JP4984419B2 - Plastic molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molded product with excellent properties such as scratch, weather and heat resistances, and transparency despite of being capable of melt molding such as injection molding. <P>SOLUTION: The resin molded product contains (i) 25-50 wt.% of glutaric anhydride structure unit shown by general formula (1), (ii) 50-75 wt.% of an alkyl unsaturated carboxylate unit, (iii) 5 wt.% or less of an unsaturated carboxylic acid unit and/or (iv) 10 wt.% or less of another vinyl monomer unit. The resin molded product has a hard coat film on at least one surface of the base body composed of a thermoplastic resin molded product of the thermoplastic polymer (A). The composition ratios X (wt.%) of the glutaric anhydride structure unit shown by (i) general formula (1) in the copolymer (A) and Y (wt.%) of (iii) the unsaturated carboxylic acid unit represent 0&le;Y/X&le;0.2. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a resin molded article having excellent transparency, scratch resistance, abrasion resistance, heat resistance, weather resistance, and the like, and further excellent adhesion between a hard coat layer and a substrate.

  Resin-molded products are widely used for building materials, industrial materials, automobile parts, and the like, taking advantage of their low cost, light weight, excellent moldability, and impact resistance. In recent years, for example, due to the widespread use of automobile navigation systems, mobile phones, handy cameras, etc., the use range of the equipment is severe under the use environment conditions that require weather resistance and (humidity) heat resistance such as outdoors and in car interiors. Has expanded to. When used under such harsh environmental conditions, a molded product having a polymethyl methacrylate resin as a substrate has excellent transparency and weather resistance, but has a problem of deformation due to low heat resistance. . Molded products using polycarbonate resin as a substrate are excellent in heat resistance and impact resistance, but are inferior in weather resistance, so deterioration of appearance such as coloring due to deterioration due to light or hydrolysis, and machinery such as impact resistance Applications are limited due to the problem of causing deterioration in physical properties.

  In addition, resin molded products generally have low surface hardness, and the surface is damaged due to scratches during product processing, installation, or when using equipment equipped with these resin components, resulting in a decrease in yield. There is a problem that the product value is likely to decrease.

  As a means for improving such a defect, a method of performing a hard coat treatment on the surface of a resin molded product has been conventionally studied. However, when a base resin having low heat resistance is used, there is a problem that in the drying process after hard coating, the heat resistance is low, so that the base material is thermally deformed and flatness is likely to deteriorate. .

  As a method for solving such problems, it contains a glutaric anhydride unit obtained by heating a copolymer containing an unsaturated carboxylic acid monomer unit using an extruder to cause a cyclization reaction. A method of hard-coating the copolymer resin sheet is disclosed (Patent Document 1).

  However, as described in the above document, when an ordinary extruder having L / D = 28 is used for the cyclization reaction, the residence time in the extruder is short, and the cyclization reaction is sufficiently performed. Unable to proceed, a large amount of unreacted unsaturated carboxylic acid monomer units remain. For this reason, there are problems that silver or the like is generated at the time of heat forming, and that strong adhesiveness cannot be obtained when the hard coat treatment is performed, and sufficient scratch resistance cannot be imparted.

Moreover, in order to fully advance a cyclization reaction, the method using the extruder which is L / D = 44.5 is disclosed (patent document 2). However, there is no disclosure regarding the hard coat in the above-mentioned document, and the factor and mechanism affecting the adhesiveness, particularly the adhesiveness under harsh usage environments such as high temperature and high humidity, were unknown.
Japanese Patent Laid-Open No. 7-268036 (second embodiment) JP 2004-2711 A (page 2, example)

  The inventors of the present invention have made extensive studies in order to solve the above-mentioned drawbacks, and by using a specific thermoplastic polymer, while being capable of melt processing molding such as injection molding, excellent transparency, weather resistance, heat resistance, etc. Thus, the present inventors have found that a resin molded product having excellent properties and excellent adhesion to the hard coat layer and significantly improved scratch resistance on the surface can be obtained. The subject of this invention is providing the resin molded product excellent in scratch resistance, transparency, a weather resistance, heat resistance, etc.

In order to solve the above problems, the present invention has the following configuration. That is,
[1] Glutaric anhydride structural unit represented by the following general formula (1): 25 to 50% by weight, (ii) 50 to 75% by weight of unsaturated carboxylic acid alkyl ester unit, (iii) unsaturated carboxylic acid unit 5 (B) The core layer is a butyl acrylate / styrene polymer with respect to 100 parts by weight of the thermoplastic polymer (A) having 10% by weight or less of (iv) other vinyl monomer units. Then, the outermost layer is molded into a thermoplastic resin composition obtained by heat- melting and kneading 1 to 100 parts by weight of a rubber-containing polymer which is a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit. A resin molded product formed by forming a hard coat film on at least one surface of a substrate made of a thermoplastic resin molded product, and (i) the above general formula (A) in the thermoplastic polymer (A) Guru represented by 1) 0 ≦ Y / X ≦ 0.2, where X (wt%) is the composition ratio of the tartric anhydride structural unit and (iii) Y (wt%) is the composition ratio of the unsaturated carboxylic acid unit. A resin molded product characterized by

（Ｒ^１、Ｒ^２は、同一または相異なる水素原子または炭素数１〜５のアルキル基を表す）

(R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms)

[ 2 ] A thermoplastic polymer (A) is obtained by converting a raw copolymer containing (ii) an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit into a screw length / diameter ratio (L / D ) is 30 or more, and heat treatment using a 110 following the extruder, (b) by performing a dehydration and / or (b) dealcoholization reaction, be those obtained in [1], wherein the The resin molded product described.

[ 3 ] The resin molded product according to [1] or [2] , wherein a single-layer or multilayer antireflection film is further formed by vapor deposition of an inorganic compound on the surface of the film having hard coat properties.

[ 4 ] The resin molded product according to any one of [1] to [ 3 ], wherein the resin molded product is an injection molded product.

[ 5 ] The resin molded product according to any one of [1] to [ 4 ], wherein the resin molded product is a sheet.

  The resin molded product formed by forming a film having hard coat properties of the present invention is excellent in colorless transparency, in particular, has a highly scratch-resistant surface, and is excellent in heat resistance and durability.

  Hereinafter, the thermoplastic polymer of the present invention will be specifically described.

  As described above, the thermoplastic polymer (A) of the present invention includes (i) a glutaric anhydride-containing unit represented by the following general formula (1), (ii) an unsaturated carboxylic acid alkyl ester unit, (iii) It is a copolymer having an unsaturated carboxylic acid unit and / or (iv) another vinyl monomer unit.

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.)
The (i) glutaric anhydride-containing unit contained in the thermoplastic polymer (A) in the present invention is 25 to 50% by weight, preferably 30 to 45% by weight, in the copolymer. When the glutaric anhydride content unit is less than 25% by weight, not only the effect of improving heat resistance is reduced, but also optical isotropy and surface hardness tend to be lowered. Further, (ii) the unsaturated carboxylic acid alkyl ester unit is 50 to 75% by weight, preferably 55 to 70% by weight. Further, (iii) the unsaturated carboxylic acid unit is preferably 5% by weight or less, more preferably 3% by weight or less, and most preferably 1% by weight or less. In addition, (iv) other vinyl monomer units are 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, and most preferably 1% by weight or less.

  In the thermoplastic polymer (A) in the present invention, the composition ratio of (i) glutaric anhydride units in the polymer is X (% by weight), and (iii) the composition ratio of unsaturated carboxylic acid units is Y ( Weight%), it is necessary that 0 ≦ Y / X ≦ 0.2. More preferably, 0 ≦ Y / X ≦ 0.15, and most preferably 0 ≦ Y / X ≦ 0.1. When Y / X is larger than 0.2, the adhesion with the hard coat layer is lowered, and excellent surface hardness is not exhibited, and the object of the present invention cannot be achieved.

In general, an infrared spectrophotometer or a proton nuclear magnetic resonance ( ¹ H-NMR) measuring instrument is used for quantification of each component unit in the thermoplastic polymer (A) of the present invention. In infrared spectroscopy, glutaric anhydride containing units, absorption of 1800 cm ^-1 and 1760 cm ^-1 are characteristic can be distinguished from unsaturated carboxylic acid units and unsaturated carboxylic acid alkyl ester unit. In the ¹ H-NMR method, the copolymer composition can be determined from the integral ratio of the spectrum. For example, in the case of a copolymer consisting of a glutaric anhydride-containing unit, a methacrylic acid unit, and a methyl methacrylate unit, the attribution of the spectrum measured in dimethyl sulfoxide heavy solvent has a peak of 0.5 to 1.5 ppm. Α-methyl group hydrogen of methacrylic acid, methyl methacrylate and glutaric anhydride ring compound, peak of 1.6-2.1 ppm is hydrogen of methylene group of polymer main chain, peak of 3.5 ppm is methyl methacrylate Carboxylic acid ester (—COOCH ₃ ) hydrogen, 12.4 ppm peak methacrylic acid carboxylic acid hydrogen. In addition to the above, in the case of a copolymer containing styrene as another copolymer component, hydrogen of an aromatic ring of styrene is seen at 6.5 to 7.5 ppm, and the copolymer is similarly obtained from the spectral ratio. The composition can be determined.

  As the unsaturated carboxylic acid unit (iii), those having a structure represented by the following general formula (2) are preferable.

（ただし、Ｒ^３は水素または炭素数１〜５のアルキル基を表す）

(However, R ³ represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)

  The unsaturated carboxylic acid alkyl ester unit (ii) preferably has a structure represented by the following general formula (3).

（ただし、Ｒ^４は水素または炭素数１〜５のアルキル基を表し、Ｒ^５は炭素数１〜６の脂肪族もしくは脂環式炭化水素基または１個以上炭素数以下の数の水酸基もしくはハロゲンで置換された炭素数１〜６の脂肪族もしくは脂環式炭化水素基を示す）

(However, R ⁴ represents hydrogen or an alkyl group having 1 to ⁵ carbon atoms, and R ⁵ represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, or a hydroxyl group or halogen having a number of 1 to ⁵ carbon atoms. A C1-C6 aliphatic or alicyclic hydrocarbon group substituted with

  The thermoplastic polymer (A) preferably has a weight average molecular weight of 30,000 to 150,000, more preferably 50,000 to 130,000, and particularly preferably 70,000 to 110,000. When the weight average molecular weight is within this range, coloring during heat deaeration in the subsequent step can be reduced, a polymer having a small yellowness can be obtained, and the mechanical strength of the molded product can also be increased. . In addition, the weight average molecular weight as used in the field of this invention shows the weight average molecular weight in the absolute molecular weight measured by multi-angle light scattering gel permeation chromatography (GPC-MALLS).

  The thermoplastic polymer (A) preferably has a glass transition temperature (Tg) of 130 ° C. or higher from the viewpoint of heat resistance. The glass transition temperature is more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. Moreover, as an upper limit, it is about 170 degreeC normally. If the glass transition temperature is less than 130 ° C., problems such as deformation of the substrate may occur during post-processing steps such as formation of a film having a hard coat property and imparting antireflection properties. In addition, the glass transition temperature here is a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer).

  Such a thermoplastic polymer (A) containing the glutaric anhydride-containing unit represented by the general formula (1) of the present invention can be basically produced by the method shown below. That is, an unsaturated carboxylic acid monomer and an unsaturated carboxylic acid alkyl ester monomer that give the glutaric anhydride-containing unit (i) represented by the general formula (1) by the subsequent heating step are copolymerized, The raw copolymer (a) is obtained. At that time, when the other vinyl monomer unit (iv) is included, a vinyl monomer giving the unit may be copolymerized. The obtained original copolymer (a) is heated in the presence or absence of a suitable catalyst, and an intramolecular cyclization reaction is carried out by dealcoholization and / or dehydration, whereby a thermoplastic polymer (A) is obtained. Can be manufactured. In this case, typically, by heating the original copolymer (a), by dehydration reaction between the carboxyl groups of two adjacent unsaturated carboxylic acid units (iii), or adjacent unsaturated The dealcoholization reaction between the carboxylic acid unit (iii) and the unsaturated carboxylic acid alkyl ester unit (ii) produces 1 unit of the (i) glutaric anhydride-containing unit.

  As the unsaturated carboxylic acid monomer used in this case, any unsaturated carboxylic acid monomer that can be copolymerized with another vinyl compound can be used. As a preferable unsaturated carboxylic acid monomer, the following general formula (4)

（ただし、Ｒ^３は水素または炭素数１〜５のアルキル基を表す）
で表される化合物、マレイン酸、および無水マレイン酸の加水分解物などが挙げられる。特に熱安定性が優れる点でアクリル酸、メタクリル酸が好ましく、より好ましくはメタクリル酸である。これらはその１種または２種以上用いることができる。なお、上記一般式（４）で表される不飽和カルボン酸単量体は、共重合すると上記一般式（２）で表される構造の不飽和カルボン酸単位(iii)を与える。

(However, R ³ represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)
And a hydrolyzate of maleic anhydride and maleic anhydride. In particular, acrylic acid and methacrylic acid are preferable from the viewpoint of excellent thermal stability, and methacrylic acid is more preferable. These can be used alone or in combination. The unsaturated carboxylic acid monomer represented by the general formula (4) gives an unsaturated carboxylic acid unit (iii) having a structure represented by the general formula (2) when copolymerized.

  Moreover, what is represented by following General formula (5) can be mentioned as a preferable example of an unsaturated carboxylic-acid alkylester monomer.

（ただし、Ｒ^４は水素または炭素数１〜５のアルキル基を表し、Ｒ^５は炭素数１〜６の脂肪族基もしくは脂環式炭化水素基を示す。ここで、Ｒ^５は１個以上炭素数以下の数の水酸基もしくはハロゲンで置換されていてもよい。）

(However, R ⁴ represents hydrogen or an alkyl group having 1 to ⁵ carbon atoms, and R ⁵ represents an aliphatic group or alicyclic hydrocarbon group having 1 to 6 carbon atoms. Here, R ⁵ is one or more. (It may be substituted with a hydroxyl group or halogen having a number of carbon atoms or less.)

  Of these, acrylic esters and / or methacrylic esters are particularly preferred. The unsaturated carboxylic acid alkyl ester monomer represented by the general formula (5) gives an unsaturated carboxylic acid alkyl ester unit (ii) having a structure represented by the general formula (3) when copolymerized. .

  Specific preferred examples of the unsaturated carboxylic acid alkyl ester monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, N-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, chloromethyl acrylate, chloromethyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,4,5, acrylic acid 6-Penta Examples include droxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, and 2,3,4,5-tetrahydroxypentyl methacrylate. Among them, methyl methacrylate is most preferably used. These can be used alone or in combination of two or more thereof.

  Moreover, in manufacture of the copolymer (a) used by this invention, you may use another vinyl monomer in the range which does not impair the effect of this invention. This other vinyl monomer, when copolymerized, gives the other vinyl monomer unit (iv). Preferred specific examples of other vinyl monomers include aromatics such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and pt-butylstyrene. Vinyl monomers, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic anhydride, itaconic anhydride, N-methyl Maleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylene acrylate Aminoethyl, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p- Examples include aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, and 2-styryl-oxazoline. From the viewpoint of transparency, optical isotropy, and solvent resistance, a monomer that does not contain an aromatic ring can be used more preferably. These may be used alone or in combination of two or more.

  As a polymerization method of the copolymer (a), a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization or the like basically by radical polymerization can be used. Solution polymerization, bulk polymerization, suspension polymerization, and precipitation polymerization are particularly preferable in terms of fewer impurities, and among these, solution polymerization and precipitation polymerization that do not use water as a polymerization solvent are preferable. In the case of a polymerization method using water as a medium (for example, suspension polymerization or emulsion polymerization), since the solubility of the unsaturated carboxylic acid monomer in water is large, the copolymerization with the unsaturated carboxylic acid ester is prepared as designed. There is a tendency not to proceed, and there is a tendency that many appearance defects and coarse foreign matters are observed in the resin molded product of the present invention.

  About polymerization temperature, it is preferable to superpose | polymerize at the polymerization temperature of 95 degrees C or less from a viewpoint of a color tone. Furthermore, in order to further suppress coloring after the heat treatment, a preferable polymerization temperature is 85 ° C. or lower, and particularly preferably 75 ° C. or lower. The lower limit of the polymerization temperature is not particularly limited as long as the polymerization proceeds, but is preferably 50 ° C. or higher, more preferably 60 ° C. or higher from the viewpoint of productivity in consideration of the polymerization rate. For the purpose of improving the polymerization yield or polymerization rate, the polymerization temperature can be raised as the polymerization proceeds. Also in this case, it is preferable to control the upper limit temperature to be raised to 95 ° C. or lower, and it is preferable to carry out the polymerization initiation temperature at a relatively low temperature of 75 ° C. or lower. The polymerization time is not particularly limited as long as it is a sufficient time to obtain the required degree of polymerization, but is preferably in the range of 60 to 360 minutes, particularly preferably in the range of 90 to 180 minutes from the viewpoint of production efficiency.

  In the present invention, the preferred proportion of these monomer mixtures used in the production of the copolymer (a) is such that the total amount of the monomer mixture is 100% by weight and the unsaturated carboxylic acid monomer is 15 to 50% by weight. %, More preferably 20 to 45% by weight, and the unsaturated carboxylic acid alkyl ester monomer is 50 to 85% by weight, more preferably 55 to 80% by weight. When other vinyl monomers copolymerizable with these are used, the preferred ratio is 0 to 10% by weight. When the other vinyl monomer is an aromatic vinyl monomer, the preferable ratio is 0 to 5% by weight, and the more preferable ratio is 0 to 3% by weight.

  When the content of the unsaturated carboxylic acid monomer is less than 15% by weight, when the thermoplastic polymer (A) is produced by heating the copolymer (a), the general formula (1) The amount of the glutaric anhydride-containing unit (i) represented is reduced, and the heat resistance improvement effect of the thermoplastic polymer (A) tends to be reduced. On the other hand, when the content of the unsaturated carboxylic acid monomer (iii) exceeds 50% by weight, the unsaturated polymer is produced when the thermoplastic polymer (A) is produced by heating the copolymer (a). The carboxylic acid unit (iii) tends to remain in a large amount, and the colorless transparency and residence stability of the thermoplastic polymer (A) tend to decrease.

  As described above, the thermoplastic polymer (A) of the present invention preferably has a weight average molecular weight of 30,000 to 150,000. The thermoplastic polymer (A) having such a molecular weight is obtained by controlling the copolymer (a) to 30,000 to 150,000 in a weight average molecular weight in advance during the production of the copolymer (a). Can be achieved.

  As for the molecular weight control method of the copolymer (a), for example, the addition amount of radical polymerization initiators such as azo compounds and peroxides, or alkyl mercaptans, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, It can be controlled by the addition amount of a chain transfer agent such as triethylamine. In particular, a method of controlling the amount of alkyl mercaptan added as a chain transfer agent can be preferably used from the viewpoint of stability of polymerization, ease of handling, and the like.

  Examples of the alkyl mercaptan used in the present invention include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and the like. Among them, t-dodecyl mercaptan, n-dodecyl mercaptan is preferably used.

  The addition amount of these alkyl mercaptans is preferably 0.2 to 5 parts by weight, more preferably 0.3 to 4 parts by weight with respect to 100 parts by weight of the total amount of the monomer mixture in order to control the molecular weight to a preferable level. More preferably, it is 0.4 to 3 parts by weight.

  The method for producing a thermoplastic polymer (A) containing a glutaric anhydride-containing unit by heating the copolymer (a) in the present invention, performing an intramolecular cyclization reaction by dehydration and / or dealcoholization, As long as the copolymer composition of the thermoplastic polymer is finally within the scope of the present invention, there is no particular limitation. However, a method of passing the copolymer (a) through a heated extruder having a vent or an inert gas atmosphere Alternatively, a method of heating and devolatilizing under vacuum is preferable. When an intramolecular cyclization reaction is carried out by heating in the presence of oxygen, the yellowness tends to deteriorate, so it is preferable to sufficiently replace the system with an inert gas such as nitrogen. As a particularly preferred apparatus, for example, a single-screw extruder, a twin-screw or three-screw extruder equipped with a “unimelt” type screw, a continuous or batch kneader type kneader, or the like can be used.

  In addition, the heating and devolatilization time in this case is preferably 3 minutes to 60 minutes, more preferably 5 minutes to 30 minutes, especially in order to make the copolymer composition of the thermoplastic polymer within the scope of the present invention. Preferably it is the range for 7 to 20 minutes. When an extruder is used as the heating devolatilizer, the length / diameter ratio of the extruder screw (L / D) from the viewpoint of allowing sufficient intramolecular cyclization reaction to proceed and preventing abnormal heat retention. Is preferably 30 or more and 110 or less. In particular, an extruder having 40 or more and 90 or less can be preferably used. When an extruder with a short L / D is used, it is difficult to make the copolymer composition of the thermoplastic polymer within the scope of the present invention, that is, a large amount of unreacted unsaturated carboxylic acid units remain. The reaction re-advances during the thermoforming process, and there is a tendency that silver and bubbles are seen in the molded product, and a sufficient surface hardness cannot be obtained even after hard coating.

  Also, among the extruders, by using a biaxial / uniaxial composite continuous kneading extruder, it is excellent in colorless transparency, and a hard-coated resin molded product tends to be excellent in surface hardness, so it is preferably used. be able to. Here, the biaxial / single-shaft combined continuous kneading extruder is a biaxial screw portion in which a first shaft and a second shaft in which a screw portion is formed are arranged in parallel in an extruder casing, and a biaxial screw A single screw portion in which a first shaft extended from the screw portion is disposed, and a flow rate adjusting mechanism is provided in a communication portion between the biaxial screw portion and the single screw portion, and the casing communicates with the biaxial screw portion. A twin-screw / single-shaft composite continuous kneading extruder having a raw material supply port and a discharge port communicating with the end of the extended first shaft, and as a commercially available extruder of this type Is an “HTM type extruder” manufactured by CTE. When the copolymer (a) as a raw material is heated in a continuous manner and the cyclization reaction proceeds, due to the progress of the reaction, the melt viscosity increases, and the heat generated by the shearing of the extrusion apparatus increases. There is a tendency for coloring due to thermal decomposition of the molecular main chain to increase. Further, the shear heat generation becomes larger when melt kneading with a twin screw than with a single screw. On the other hand, from the viewpoint of reaction rate, it is preferable to melt and knead with a twin screw. From the above, by using a specific twin-screw / single-screw composite continuous kneading extruder, in the initial reaction stage where the melt viscosity is relatively low, the melt viscosity is secured while ensuring a sufficient reaction speed with a twin screw. In the late stage of the reaction when the temperature is relatively high, it is considered that the reaction proceeds sufficiently while the thermal decomposition of the molecular main chain is suppressed by heat treatment with a single screw part that suppresses shearing heat generation.

  The thermoplastic polymer (A) thus obtained is excellent in color tone and mechanical properties, and leads to excellent adhesion with a film having hard coat properties, specifically excellent surface hardness of the resin molded product after hard coating. Inferred.

  An apparatus having a structure capable of introducing an inert gas such as nitrogen is more preferable. For example, as a method for introducing an inert gas such as nitrogen into a twin-screw extruder, a method of connecting a pipe of an inert gas stream of about 10 to 100 liters / minute from the upper part and / or the lower part of the hopper can be mentioned. .

  The temperature for devolatilization by the above method is a temperature at which an intramolecular cyclization reaction occurs due to dehydration and / or dealcoholization, and finally the copolymer composition of the thermoplastic polymer is within the scope of the present invention. Although there is no restriction | limiting in particular, Preferably it is the range of 180-320 degreeC, Most preferably, it is the range of 200-300 degreeC.

  Furthermore, in the present invention, at least one selected from acids, alkalis and salt compounds is added as a catalyst for promoting the cyclization reaction to glutaric anhydride when the copolymer (a) is heated by the above method or the like. can do. The addition amount is preferably about 0.01 to 1 part by weight per 100 parts by weight of the copolymer (a). Examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, and methyl phosphate. Examples of the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides and the like. Furthermore, examples of the salt compound catalyst include metal acetates, metal stearates, metal carbonates, ammonium salts including various alkylammonium salts, and the like. However, it is preferable to add the catalyst in such a range that the color of the catalyst does not adversely affect the coloring of the thermoplastic polymer and the transparency is not lowered. Among them, the compound containing an alkali metal can be preferably used because it exhibits an excellent reaction promoting effect with a relatively small addition amount. Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkoxide compounds such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, and potassium phenoxide, lithium acetate And organic carboxylates such as sodium acetate, potassium acetate and sodium stearate. In particular, sodium hydroxide, sodium methoxide, lithium acetate, and sodium acetate can be preferably used.

  The thermoplastic polymer (A) used in the present invention usually has a surface hardness of 3H or more as measured by pencil hardness (JIS-K-5401), and in a preferred embodiment, the surface hardness is 4H or more. Have. Therefore, sufficient hard coat performance can be obtained even if the film thickness is relatively thin.

  Further, the total light transmittance of the thermoplastic copolymer used in the present invention is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.

  In the present invention, by adding (B) a rubber-containing polymer to the (A) thermoplastic polymer, (A) excellent impact resistance without significantly detracting from the excellent characteristics of the thermoplastic polymer. Can be granted.

(B) The rubber-containing polymer is composed of a layer containing one or more rubber-like polymers and one or more layers made of different polymers, and one or more layers of rubber inside. structure having a layer including the quality polymers, multi-layer structure polymer so-called core-shell type can be used.

The number of layers constituting the core-shell type multilayer structure polymer used in the present invention may be two or more, and may be three or more or four or more. Ru multilayer structure polymer der having a layer (core layer). Type of rubber layer, the acrylic component, and the rubber is composed of those obtained by polymerizing a styrene component. Preferred rubbers, e.g., styrene formed divided that consists of a rubber such as acrylic component, styrene units and α- methyl styrene unit, such as ethyl acrylate units or butyl acrylate units. A rubber composed of a combination of two or more of these components is also preferred. For example, it constituted rubber styrene component such as an acrylic component and a styrene unit and α- methyl styrene unit, such as A acrylic acid ethyl units or butyl acrylate units. Of these, rubbers containing alkyl acrylate units and substituted or unsubstituted styrene units are most preferred from the viewpoint of transparency and mechanical properties. In addition to these components, a rubber obtained by crosslinking a copolymer composed of a crosslinking component such as a divinylbenzene unit, an allyl acrylate unit, and a butylene glycol diacrylate unit is also preferable.

In the multilayer structure polymer of the present invention, types of layers other than the rubber layer, Ri high polymer component der glass transition temperature than the rubber layer, an unsaturated carboxylic acid alkyl ester unit, an unsaturated carboxylic acid unit, an unsaturated polymer containing dicarboxylic acid anhydride unit of whether we least one unit selected and the like. Among these, a polymer containing an unsaturated carboxylic acid alkyl ester unit is preferable, and a polymer containing one or more units selected from unsaturated dicarboxylic anhydride units in addition to the polymer is more preferable.

As the monomer as a raw material of the unsaturated carboxylic acid alkyl ester unit, methyl main methacrylic acid is used.

  The unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, and further a hydrolyzate of maleic anhydride. In particular, acrylic acid and methacrylic acid are preferable from the viewpoint of excellent thermal stability, and methacrylic acid is more preferable. These can be used alone or in combination.

In the multilayer structure polymer containing a rubber polymer of the present invention, the type of the outermost (shell layer) is a polymer having an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit.

In the present invention, Ri polymer der containing outermost layer unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit in the above multi-layered polymer, by heating, the thermoplastic copolycondensates of this invention described above It was found that the intramolecular cyclization reaction proceeded to produce the glutaric anhydride-containing unit represented by the general formula (1) in the same manner as in the production of the union (A). Therefore, a multilayer structure polymer having a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit in the outermost layer is blended with the thermoplastic copolymer (A), and heated and melt-kneaded under appropriate conditions. By doing so, a multilayer structure polymer containing the glutaric anhydride-containing unit represented by the general formula (1) in the outermost layer is obtained. As a result, the multilayer structure polymer can be favorably dispersed in the thermoplastic copolymer (A) to be a continuous phase (matrix phase) without agglomeration, and the thermoplastic resin composition of the present invention. It is considered that a very high degree of transparency can be developed with improvement in mechanical properties such as impact resistance.

As the monomer as a raw material for the unsaturated carboxylic acid alkyl ester unit here, methyl main methacrylic acid is used.

Further, as the monomer as a raw material for the unsaturated carboxylic acid unit, main methacrylic acid is used.

As a multi-layer polymer of the present invention, the core layer is an acrylic acid-butyl / styrene copolymers, consisting of glutaric anhydride containing units outermost layer is represented by methylmethacrylate / Formula (1) The core layer is butyl acrylate / styrene copolymer, and the outermost layer is methyl methacrylate / glutaric anhydride-containing unit represented by the general formula (1) / methacrylic acid copolymer. there may be mentioned of is. Here, “/” indicates copolymerization. Furthermore, a preferable example is one in which either one or both of the rubber layer and the outermost layer is a polymer containing a glycidyl methacrylate unit. The core layer is an acrylic acid-butyl / styrene polymer, the outermost layer that also a copolymer consisting of glutaric anhydride-containing unit represented by methyl methacrylate / Formula (1), the continuous phase (matrix It is possible to approximate the refractive index with the thermoplastic copolymer (A), which is a phase, and to obtain a good dispersion state in the resin composition, and to satisfy the demand for more advanced in recent years Since it exhibits sex, it can be preferably used.

  About the average particle diameter of the multilayer structure polymer (B-1) of this invention, it is preferable that they are 0.01 micrometer or more and 1000 micrometers or less. The average particle diameter is more preferably 0.02 μm or more and 100 μm or less, further preferably 0.05 μm or more and 10 μm or less, and most preferably 0.05 μm or more and 1 μm or less. If it is less than the above range, the impact strength of the resulting thermoplastic composition tends to decrease, and if it exceeds the above range, transparency may decrease.

  In the multilayer structure polymer of the present invention, the weight ratio of the core to the shell is preferably 50% by weight or more and 90% by weight or less, and more preferably 60% by weight or more, based on the whole multilayer structure polymer. 80% by weight or less is more preferable.

  As the multilayer structure polymer of the present invention, a commercially available product that satisfies the above-described conditions may be used, or it may be prepared by a known method.

  There is no restriction | limiting in particular in the manufacturing method of the rubber-containing polymer (B) in this invention, It can obtain by well-known polymerization methods, such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

  Moreover, since the thermoplastic resin composition excellent in transparency can be obtained when each refractive index of (A) thermoplastic polymer and (B) rubber-like polymer is approximated, it is preferable. Specifically, the difference in refractive index between the two is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less. In order to satisfy such a refractive index condition, (A) a method of adjusting the monomer unit composition ratio of the thermoplastic polymer, and / or (B) a rubber weight used in the rubber-containing polymer. Examples thereof include a method of adjusting the composition ratio of the coalesced or monomer.

  In addition, the refractive index difference said here is the value measured by the method shown below. (A) The thermoplastic resin composition of the present invention is sufficiently dissolved in a solvent in which the thermoplastic polymer is soluble to obtain a cloudy solution, which is insoluble in the solvent-soluble portion by an operation such as centrifugation. Separate into parts. After refining this soluble part (part containing (A) thermoplastic polymer) and insoluble part (part containing (B) rubber-containing polymer), the measured refractive index (23 ° C., measurement wavelength: 550 nm). ) Is defined as the difference in refractive index.

  In addition, the copolymer composition of (A) the thermoplastic polymer and (B) the rubber-containing polymer in the resin composition is obtained by separating each component after the separation operation of the soluble component and the insoluble component by the above solvent. To analyze.

  In the present invention, the addition amount of the (B) rubber-containing polymer is 1 to 100 parts by weight, preferably 5 to 90 parts by weight, particularly 10 to 80 parts by weight, based on 100 parts by weight of the (A) thermoplastic polymer. Most preferred is the range of parts.

  In the present invention, (A) the thermoplastic polymer and (B) the rubber-containing polymer are blended in advance, after (A) the thermoplastic polymer and other optional components are blended in advance, usually at 200 to 350 ° C. A method of uniformly melting and kneading with a single or twin screw extruder is preferably used. Moreover, the method of removing a solvent after mixing (A) component and (B) component in the solution of the solvent which can melt | dissolve both can also be used.

  Further, as a method for producing the thermoplastic resin composition of the present invention, the above-mentioned copolymer (a) and (B) rubber-containing polymer are blended in advance, and then usually at 200 to 350 ° C., uniaxial or biaxial extrusion. By uniformly melt-kneading with a machine, the component (B) can be blended simultaneously with the conversion of the copolymer (a) to the thermoplastic polymer (A) by the cyclization reaction described above. At this time, a cyclization reaction can be simultaneously performed in the case where a part of the component (B) includes a copolymer composed of an unsaturated carboxylic acid monomer unit and an unsaturated carboxylic acid alkyl ester monomer unit. .

  Further, the thermoplastic polymers used in the present invention include hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based UV absorbers and antioxidants, higher fatty acids, acid esters, and acid amides. Lubricants and plasticizers such as higher alcohols, montanic acid and salts thereof, esters thereof, half esters thereof, release agents such as stearyl alcohol, stearamide and ethylene wax, phosphites, hypophosphites, etc. Additives such as anti-coloring agents, halogen-based flame retardants, phosphorus-based and silicone-based non-halogen-based flame retardants, nucleating agents, amine-based, sulfonic acid-based, polyether-based anti-static agents, pigments and other colorants You may make it contain arbitrarily. However, it is necessary to add in a range where the color of the additive does not adversely affect the thermoplastic polymer and the transparency is not lowered. These additives can be blended into the thermoplastic polymer by a method such as adding at the time of melt kneading using an extruder or injection molding.

  The thermoplastic polymer of the present invention is excellent in mechanical properties and molding processability, and can be melt-molded. Therefore, extrusion molding, injection molding, press molding, etc. are possible. Sheets, tubes, rods, etc. It can be used by molding into a molded product having any desired shape and size.

  For example, when forming into a sheet | seat, a well-known method can be used. That is, production methods such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method can be used. Preferably, an inflation method, a T-die method, a cast method or a hot press method can be used. In the case of a production method using an inflation method or a T-die method, an extruder type melt extrusion apparatus equipped with a single screw or twin screw can be used. The melt extrusion temperature for producing the film of the present invention is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. Moreover, when melt-kneading using a melt-extrusion apparatus, it is preferable to perform the melt-kneading under reduced pressure or the melt-kneading under nitrogen stream from a viewpoint of coloring suppression. Moreover, when forming into a sheet by the casting method, solvents such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone can be used. Preferred solvents are acetone, methyl ethyl ketone, N-methylpyrrolidone and the like. The film is prepared by dissolving the thermoplastic resin composition of the present invention in one or more of the above solvents, and using the solution with a bar coater, a T die, a T die with a bar, a die coat, etc. It can be produced by casting on a flat plate or curved plate (roll) such as a film, steel belt or metal foil and using a dry method in which the solvent is removed by evaporation or a wet method in which the solution is solidified with a coagulating liquid.

  In addition, the thickness of the sheet | seat which consists of a thermoplastic polymer (A) used for this invention is 0.03-30 mm normally, Preferably, it is 0.05-20 mm, Most preferably, it is 0.1-10 mm. If the thickness is less than 0.03 mm, it is difficult to handle such as wrinkling when performing a hard coating as a subsequent step, and if it is more than 30 mm, it tends to be difficult to obtain a smooth surface when producing a sheet. Therefore, it is not preferable.

  In the present invention, when the thermoplastic resin molded article comprising the thermoplastic polymer (A) obtained by the above method forms a film having hard coat properties, it is an extremely strong hard coat even under severe wet heat environment. It has been found that a resin molded article having adhesiveness to the layer, having a high surface hardness and excellent scratch resistance can be obtained. Here, in a preferred embodiment, the surface hardness represented by pencil hardness (JIS-K-5401) of the film surface having hard coat properties is 6H or more, and in a particularly preferred embodiment, scratch resistance of 7H or more is obtained. It is done.

  The hard coat property referred to in the present invention refers to the property of providing a coating film having a hardness higher than that of the thermoplastic polymer in order to supplement the surface hardness of the substrate made of the thermoplastic polymer and to improve the scratch resistance.

  The film having a hard coat property that can be used in the present invention is not particularly limited, and a melamine-based, acrylic-based, or silicon-based hard coat film can be used. And silicon-based hard coat films are preferred.

  In a preferred embodiment of the acrylic hard coat film according to the present invention, a coating agent containing a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is applied and then polymerized and / or reacted. Thus, a resin film is preferably used.

  Two or more (meth) acryloyl groups in one molecule in the present invention (however, the description of “(meth) acryloyl group” in the present invention is an abbreviation of acryloyl group or methacryloyl group). As the polyfunctional (meth) acrylate compound having, a compound in which the hydroxyl group of a polyhydric alcohol having two or more alcoholic hydroxyl groups in one molecule is an esterified product of two or more (meth) acrylic acids, etc. Can be used. Specifically, (a) C2-C12 alkylene glycol (meth) acrylic acid diesters: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, etc. (b) (meth) acrylate diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (C) (meth) acrylic acid diesters of polyhydric alcohols: (e) pentaerythritol di (meth) acrylate, etc. (d) bisphenol A or bisphenol A hydride ethylene oxide and propylene oxide adduct (meth) acrylic acid diester Class: 2,2′-bis (4-acryloxyethoxyphenyl) propane, 2,2′-bis (4-acryloxypropoxyphenyl) propane, etc. (e) diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds (2) Urethane (meth) acrylates having two or more (meth) acryloyloxy groups in the molecule obtained by further reacting an alcoholic hydroxyl group-containing (meth) acrylate with a terminal isocyanate group-containing compound obtained by previously reacting (F) two or more in the molecule Epoxy (meth) acrylates having two or more (meth) acryloyloxy groups in a molecule obtained by reacting acrylic acid or methacrylic acid to a compound having an epoxy group, and the like.

  In particular, it is a compound composition that forms a hard coat layer containing at least one monomer having three or more (meth) acryloyl groups in one molecule, as well as hardness and curability, and wear resistance. Since it is excellent in flexibility, it is preferable.

  Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate and trimethylolpropane tri (meth) acrylate. These monomers may be used alone or in combination of two or more.

  The proportion of the monomer having three or more (meth) acryloyl groups in one molecule is desirably 50 to 95% by weight with respect to the total solid content. When the amount of the monomer used is less than 50% by weight, it is difficult to obtain a cured film having sufficient wear resistance. When the amount exceeds 95% by weight, the shrinkage due to polymerization is large, and the cured film is hardened. This is not preferable because strain remains in the coating or the flexibility of the coating tends to decrease.

  Examples of a method of polymerizing and / or reacting the compound composition of the hard coat layer include a method of irradiating with ultraviolet rays. In this case, it is desirable to add a photopolymerization initiator to the composition.

  Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methylbenzoyl formate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiuram Sulfide, thioxanthone, 2-chlorothioxanthone, sulfur compounds such as 2-methyl thioxanthone, benzoyl peroxide, peroxide compounds such as di -t- butyl peroxide. These photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is suitably 0.01 to 10 parts by weight in the solid content.

  As another method, electron beam or radiation can be used as a polymerization and / or reaction means. When using an electron beam or radiation, it is not always necessary to add a polymerization initiator.

  The compound composition forming the hard coat layer used in the present invention is known to include hydroquinone, hydroquinone monomethyl ether, 2,5-t-butyl hydroquinone, etc. in order to prevent thermal polymerization during production and dark reaction during storage. It is desirable to add a thermal polymerization inhibitor. The addition amount of the thermal polymerization inhibitor is preferably 0.005 to 0.05% by weight in the solid content.

  For the purpose of improving the workability during coating and controlling the coating film thickness, an organic solvent is blended in the compound composition forming the hard coat layer used in the present invention within a range that does not impair the purpose of the present invention. be able to.

  As the organic solvent, it is necessary to select a solvent type that does not basically attack the substrate, but usually the one having a boiling point of 50 to 150 ° C. is before and after the workability at the time of coating, polymerization, and / or reaction. Easy to use from the viewpoint of drying. Specific examples include alcohol solvents such as methanol, ethanol and isopropyl alcohol, acetate solvents such as methyl acetate, ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene. And cyclic ether solvents such as dioxane. These solvents can be used alone or in admixture of two or more.

  Examples of the means for applying the acrylic hard coat layer include known methods such as spraying, dipping, roll coating, die coating, and gravure coating.

  As a preferable aspect of the silicon-based hard coat film in the present invention, (a) the general formula (6)

（ただしＲ^６は炭素数１〜５の炭化水素基または炭素数１〜４のアシル基である）で示されるケイ素化合物の加水分解物１００重量部、（ｂ）一般式（７）

(Wherein R ⁶ is a hydrocarbon group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms) 100 parts by weight of a hydrolyzate of a silicon compound represented by formula (7)

（ただしＲ^７は炭素数１または２の炭化水素基、Ｒ^８は炭素数１〜５の炭化水素基または炭素数１〜４のアシル基である）で示されるケイ素化合物の加水分解物４００〜２０重量部、および（ｃ）硬化剤からなる組成物が例示できる。一般式（６）で示されるケイ素化合物において、Ｒ^６の具体例はメチル、エチル、プロピルなどのアルキル基やアセチル基などのアシル基である。また一般式（７）のケイ素化合物における炭素数１または２の炭化水素とはメチルまたはエチル基であり、さらにＲ^８はＲ^６と同一群から選ばれるものであるが、両基は同一のものであっても異なっていてもよい。これらのケイ素化合物は既知の化合物であり、公知の方法により調製し得る。

(Wherein R ⁷ is a hydrocarbon group having 1 or 2 carbon atoms, and R ⁸ is a hydrocarbon group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms) A composition comprising 20 parts by weight and (c) a curing agent can be exemplified. In the silicon compound represented by the general formula (6), specific examples of R ⁶ are alkyl groups such as methyl, ethyl and propyl, and acyl groups such as acetyl group. In the silicon compound of the general formula (7), the hydrocarbon having 1 or 2 carbon atoms is a methyl or ethyl group, and R ⁸ is selected from the same group as R ⁶ , but both groups are the same. Or different. These silicon compounds are known compounds and can be prepared by known methods.

  The silicon compounds of the general formulas (6) and (7) are hydrolyzed by adding water alone or water and a solution (organic solvent) and, if necessary, a small amount of acid separately or mixed.

  The curing agent (c) is an organic carboxylic acid having 1 to 4 carbon atoms (for example, acetic acid, propionic acid, etc.), at least one of alkali metal salts of nitrous acid, sulfurous acid, aluminate and carbonic acid, or water. Examples thereof include tetramethylammonium oxide, tetra-n-butylphosphonium hydroxide, quaternary ammonium hydroxide, and quaternary phosphonium hydroxide. (C) The curing agent is used by uniformly dissolving in the hydrolyzate solution of the silicon compound of the above (a) and (b). As the solvent, usually dioxane and alcohols can be preferably used. A coating film having a hard coat property is formed by applying the above solution to a substrate made of a thermoplastic resin molded article and then heating the surface. As a coating method, a known method such as a dipping method, a spin coating method, a spray method, or roll coating can be used. As for the heating conditions, curing is possible at a low temperature of 100 ° C. or lower.

  Furthermore, as another preferable mode of the silicon-based film having hard coat properties, (d) General formula (8)

（ただし式中Ｒ^９は炭素数１〜６の炭化水素基、メタクリロキシ基またはエポキシ基を有する有機基、Ｒ^１０は炭素数１〜４の炭化水素基、Ｒ^１１は炭素数１から５の炭化水素基、アルコキシアルキル基または水素原子、ｍは０または１を表す）で示される有機ケイ素化合物の１種もしくは２種以上、（ｅ）粒子径１〜１００ｎｍのシリカ微粒子、（ｆ）多官能エポキシ化合物および（ｇ）硬化触媒からなる組成物の溶液を熱可塑性樹脂成形品からなる基体に塗布した後、加熱硬化させる手法が挙げられる。

(Wherein R ⁹ is an organic group having a hydrocarbon group having 1 to 6 carbon atoms, a methacryloxy group or an epoxy group, R ¹⁰ is a hydrocarbon group having 1 to 4 carbon atoms, and R ¹¹ is a carbon group having 1 to 5 carbon atoms. 1 or 2 or more types of organosilicon compounds represented by hydrogen group, alkoxyalkyl group or hydrogen atom, m represents 0 or 1, (e) silica fine particles having a particle diameter of 1 to 100 nm, (f) polyfunctional epoxy An example is a method in which a solution of a composition comprising a compound and (g) a curing catalyst is applied to a substrate comprising a thermoplastic resin molded article and then cured by heating.

  Specific examples of the silicon compound represented by the general formula (8) include methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and the like, and hydrolysates thereof. (E) As silica fine particles, those in which water or alcohol solvent fine particles generally called colloidal silica or silica sol are dispersed are preferable.

  (F) Specific examples of polyfunctional epoxy compounds include glycidyl ethers of polyfunctional alcohols such as diglycidyl ethers such as glycerin, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol. Moreover, (g) As a curing catalyst, perchloric acid can be illustrated as a suitable epoxy curing catalyst.

  For the purpose of improving the workability during coating and controlling the coating film thickness, an organic solvent is blended in the compound composition forming the hard coat layer used in the present invention within a range that does not impair the purpose of the present invention. be able to. As the organic solvent, it is necessary to select a solvent type that does not basically attack the substrate, but usually the one having a boiling point of 50 to 150 ° C. is before and after the workability at the time of coating, polymerization, and / or reaction. Easy to use from the viewpoint of drying.

  Specific examples include alcohol solvents such as methanol, ethanol and isopropyl alcohol, acetate solvents such as methyl acetate, ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene. And cyclic ether solvents such as dioxane. These solvents can be used alone or in admixture of two or more.

  The refractive index of the film having a hard coat property in the present invention is preferably used between 1.40 and 1.65 in order to impart antireflection properties or obtain a resin molded product having no interference fringes. In order to obtain a high-quality resin molded product having no interference fringes, it is preferable to set the difference in refractive index between the thermoplastic polymer substrate and the film having hard coat properties to ± 0.05. In particular, in applications where it is necessary to suppress the occurrence of interference fringes as much as possible, the refractive index difference is preferably set within ± 0.02. This refractive index difference can be adjusted by changing the copolymer composition of the thermoplastic polymer substrate or changing the compound composition forming the hard coat layer. Although the film thickness of the film having hard coat properties in the present invention is not particularly limited, it is preferably used in the range of 10 to 20,000 nm from the viewpoints of maintaining adhesion strength and scratch resistance. That is, if the thickness is less than 10 nm, the coating effect is not recognized, and if it exceeds 20,000 nm, uneven coating or the like tends to occur.

  In addition, the resin molded product of the present invention may be one in which an intermediate layer called a primer layer is formed between a base material made of a thermoplastic polymer and a hard coat film. Here, the primer layer can be applied for the purpose of increasing the adhesion between a base material made of a thermoplastic polymer and a film having hard coat properties, or improving flexibility and impact resistance.

  As the primer layer applied to the resin molded product of the present invention, any of the known primer layers, such as a cured product of polyurethane, epoxy, acrylic and / or methacrylic compound and styrene, can be preferably used. .

  The polyurethane primer that can be preferably used as a primer layer in the present invention includes a thermoplastic polyurethane obtained by the reaction of a compound having active hydrogen at both ends and a diisocyanate compound, a curing catalyst acting on a polyol and a polyisocyanate, and a curing reaction by heating. The thermosetting polyurethane obtained by carrying out is mentioned.

  In the case of thermoplastic polyurethane, compounds having active hydrogen at both ends, for example, alkylene glycols such as ethylene glycol, propylene glycol and butanediol, polyalkylene adipates such as polytetramethylene adipate, and polyalkylenes such as polyhexamethylene carbonate In the presence of a catalyst such as carbonates, silicone polyols and the like, diisocyanate compounds, for example, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, etc. The primer layer is formed by appropriately diluting the thermoplastic polyurethane reacted in step 1 with a solvent and applying it to a lens substrate, followed by drying by heating. Can. As a coating method to a base material made of a thermoplastic polymer, it can be selected from known coating methods such as a spin coating method and a dipping method.

  On the other hand, in the case of thermosetting polyurethane, a primer layer can be formed by applying a composition comprising a polyol compound, a polyisocyanate compound, and a curing catalyst on a substrate made of a thermoplastic polymer and curing it by heating. . In this case, either a non-block type or a block type can be used as the polyisocyanate compound. However, since the curing reaction proceeds at room temperature in the non-block type, there is a problem that the pot life of the composition is short, and blocking by heating. A block-type isocyanate in which the curing reaction proceeds only upon removal of the agent can be preferably used. Specific examples of the polyol compound include polyesters, polyethers, polyacrylates and polycarbonates having a plurality of hydroxyl groups in the molecule. Commercially available block-type polyisocyanates can be used, but compounds obtained by blocking various diisocyanate compounds with acetoacetic acid, malonic acid, and the like can be used. Application to a substrate made of a thermoplastic polymer can be carried out by a known method such as spin coating or dipping by appropriately diluting with a solvent. The curing reaction is carried out at an appropriately set temperature and reaction time, but usually requires a curing time of 10 minutes to 2 hours at a temperature of 100 ° C. or higher.

  Examples of the epoxy primer layer include those obtained by curing diglycidyl ether of diol or polyol with an epoxy curing catalyst. Specific examples include a primer layer obtained by curing diglycidyl ether such as glycerin, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol with an epoxy curing catalyst such as perchloric acid.

  For application to a substrate made of a thermoplastic polymer, known methods such as spin coating, dipping and spraying can be applied. After applying a composition comprising an epoxy compound and a curing catalyst, the primer layer can be formed by heating at an appropriately set temperature, preferably at a temperature of 100 ° C. or higher, usually for 1 to 60 minutes.

  In addition, a cured product of a copolymer of an acrylic and / or methacrylic compound and styrene can be used as the primer layer.

  When applying a primer layer to a lens substrate, additives such as leveling agents, UV absorbers, antioxidants, dyes, pigments, photochromic agents, etc. may be added as necessary to impart various functions to the lens. You can also.

In the resin molded product of the present invention, antireflection properties can be further provided as necessary. Anti-reflective property is to prevent this because it is troublesome that the reflected light is strong and the reflected image is clear when looking at the object through the transparent molded body, and the reflected image is uncomfortable to the eyes. For example, in the case of a single-layer antireflection film, a minimum reflectance, that is, a maximum is obtained by selecting a film having a refractive index lower than that of the substrate so that the optical film thickness is 1/4 or an odd multiple of the light wavelength. It is to give the transmittance. Here, the optical film thickness is given by the product of the refractive index of the film and the film thickness of the film. Examples of the method for imparting antireflection properties include wet coating or dry coating such as vacuum deposition. Further, the film structure for imparting antireflection properties may be a single layer or multiple layers, and the material thereof is also the refractive index of thermoplastic transparent resin, the refractive index and film thickness of a film having hard coat properties, or the requirement. The optimum combination is determined by the antireflection performance to be performed. Many combinations of antireflection properties have already been proposed (Optical Technology Contact, Vol. 9, No. 8.17 to 23. (1971), OPTICS OF THIN FILMS, 159 to 282. A. VASICEK ( NORTH-HOLLAND PUBLISHING COMPANY). AMSTERDAM (1960)), and there is no problem using these combinations in the present invention. However, when the film having hard coat properties is an acrylic hard coat layer, TiO ₂ , Metal oxides such as ZrO ₂ , ITO, SnO ₂ , Y ₂ O ₃ , ZnO, SiO ₂ and MgF ₂ are preferred. In addition, pretreatment such as formation of the above-described primer layer is effective as means for improving adhesion between the layers.

  The resin molded product of the present invention is particularly excellent in its good transparency, mechanical properties, scratch resistance, and molding processability, and can be easily applied to large molded products or precision molded products. Since it has weather resistance, it can be used for various applications such as electrical and electronic parts, optical filters, automobile parts, mechanical mechanism parts, OA equipment, housings such as home appliances and their parts, general goods, etc. .

  Specific applications of the molded product include, for example, various covers, various terminal boards, printed wiring boards, speakers, microscopes, binoculars, cameras, optical instruments represented by watches, and excellent transparency and heat resistance. From the point of view, finder such as camera, VTR, projection TV, filter, prism, Fresnel lens, etc. as video equipment related parts, various optical disc (VD, CD, DVD, MD, LD, etc.) substrates as optical recording / optical communication related parts Information equipment related parts such as protective films, optical switches, optical connectors, etc., liquid crystal displays, flat panel displays, plasma display light guide plates, Fresnel lenses, polarizing plates, polarizing plate protective films, retardation films, light diffusion films, viewing angles Magnifying film, reflective film, antireflection film, antiglare film Brightness enhancement film, conductive films for touch panels, covers, etc., is very useful for these various applications.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Each measurement and evaluation was performed by the following method.

(1) Composition of each component In heavy dimethyl sulfoxide, ¹ H-NMR was measured at 30 ° C. to determine the composition of each copolymer unit of the thermoplastic polymer.

(2) Glass transition temperature (Tg)
The Tg of the thermoplastic polymer was measured using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer) at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere.

(3) Transparency (total light transmittance, haze)
Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., the total light transmittance (%) and haze (cloudiness) (%) of each molded product at 23 ° C. were measured to evaluate transparency.

(4) Surface hardness (pencil hardness)
The pencil hardness under a 1 kg load was measured in accordance with JIS-5400 on the surface of the coated film having various hardened properties or the surface of the antireflection film.

(5) Adhesiveness 100 grids that reach a 1 mm base material on the coating surface are put with a rope knife from the top of the coating, and cellophane adhesive tape (trade name “Cellotape (registered trademark)” manufactured by Nichiban Co., Ltd.) is strongly applied. The case where the film was peeled off rapidly in the 90-degree direction and no film was peeled off was marked as ◯.

(6) Falling ball impact strength Height at which a 1 kg iron ball is dropped on a resin molded product in which a hard coat film is formed on a 3 mm thick square plate obtained by injection molding, and the resin molded product is cracked. Was measured.

<Reference Example (1) Synthesis of Copolymer (a)>
(A-1): Suspension polymerization method 20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide, 0.3 part by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water are charged into the reactor, and nitrogen gas is supplied into the reactor. And kept at 70 ° C. The reaction was continued until the monomer was completely converted into a polymer to obtain an aqueous solution of methyl methacrylate / acrylamide copolymer. The resulting aqueous solution was used as a suspending agent. A solution prepared by dissolving 0.05 parts by weight of the above-mentioned methyl methacrylate / acrylamide copolymer suspension in 165 parts by weight of ion-exchanged water in a stainless steel autoclave having a volume of 5 liters and equipped with a baffle and a foudra-type stirring blade. The mixture was supplied and stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 70 ° C. The time when the internal temperature reached 70 ° C. was set as the start of polymerization, and kept for 180 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried according to the usual method to obtain a bead-shaped copolymer (a-1). The polymerization rate of this copolymer (a-1) was 98%, and the weight average molecular weight was 130,000.
Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight n-dodecyl mercaptan 0.4 part by weight 2,2′-azobisisobutyronitrile 0.2 part by weight.

(A-2): Suspension polymerization method Copolymer (a-2) was obtained by the same production method as (a-1) except that the charged composition of the monomer mixture and chain transfer agent was changed to the following. . The polymerization rate was 95% and the weight average molecular weight was 100,000.
Methacrylic acid 15 parts by weight Methyl methacrylate 75 parts by weight Styrene 10 parts by weight t-dodecyl mercaptan 0.8 parts by weight

(A-3) Precipitation polymerization method The following mixed substances are supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, and nitrogen gas is supplied at 10 L / min while stirring at 250 rpm. And bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 80 ° C. while stirring. When the internal temperature reached 80 ° C., the polymerization was started. The internal temperature was maintained at 80 ° C. for 90 minutes, and after raising the temperature to 95 ° C., the polymerization was further continued for 90 minutes to complete the polymerization. Thereafter, the reaction system was cooled in accordance with a usual method, and the resulting slurry was centrifuged and dried to obtain a powdery copolymer (a-3). The copolymer composition of the copolymer (a-3) was MMA / MAA (weight ratio) = 72/28. The polymerization rate was 75%. The weight average molecular weight was 130,000.
Methacrylic acid 25 parts by weight Methyl methacrylate 75 parts by weight Butyl acetate 900 parts by weight Laurolyl peroxide 0.9 parts by weight.

<Reference Example (2) Production of Thermoplastic Polymer (A)>
<A-1>
The copolymer (a-1) obtained in Reference Example (1) was supplied to a 38 mmφ biaxial / uniaxial composite continuous kneading extruder (HTM38 (manufactured by CTE, L / D = 47.5)). While purging nitrogen at a rate of 10 L / min from the part, an intramolecular cyclization reaction was performed at a screw rotation speed of 75 rpm, a raw material supply rate of 10 kg / h, and a cylinder temperature of 290 ° C. to produce a pellet-like thermoplastic polymer <A-1 > Was obtained.

<A-2>
In 100 parts by weight of the copolymer (a-1) obtained in Reference Example (1), 0.2 part by weight of lithium acetate is blended as a catalyst, and a biaxial / uniaxial composite as in <A-1>. While feeding into a continuous mold kneading extruder (HTM38 (CTE), L / D = 47.5) and purging nitrogen from the hopper at a rate of 10 L / min, the screw rotation speed is 75 rpm, the feed rate is 10 kg / h. An intramolecular cyclization reaction was performed at a cylinder temperature of 290 ° C. to obtain a pellet-shaped thermoplastic polymer <A-2>.

<A-3>
To 100 parts by weight of the copolymer (a-1) obtained in Reference Example (1), 0.03 part by weight of sodium hydroxide was blended as a catalyst, and this was mixed with a 44 mmφ twin screw extruder (TEX-44 (Nippon Steel). (L / D = 28.0) manufactured by Tosho Co., Ltd., while purging nitrogen from the hopper at an amount of 10 L / min, the rotational speed of the screw was 75 rpm, the feed rate was 5 kg / h, and the cylinder temperature was 280 ° C. A cyclization reaction was performed to obtain a pellet-shaped thermoplastic polymer <A-3>.

<A-4>
In 100 parts by weight of the copolymer (a-2) obtained in Reference Example (1), 0.2 part by weight of lithium acetate is blended as a catalyst, and, as in <A-1>, biaxial / uniaxial composite Was supplied to a continuous mold kneading extruder (HTM38 (manufactured by CTE, L / D = 47.5) to obtain a pellet-shaped thermoplastic polymer <A-2>. Amount of nitrogen of 10 L / min from the hopper part) The pellet was subjected to an intramolecular cyclization reaction at a screw rotation speed of 75 rpm, a raw material supply rate of 10 kg / h, and a cylinder temperature of 290 ° C. to obtain a pellet-shaped thermoplastic polymer <A-4>.

<A-5>
The copolymer (a-3) obtained in Reference Example (1) was supplied to a 38 mmφ biaxial / uniaxial composite continuous kneading extruder (HTM38 (manufactured by CTE, L / D = 47.5)). While purging nitrogen at a rate of 10 L / min from the part, an intramolecular cyclization reaction was performed at a screw rotation speed of 75 rpm, a raw material supply rate of 10 kg / h, and a cylinder temperature of 290 ° C., and a pellet-shaped thermoplastic polymer <A-5 > Was obtained.

<Reference Example (3) Production of Rubber-Containing Polymer (B)>
The following composition was added as an initial adjustment solution in a glass container (capacity 5 liters) with a cooler.
Deionized water: 120% by mass
Potassium carbonate: 0.5% by mass
Dioctyl sulfosuccinate: 0.5% by mass
Potassium persulfate: 0.005% by mass.

While stirring the initial adjustment solution under a nitrogen atmosphere, the following composition was added and reacted at 70 ° C. for 30 minutes to obtain a rubbery polymer.
Butyl acrylate: 53% by mass
Styrene: 17% by mass
Allyl methacrylate (crosslinking agent): 1% by mass.

The following composition was continuously added at 70 ° C. for 90 minutes while stirring, and after the addition was completed, the mixture was further maintained for 90 minutes to form a shell layer.
Methyl methacrylate: 21% by mass
Methacrylic acid: 9% by mass
Potassium persulfate: 0.005% by mass.

  The polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a core-shell type rubbery polymer <B-1>. The average particle size of the rubbery polymer portion of the rubbery polymer <B-1> measured with an electron microscope was 170 nm.

<Reference Example (4) Production of Thermoplastic Resin Composition>
20 parts by weight of the rubber-containing polymer <B-1> obtained in Reference Example (3) is blended with 100 parts by weight of the thermoplastic polymer <A-5> obtained in Reference Example (2). Using a twin screw extruder TEX30 (L / D = 44.5) manufactured by Nippon Steel Co., Ltd., while purging nitrogen from the hopper at an amount of 10 L / min, the screw rotation speed is 100 rpm, the raw material supply rate is 10 kg / hour, The mixture was kneaded at a cylinder temperature of 280 ° C. to obtain a pellet-shaped thermoplastic resin composition <C-1>.

Regarding the obtained pellets, PMMA (“SUMIPEX LG” manufactured by Sumitomo Chemical Co., Ltd.), and PC (“Iupilon H4000” manufactured by Mitsubishi Engineering Plastics), each copolymer component composition and glass transition temperature determined by ¹ H-NMR. The evaluation results and each pellet were subjected to an injection molding machine (M-50AII-SJ, manufactured by Meiki Seisakusho Co., Ltd.) to form a square plate-shaped test piece having a thickness of 80 mm × 80 mm × 3 mm (molding conditions are molding temperature: Glass transition temperature + 150 ° C., mold temperature: 80 ° C., injection speed: 90 cm ³ / second, injection time: 10 seconds, cooling time: 30 seconds, molding pressure: pressure at which resin is filled in the mold (molding lower limit pressure) Table 1 shows the surface hardness and total light transmittance of each of the obtained square plate specimens.

<Reference Example (5) Formation of Hard Coat Coating>
<Hard coat method-1>
90 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.), macromonomer AN-6S (terminal group is methacryloyl group, high molecular weight (segment) component is styrene / acrylonitrile, number average molecular weight is 6 , 000 macromonomer) (Toagosei Co., Ltd., solid content 40 wt%) 20 parts by weight, photoinitiator 1-hydroxyphenyl ketone (Ciba Specialty Chemicals Co., Ltd.) 5 parts by weight, 50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone were mixed with stirring to obtain a coating solution A. The coating liquid A is applied to the upper surface of each resin molded product so that the thickness after drying is 5 μm, and dried in two steps in an oven at 80 ° C. for 5 minutes and at 100 ° C. for 5 minutes. A hard coat layer was formed by irradiating with a high-pressure mercury lamp having an intensity of 80 W / cm set at a height of 12 cm from 5 minutes.

<Hard coat method-2>
Commercially available polyurethane solution LQ3510 (manufactured by Sanyo Chemical Co., Ltd., solid content concentration 30%, toluene / isopropyl alcohol solution) was further diluted with toluene / isopropyl alcohol (volume ratio 2/1) to a solid content concentration of 10%. Then, 0.05 parts by weight of a silicon surfactant (manufactured by Nihon Unicar Co., Ltd., L-7002) was added to 100 parts by weight of this solution to obtain a primer solution. This solution was applied to both surfaces of each resin molded article by a dipping method. After applying the primer solution, heat treatment was performed at 110 ° C. for 40 minutes to form a primer layer (C-1) on each resin molded product. Next, 130 parts by weight of vinyltriethoxysilane and 190 parts by weight of methyltrimethoxysilane were mixed, and 110 parts by weight of 0.01N hydrochloric acid was added thereto, followed by hydrolysis, and stirring was continued until a transparent uniform solution was obtained. After natural cooling to room temperature, 250 parts by weight of dioxane, 1.2 parts by weight of glacial acetic acid and 0.8 parts by weight of sodium acetate were added, and the coating solution B was applied by dipping method and dried by heating at 90 ° C. for 30 minutes. The hard coat film was cured.

Reference Example 6 Formation of Antireflection Film A mixture of ZnO ₂ / SiO _{2 as} an inorganic substance (optical film thickness nd = λ) on a hard coat film of a resin molded article on which a film having the hard coat property is formed. / 2), ZnO ₂ (nd = λ / 2), and SiO ₂ (nd = λ / 4) were sequentially coated in multiple layers by vacuum deposition.

[Example 1 and Comparative Examples 1 to 8 ]
Each pellet-shaped thermoplastic polymer obtained in Reference Example (2) or the thermoplastic resin composition obtained in Reference Example (4) was dried at 100 ° C. for 3 hours, and then an injection molding machine (a famous machine). A square plate-shaped test piece having a thickness of 80 mm × 80 mm × 3 mm was formed using M-50AII-SJ manufactured by Seisakusho. Molding conditions are: molding temperature: glass transition temperature of thermoplastic polymer + 150 ° C., mold temperature: 80 ° C., injection speed: 90 cm 3 / sec, injection time: 10 seconds, cooling time: 30 seconds, molding pressure: resin on mold Was carried out at a pressure (molding lower limit pressure) +1 MPa. Each obtained square plate-shaped test piece was processed by the hard coat method shown in Table 2 (the method described in Reference Example (3)), and various properties were evaluated. In Comparative Examples 2 and 3, PMMA (“SUMIPEX LG” manufactured by Sumitomo Chemical Co., Ltd.) and PC (“Iupilon H4000” manufactured by Mitsubishi Engineering Plastics Co., Ltd.) were used, respectively, and the above thermoplastic polymer was injected under molding conditions. Similar to the molding method and the hard coat method, a square plate-like test piece having a hard coat layer was prepared and evaluated.

From the results of Example 1 and Comparative Examples 1 to 8 , the thermoplastic polymer (A) whose copolymer composition was controlled within the scope of the present invention (A) was 100 parts by weight, and (B) the rubber-containing polymer 1 to 100. By using a thermoplastic resin composition containing parts by weight, it had excellent transparency, heat resistance , falling ball impact strength , high surface hardness, and adhesion to a hard coat layer that was strong even after wet heat treatment. It turns out that a resin molded product is obtained. The thermoplastic resin composition added pressure to the rubber-containing polymer, a thermoplastic polymer (A) without significantly impairing the original properties, impact strength it can be seen that improved.

[Example 2 and Comparative Example 9 ]
After the thermoplastic resin composition obtained in Reference Example (4) (C-1), and dried 3 hours at 100 ° C., a single-screw extruder of 65 mm-diameter (Japan Steel Works, Ltd., NS65) lip gap with The sheet was extruded through a 0.5-mm T-die (set temperature: 270 ° C.) and cooled so that both surfaces were completely adhered to a stainless steel polishing roll (70 ° C.) having a surface finish of 1S to obtain a sheet having a thickness of 200 μm. . After the obtained sheet was processed by the hard coat method shown in Table 3 (the method described in Reference Example (5)), the antireflection film described in Reference Example (6) was formed, and various properties were obtained. Evaluated.

From the results of Example 2 and Comparative Example 9 , even in the case of a sheet, the thermoplastic polymer (A) having a copolymer composition controlled within the scope of the present invention contains (B) a rubber-containing polymer. By using the resin composition, it is possible to obtain a resin molded product having high surface hardness, strong adhesion to the hard coat layer even after wet heat treatment, and sufficiently strong adhesion to the antireflection film. You can see that

Claims (5)

(i) 25 to 50% by weight of a glutaric anhydride structural unit represented by the following general formula (1), (ii) 50 to 75% by weight of an unsaturated carboxylic acid alkyl ester unit, (iii) an unsaturated carboxylic acid unit 5 (B) The core layer is a butyl acrylate / styrene polymer with respect to 100 parts by weight of the thermoplastic polymer (A) having 10% by weight or less of (iv) other vinyl monomer units. Then, the outermost layer is molded into a thermoplastic resin composition obtained by heat- melting and kneading 1 to 100 parts by weight of a rubber-containing polymer which is a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit. A resin molded product formed by forming a hard coat film on at least one surface of a substrate made of a thermoplastic resin molded product, and (i) the above general formula (A) in the thermoplastic polymer (A) Glutar represented by 1) When the composition ratio of the acid anhydride structural unit is X (wt%) and (iii) the composition ratio of the unsaturated carboxylic acid unit is Y (wt%), 0 ≦ Y / X ≦ 0.2 Characteristic resin molded product.

(R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms) The thermoplastic polymer (A) is obtained by converting an original copolymer containing (ii) an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit into a screw length / diameter ratio (L / D) of 30. The resin molding according to claim 1, wherein the resin molding is obtained by heat treatment using an extruder of 110 or less and (i) dehydration and / or (b) dealcoholization reaction. Goods. The resin molded product according to claim 1 or 2, further comprising a single-layer or multi-layer antireflection film formed by vapor deposition of an inorganic compound on the surface of the film having hard coat properties. The resin molded product according to claim 1, wherein the resin molded product is an injection molded product. The resin molded product according to claim 1, wherein the resin molded product is a sheet.