can be suitably used as a transparent film.

  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 N-substituted maleimide olefin copolymer measured using the gel permeation chromatography (GPC) (The Tosoh Corporation make, brand name HLC-802A).

~Glass-transition temperature~
Using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., trade name DSC2000), the measurement was performed at a heating rate of 10 ° C./min.

~ Refractive index ~
Based on ASTM D542, the measurement was performed under conditions of a measurement temperature of 25 ° C. and a measurement wavelength of 589 nm.

~ Average particle diameter of rubber particles ~
It measured using the laser diffraction type particle size distribution measuring apparatus (the Horiba make, brand name LA500).

~ Composition of graft modified copolymer rubber ~
Graft-modified copolymer rubber is extracted and separated into soluble and insoluble components with acetone, and ¹ H-NMR measurement of the soluble component is used to determine the styrene monomer residue unit of the styrene / acrylonitrile copolymer and the acrylonitrile monomer residue. The composition was determined by determining the proportion of the base unit and further performing elemental analysis of the insoluble matter.

~ Melt viscosity ~
Using a Koka type flow tester (manufactured by Shimadzu Corporation, trade name: CFT-500), measurement was performed under conditions of a measurement temperature of 270 ° C., a load of 150 kg, a nozzle diameter of 1 mmφ, and a nozzle length of 10 mm.

~ Haze ~
The measurement was made according to JIS K7136.

~ Elongation at break ~
In accordance with ASTM D882, the tensile elongation at break in the take-up direction during film formation was measured.

Synthesis Example 1 (Synthesis of N-methylmaleimide / isobutene copolymer)
A stainless steel autoclave is filled with 100 parts by weight of maleic anhydride / isobutene copolymer (trade name Isoban 6 manufactured by Kuraray Co., Ltd.) and 500 parts by weight of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a solvent. The maleic anhydride / isobutene copolymer was dissolved in NMP by stirring at room temperature. Next, after 40 parts by weight of methylamine was introduced at room temperature, the temperature was raised to 80 ° C. and stirred for 1 hour to carry out amidation reaction of maleic anhydride units. Subsequently, after the temperature was raised to 205 ° C. and the mixture was stirred for 1 hour to carry out an imidization reaction, the mixture was cooled to room temperature and reprecipitated using isopropanol to obtain a copolymer.

From the elemental analysis, infrared absorption spectrum measurement and ¹³ C-NMR measurement, the resulting copolymer was N-methylmaleimide residue / isobutene residue = 0.50 / 0.50 (molar ratio). It was confirmed to be an isobutene copolymer (hereinafter sometimes referred to as A). The number average molecular weight was 60000, and the refractive index was 1.5276.

Synthesis Example 2 (Synthesis of 1,3-butadiene / styrene copolymer rubber particles)
A stainless steel autoclave was charged with 180 parts by weight of deionized water, 3.5 parts by weight of a higher fatty acid soap, and 0.08 parts by weight of sodium hydroxide. After purging with nitrogen, the temperature was raised to 65 ° C. Next, 30% by weight of a monomer mixture consisting of 80 parts by weight of 1,3-butadiene monomer, 20 parts by weight of styrene monomer and 0.2 parts by weight of t-dodecyl mercaptan is added to the autoclave. Then, 0.15 part by weight of potassium persulfate was added and the polymerization reaction was carried out by stirring for 1 hour. Thereafter, the remaining 70% by weight of the monomer mixture was continuously added, and after the addition was completed, the temperature was raised to 75 ° C. and the mixture was further stirred for 1 hour to conduct a polymerization reaction. A latex of coalesced rubber particles (hereinafter sometimes referred to as B-1) was obtained.

  The obtained 1,3-butadiene / styrene copolymer rubber particles had an average particle diameter of 0.1 μm and a refractive index of 1.5287.

Synthesis Example 3 (Synthesis of 1,3-butadiene / butyl acrylate copolymer rubber particles)
A stainless steel autoclave was charged with 200 parts by weight of deionized water, 3.5 parts by weight of higher fatty acid soap, and 1 part by weight of sodium hydrogen carbonate, and the temperature was raised to 65 ° C. after purging with nitrogen. Next, 20% by weight of a monomer mixture consisting of 80 parts by weight of 1,3-butadiene monomer and 20 parts by weight of butyl acrylate monomer was added to the autoclave, and then 0.15 weight of potassium persulfate. A polymerization reaction was carried out by adding 1 part and stirring for 1 hour. Thereafter, the remaining 80% by weight of the monomer mixture was continuously added, and after the addition was completed, the temperature was raised to 75 ° C. and the mixture was further stirred for 1 hour to conduct a polymerization reaction, and 1,3-butadiene / butyl acrylate A latex of copolymer rubber particles (hereinafter sometimes referred to as B-2) was obtained.

  The obtained 1,3-butadiene / butyl acrylate copolymer rubber particles had an average particle diameter of 0.1 μm and a refractive index of 1.5046.

Synthesis Example 4 (Synthesis of butyl acrylate polymer rubber particles)
A stainless steel autoclave was charged with 200 parts by weight of deionized water, 3.5 parts by weight of higher fatty acid soap, and 1 part by weight of sodium hydrogen carbonate, and the temperature was raised to 65 ° C. after purging with nitrogen. Next, 10% by weight of a monomer mixture consisting of 100 parts by weight of butyl acrylate monomer and 0.6 parts by weight of diallyl maleate was added to the autoclave, and then 0.15 part by weight of potassium persulfate was added. The polymerization reaction was carried out by adding and stirring for 1 hour. Thereafter, the remaining 90% by weight of the monomer mixture was continuously added, and after the addition was completed, the temperature was raised to 75 ° C. and the mixture was further stirred for 1 hour to carry out the polymerization reaction, and the latex of butyl acrylate polymer rubber particles (Hereinafter sometimes referred to as B-3).

  The resulting butyl acrylate polymer rubber particles had an average particle size of 0.1 μm and a refractive index of 1.4896.

Synthesis Example 5 (Synthesis of graft-modified 1,3-butadiene / styrene copolymer rubber)
In a stainless steel autoclave, 15 parts by weight of acrylonitrile monomer, 35 parts by weight of styrene monomer, deionized with respect to 100 parts by weight of latex of 1,3-butadiene / styrene copolymer rubber particles obtained in Synthesis Example 2 300 parts by weight of water (including water in latex), 1.5 parts by weight of disproportionated potassium rosinate, 1 part by weight of dextrose, 0.5 parts by weight of sodium pyrophosphate, 0.01 parts by weight of ferrous sulfate, t -It filled with 0.3 weight part of dodecyl mercaptan, and it heated up at 60 degreeC after nitrogen substitution. Next, 0.1 part by weight of cumene hydroperoxide as an initiator was added into the autoclave, and heat generation due to polymerization occurred. After the heat generation was completed, 15 parts by weight of acrylonitrile monomer, 35 parts by weight of styrene monomer, and 0.85 parts by weight of t-dodecyl mercaptan were continuously added. After the addition was completed, cumene hydroper was used as an initiator. 0.05 parts by weight of oxide was added to the autoclave and stirred for 30 minutes to complete the polymerization reaction. Next, the polymerization reaction solution was added and coagulated in an aqueous magnesium sulfate solution, and the coagulated product was washed with water and dried to obtain a graft-modified copolymer rubber (hereinafter referred to as C-1).

  The obtained C-1 was 51% by weight of 1,3-butadiene / styrene copolymer rubber particles, and 26% by weight of acrylonitrile / styrene copolymer grafted on the 1,3-butadiene / styrene copolymer rubber particles. It was confirmed that the rubber was a graft-modified 1,3-butadiene / styrene copolymer rubber composed of 23% by weight of acrylonitrile / styrene copolymer.

  Further, the graft-modified 1,3-butadiene / styrene copolymer rubber (hereinafter referred to as C-1 ′) obtained by extracting and removing ungrafted acrylonitrile / styrene copolymer by subjecting the C-1 to Soxhlet extraction with acetone. Was prepared).

Synthesis Example 6 (Synthesis of graft-modified 1,3-butadiene / styrene copolymer rubber)
Table 1 shows the blending ratio of acrylonitrile monomer, styrene monomer, deionized water, disproportionated potassium rosinate, dextrose, sodium pyrophosphate, ferrous sulfate, t-dodecyl mercaptan, cumene hydroperoxide. Except for the amount, a graft-modified copolymer rubber (hereinafter referred to as C-2, 3) was obtained in the same manner as in Synthesis Example 5.

  The resulting C-2 was 50% by weight of 1,3-butadiene / styrene copolymer rubber particles, and 26% by weight of acrylonitrile / styrene copolymer grafted on the 1,3-butadiene / styrene copolymer rubber particles. Graft modified 1,3-butadiene / styrene copolymer rubber comprising 24% by weight of acrylonitrile / styrene copolymer; C-3 is 66% by weight of 1,3-butadiene / styrene copolymer rubber particles; Graft-modified 1,3-butadiene / styrene copolymer rubber comprising 26% by weight of acrylonitrile / styrene copolymer grafted on 3-butadiene / styrene copolymer rubber particles and 8% by weight of acrylonitrile / styrene copolymer I confirmed that there was.

Synthesis Example 7 (Synthesis of graft-modified 1,3-butadiene / butyl acrylate copolymer rubber)
In a stainless steel autoclave, 15 parts by weight of acrylonitrile monomer, 35 parts by weight of styrene monomer with respect to 100 parts by weight of latex of 1,3-butadiene / butyl acrylate copolymer rubber particles obtained in Synthesis Example 3, 300 parts by weight of deionized water (including water in the latex), 2.5 parts by weight of disproportionated potassium rosinate, 2 parts by weight of dextrose, 1 part by weight of sodium pyrophosphate, 0.01 parts by weight of ferrous sulfate, t -It filled with 0.3 weight part of dodecyl mercaptan, and it heated up at 60 degreeC after nitrogen substitution. Next, 0.1 part by weight of cumene hydroperoxide as an initiator was added into the autoclave, and heat generation due to polymerization occurred. After the heat generation was completed, 15 parts by weight of acrylonitrile monomer, 35 parts by weight of styrene monomer, and 0.85 parts by weight of t-dodecyl mercaptan were continuously added. After the addition was completed, cumene hydroper was used as an initiator. The polymerization reaction was completed by adding 0.35 parts by weight of oxide into the autoclave and stirring for 30 minutes. Next, the polymerization reaction solution was added and coagulated in an aqueous magnesium sulfate solution, and the coagulated product was washed with water and dried to obtain a graft-modified copolymer rubber (hereinafter referred to as C-4).

  The obtained C-4 was 50% by weight of 1,3-butadiene / butyl acrylate copolymer rubber particles, and acrylonitrile / styrene copolymer grafted on the 1,3-butadiene / butyl acrylate copolymer rubber particles. It was confirmed that the rubber was a graft-modified 1,3-butadiene / butyl acrylate copolymer rubber composed of 28% by weight of the polymer and 22% by weight of the acrylonitrile / styrene copolymer.

Synthesis Example 8 (Synthesis example of graft-modified butyl acrylate polymer rubber)
In a stainless steel autoclave, 15 parts by weight of acrylonitrile monomer, 35 parts by weight of styrene monomer, deionized water (in the latex) with respect to 100 parts by weight of latex of the butyl acrylate polymer rubber particles obtained in Synthesis Example 4 300 parts by weight (including water), 2.5 parts by weight of disproportionated potassium rosinate, 2 parts by weight of dextrose, 1 part by weight of sodium pyrophosphate, 0.01 parts by weight of ferrous sulfate, 0.3 parts by weight of t-dodecyl mercaptan The temperature was raised to 60 ° C. after nitrogen replacement. Next, 0.1 part by weight of cumene hydroperoxide as an initiator was added into the autoclave, and heat generation due to polymerization occurred. After the heat generation was completed, 15 parts by weight of acrylonitrile monomer, 35 parts by weight of styrene monomer, and 0.85 parts by weight of t-dodecyl mercaptan were continuously added. After the addition was completed, cumene hydroper was used as an initiator. The polymerization reaction was completed by adding 0.35 parts by weight of oxide into the autoclave and stirring for 30 minutes. Next, the polymerization reaction solution was added and coagulated in an aqueous magnesium sulfate solution, and the coagulated product was washed with water and dried to obtain a graft-modified polymer rubber (hereinafter referred to as C-5).

  The resulting C-5 was 50% by weight of butyl acrylate polymer rubber particles, 15% by weight of acrylonitrile / styrene copolymer grafted on the butyl acrylate polymer rubber particles, and 35% by weight of acrylonitrile / styrene copolymer. It was confirmed that the rubber was a graft-modified butyl acrylate polymer rubber comprising:

Example 1
75% by weight of N-methylmaleimide / isobutene copolymer obtained in Synthesis Example 1, 20% by weight of C-1 obtained in Synthesis Example 5, and an acrylic plasticizer (trade name ARUFON UP1061 manufactured by Toagosei Co., Ltd.) , Weight average molecular weight = 1600) (hereinafter referred to as D-1) in a proportion of 5% by weight, extruded through a 30 mmφ twin-screw extruder (trade name: TEX30, manufactured by Nippon Steel Works, Ltd.), transparency A resin composition was obtained. The transparent resin composition obtained had a glass transition temperature of 146 ° C. and a melt viscosity of 240 Pa · s.

  Next, the obtained transparent resin composition was subjected to a twin-screw extruder equipped with a T die, and extruded under conditions of a T die temperature of 260 to 285 ° C. and a cooling roll temperature of 110 to 140 ° C. and having a thickness of 100 μm. A film was obtained. Table 3 shows the results of physical properties measured using this transparent film. The obtained transparent film was excellent in transparency, toughness, and heat resistance.

Example 2
A transparent resin composition and a transparent film were obtained in the same manner as in Example 1 except that C-2 obtained by Synthesis Example 6 was used instead of C-1 obtained by Synthesis Example 5, and the evaluation was made. Went. The evaluation results are shown in Table 3.

  The obtained transparent resin composition had a glass transition temperature of 146 ° C. and a melt viscosity of 232 Pa · s, and the obtained transparent film was excellent in transparency, toughness, and heat resistance.

Example 3
A transparent resin composition and a transparent film were obtained in the same manner as in Example 1 except that C-3 obtained by Synthesis Example 6 was used instead of C-1 obtained by Synthesis Example 5, and evaluation thereof was performed. Went. The evaluation results are shown in Table 3.

  The obtained transparent resin composition had a glass transition temperature of 149 ° C. and a melt viscosity of 221 Pa · s, and the obtained transparent film was excellent in transparency, toughness, and heat resistance.

Example 4
The same method as in Example 1 except that instead of D-1, an acrylic plasticizer (manufactured by Toa Gosei Co., Ltd., trade name: ARUFON UP1070, weight average molecular weight = 2000) (hereinafter referred to as D-2) was used. Thus, a transparent resin composition and a transparent film were obtained and evaluated. The evaluation results are shown in Table 3.

  The obtained transparent resin composition had a glass transition temperature of 145 ° C. and a melt viscosity of 250 Pa · s, and the obtained transparent film was excellent in transparency, toughness, and heat resistance.

Example 5
The same method as in Example 1 except that instead of D-1, an acrylic plasticizer (manufactured by Toa Gosei Co., Ltd., trade name: ARUFON UP1080, weight average molecular weight = 6000) (hereinafter referred to as D-3) was used. Thus, a transparent resin composition and a transparent film were obtained and evaluated. The evaluation results are shown in Table 3.

  The obtained transparent resin composition had a glass transition temperature of 147 ° C. and a melt viscosity of 283 Pa · s, and the obtained transparent film was excellent in transparency, toughness, and heat resistance.

Example 6
80% by weight instead of 75% by weight of N-methylmaleimide / isobutene copolymer, 15% by weight of C-2 obtained by Synthesis Example 6 instead of 20% by weight of C-1 obtained by Synthesis Example 5 A transparent resin composition and a transparent film were obtained in the same manner as in Example 1 except that they were evaluated. The evaluation results are shown in Table 3.

  The obtained transparent resin composition had a glass transition temperature of 148 ° C. and a melt viscosity of 215 Pa · s, and the obtained transparent film was excellent in transparency, toughness, and heat resistance.

Example 7
Instead of 75% by weight of N-methylmaleimide / isobutene copolymer, 72.5% by weight, C-1 obtained by Synthesis Example 5 was replaced by 20% by weight, and C-3 obtained by Synthesis Example 6 was replaced by 20% by weight. A transparent resin composition and a transparent film were obtained by the same method as in Example 1 except that 7.5% by weight was used instead of 5% by weight and D-1 was evaluated. The evaluation results are shown in Table 3.

  The obtained transparent resin composition had a glass transition temperature of 143 ° C. and a melt viscosity of 197 Pa · s, and the obtained transparent film was excellent in transparency, toughness, and heat resistance.

Example 8
A transparent resin composition and a transparent film were obtained and evaluated by the same method as in Example 1 except that C-1 ′ was used instead of C-1 obtained in Synthesis Example 5. The evaluation results are shown in Table 3.

  The obtained transparent resin composition had a glass transition temperature of 148 ° C. and a melt viscosity of 399 Pa · s, and the obtained transparent film was excellent in transparency, toughness, and heat resistance.

Comparative Example 1
The N-methylmaleimide / isobutene copolymer alone was evaluated by the same method as in Example 1. The evaluation results are shown in Table 4.

  The glass transition temperature was 159 ° C., the melt viscosity was 322 Pa · s, and the obtained film was inferior in toughness.

Comparative Example 2
Except not having used D-1, the resin composition and the film were obtained by the method similar to Example 1, and the evaluation was performed. The evaluation results are shown in Table 4.

  The obtained resin composition had a glass transition temperature of 154 ° C. and a melt viscosity of 487 Pa · s, and the fluidity was slightly inferior. Moreover, the obtained film was inferior in toughness.

Comparative Example 3
A resin composition and a film were obtained and evaluated in the same manner as in Example 1 except that C-4 obtained by Synthesis Example 7 was used instead of C-1 obtained by Synthesis Example 5. The evaluation results are shown in Table 4.

  The obtained resin composition had a glass transition temperature of 146 ° C. and a melt viscosity of 255 Pa · s, and the resulting film was inferior in transparency.

Comparative Example 4
A resin composition and a film were obtained and evaluated in the same manner as in Example 1 except that C-5 obtained by Synthesis Example 8 was used instead of C-1 obtained by Synthesis Example 5. The evaluation results are shown in Table 4.

  The obtained resin composition had a glass transition temperature of 146 ° C. and a melt viscosity of 228 Pa · s, and the obtained film was inferior in transparency and toughness.

Comparative Example 5
Example 1 except that D-1 was a phthalate polyester plasticizer (manufactured by Kuraray Co., Ltd., trade name Kuraray Polyol P-1030, number average molecular weight = 1000) (hereinafter referred to as D-4). The resin composition and the film were obtained by the method and evaluated. The evaluation results are shown in Table 4.

  The obtained resin composition had a glass transition temperature of 145 ° C. and a melt viscosity of 268 Pa · s, and the obtained film had poor toughness.

Comparative Example 6
The same method as in Example 1 except that D-1 was changed to dipentaerythritol plasticizer (manufactured by J Plus Co., Ltd., trade name D600, number average molecular weight = 943) (hereinafter referred to as D-5). Thus, a resin composition and a film were obtained and evaluated. The evaluation results are shown in Table 4.

  The obtained resin composition had a glass transition temperature of 148 ° C. and a melt viscosity of 260 Pa · s, and the obtained film was inferior in transparency and toughness.

Comparative Example 7
Similar to Example 1 except that N-methylmaleimide / isobutene copolymer was replaced by 44% by weight instead of 75% by weight and C-1 obtained in Synthesis Example 5 was replaced by 51% by weight instead of 20% by weight. A resin composition and a film were obtained by the method and evaluated. The evaluation results are shown in Table 4.

  The obtained resin composition had a glass transition temperature of 122 ° C., a melt viscosity of 944 Pa · s, and was slightly inferior in fluidity. Moreover, the obtained film was inferior in heat resistance, transparency, and toughness.

Comparative Example 8
63% by weight instead of 75% by weight of N-methylmaleimide / isobutene copolymer, 16% by weight of C-1 obtained in Synthesis Example 5 instead of 20% by weight, and 5% by weight of D-1 A resin composition and a film were obtained and evaluated by the same method as in Example 1 except that the content was 21% by weight. The evaluation results are shown in Table 4.

  The obtained resin composition had a glass transition temperature of 71 ° C. and a melt viscosity of 78 Pa · s, and the obtained film had poor heat resistance.

Claims (5)

It consists of 40 to 60 mol% of units represented by the following general formula (I) and 60 to 40 mol% of units represented by the following general formula (II), and has a number average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less. N-substituted maleimide / olefin copolymer 40-98% by weight, graft modified 1,3-butadiene / styrene copolymer obtained by grafting styrene / acrylonitrile copolymer onto 1,3-butadiene / styrene copolymer rubber particles A transparent resin composition comprising 40 to 1% by weight of a combined rubber and 1 to 20% by weight of an acrylic plasticizer.

(Here, R1 represents at least one organic group selected from an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms.)

(Here, R2 and R3 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.) Acrylic plasticizer is acrylic acid alkyl ester polymer, methacrylic acid alkyl ester polymer, acrylic acid alkyl ester-maleimide compound copolymer, methacrylic acid alkyl ester-maleimide compound copolymer, acrylic acid alkyl ester-aromatic vinyl. 2. The transparent resin composition according to claim 1, wherein the transparent resin composition is at least one plasticizer selected from the group consisting of a compound copolymer and an alkyl methacrylate-aromatic vinyl compound copolymer. 3. The transparent resin composition according to claim 1, wherein the transparent resin composition is an acrylic plasticizer having a weight average molecular weight of 5 × 10 ² or more and 1 × 10 ⁴ or less. 1 to 60 parts by weight of styrene / acrylonitrile copolymer is further added to 100 parts by weight of the total amount of N-substituted maleimide / olefin copolymer, graft-modified 1,3-butadiene / styrene copolymer rubber and acrylic plasticizer. The transparent resin composition according to claim 1, wherein the composition is blended. A transparent film comprising the transparent resin composition according to claim 1.