JP2006199774A - Hard coated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such a hard coated article excellent in the external appearance as is capable of large-sizing, wall-thinning and making the shape complicated without impairing the transparency, thermal resistance and impact resistance of an aromatic polycarbonate-based resin. <P>SOLUTION: The hard coat article has a hard coat layer set on the surface of a molded article from a resin composition that contains (A) an aromatic polycarbonate-based resin and (B) a flow improver of a polymer obtained by polymerizing a monomer mixture consisting of (b1) 0.5-99.5% by mass of an aromatic vinyl monomer, (b2) 0.5-99.5% by mass of a monomer expressed by formula (I) (wherein, R<SP>1</SP>is a hydrogen atom or a methyl group; and R<SP>2</SP>is a phenyl group which may have a substituent) and (b3) 0-40% by mass of other monomer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hard coat product in which a hard coat layer is provided on the surface of a molded product formed by molding an aromatic polycarbonate resin composition.

  Molded products made of aromatic polycarbonate resin are excellent in transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc., so electrical / electronic / OA equipment, optical components It is used in a wide range of fields such as precision machinery, automobiles, security / medical care, building materials, and miscellaneous goods. However, a molded article made of an aromatic polycarbonate resin has a problem that it is inferior in scratch resistance or the like. Therefore, as an optical information recording medium such as an optical disk, an optical lens such as an automobile lamp cover, a building material such as a window material, a glazing material for a vehicle, etc., which require abrasion resistance, a molding made of an aromatic polycarbonate resin. Hard coat products provided with a hard coat layer on the product surface are used (see, for example, Patent Documents 1 to 4).

The hard coat layer is formed by applying a hard coat agent containing an acrylic resin, a melamine resin, a urethane resin, a silicone resin, or the like to the surface of a molded product and curing it. However, a molded article made of an aromatic polycarbonate resin has a problem that it is inferior in chemical resistance (hard coat resistance). Therefore, the hard coat product has a problem that a crack occurs when the hard coat agent comes into contact with the molded product, resulting in poor appearance.
In recent years, demands for larger hard coat products, thinner walls (lighter weight), more complex shapes, higher performance, etc. are increasing, and there is a demand for aromatic polycarbonate resins with excellent moldability (melt flowability). It has been. However, since the aromatic polycarbonate resin is usually amorphous, it has a problem that the molding process temperature is high and the melt fluidity is poor.

As a method for improving the moldability of the aromatic polycarbonate resin, a method (1) of reducing the molecular weight of the aromatic polycarbonate resin and increasing the melt fluidity is well known.
Moreover, as a molded article with high hard coat resistance, (2) a window material in which an aromatic polycarbonate resin having a specific molecular weight distribution and viscosity average molecular weight is injection-molded (Patent Document 5), (3) a specific release agent , A molded product containing a specific amount of a phosphorus-based stabilizer and an ultraviolet absorber and injection-molded with an aromatic polycarbonate resin with little mass loss due to heat treatment (Patent Document 6), (4) Injecting an aromatic polycarbonate resin Proposed a press-molded product with a ratio L / D of the distance (L (mm)) from the gate portion to the flow end to the thickness (D (mm)) of 150 or more (Patent Document 7) Has been.

  However, in the method (1), although the melt fluidity is greatly improved, a decrease in molecular weight more than necessary impairs the heat resistance and impact resistance, particularly chemical resistance, of a molded article made of an aromatic polycarbonate resin. Therefore, there is a problem that cracks due to the hard coating agent and appearance defects are remarkably generated. Therefore, there is a limit to improving the melt fluidity of the aromatic polycarbonate resin composition by reducing the molecular weight of the aromatic polycarbonate resin while maintaining the excellent characteristics of the molded product, and the application of the hard coat agent Is limited.

  In addition, in the molded products of (2) to (4), although some improvement in hard coat resistance is seen, it is still insufficient, and melting of the aromatic polycarbonate resin composition that is the material of the molded product Since the fluidity is also insufficient, it does not fully meet the demands for increasing the size, thinning (lightening), complicated shape, high performance, etc. of hard coat products. In addition, there are problems such as many variations in the quality of hard coat products, which is not practical.

In this way, without sacrificing the excellent properties (transparency, heat resistance, impact resistance, etc.) of molded products made of aromatic polycarbonate resins, they are larger, thinner (lighter), more complicated in shape, and higher performance. A hard coat product that can be made into an excellent appearance and has an excellent appearance has not been obtained so far.
JP-A-3-275769 Japanese Patent Laid-Open No. 5-17706 JP-A-5-179157 JP-A-3-230397 JP 2001-354781 A JP 2004-35611 A JP 2004-35609 A

  The object of the present invention is to increase the size, reduce the thickness (light weight), make the shape more complicated, without impairing the excellent properties (transparency, heat resistance, impact resistance, etc.) of the molded product made of an aromatic polycarbonate resin. The object is to provide a hard coat product which can be improved in performance and has an excellent appearance.

  The hard coat product of the present invention is provided with a hard coat layer on the surface of a molded product obtained by molding an aromatic polycarbonate resin composition containing an aromatic polycarbonate resin (A) and a fluidity improver (B). A hard coat product, wherein the fluidity improver (B) is an aromatic vinyl monomer (b1) 0.5 to 99.5% by mass, a monomer represented by the following formula (I) (b2) ) 0.5-99.5% by mass, and other monomer (b3) monomer mixture consisting of 0-40% by mass [however, the total of the monomers (b1)-(b3) is 100% by mass It is. ] Is a polymer obtained by polymerizing].

(In formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted phenyl group.)

  The hard coat product of the present invention is large, thin (light weight), and complex in shape without impairing the excellent properties (transparency, heat resistance, impact resistance, etc.) of molded products made of aromatic polycarbonate resin. And high performance, and excellent appearance.

[Aromatic polycarbonate resin (A)]
The aromatic polycarbonate resin (A) is an aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic hydroxy compound with a carbonic acid diester such as diphenyl carbonate or phosgene. The aromatic polycarbonate resin (A) may be branched. In the case of the branched aromatic polycarbonate resin (A), an aromatic dihydroxy compound and an aromatic polyhydroxy compound are used in combination as the aromatic hydroxy compound.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxy diphenyl etc. are mentioned. Of these, bisphenol A is preferred. Furthermore, for the purpose of enhancing the flame retardancy, these aromatic dihydroxy compounds may have a structure substituted with a tetraalkylphosphonium sulfonate, a bromine atom, or a group having a siloxane structure.

  Examples of the aromatic polyhydroxy compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4 -Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1- Examples include tri (4-hydroxyphenyl) ethane, etc. The amount of the aromatic polyhydroxy compound used to obtain the branched aromatic polycarbonate resin (A) is based on the aromatic dihydroxy compound (100 mol%). Preferably, it is 0.01-10 mol%, More preferably, it is 0.1-2 mol%.

  A monovalent aromatic hydroxy compound or a monovalent aromatic hydroxy compound derivative such as a chloroformate thereof may be used for the purpose of adjusting the molecular weight of the aromatic polycarbonate resin (A), adjusting the end group, and the like. Examples of monovalent aromatic hydroxy compounds and derivatives thereof include phenol, m-cresol, p-cresol, p-propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenols, and derivatives thereof. It is done. The amount of these monovalent aromatic hydroxy compounds and / or derivatives thereof used is usually 0.1 to 10 mol%, preferably 1 to 8 mol%, based on the aromatic dihydroxy compound (100 mol%). .

The aromatic polycarbonate resin (A) has a dicarboxylic acid or dicarboxylic acid chloride for the purpose of copolymerizing a polymer or oligomer having a siloxane structure for the purpose of enhancing flame retardancy or improving the melt fluidity during molding. Derivatives such as these may be copolymerized.
The molecular weight of the aromatic polycarbonate-based resin (A) is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 10,000 to 40,000, more preferably 12,000 to 30,000, and 14,000. ˜26000 is particularly preferred. Two or more aromatic polycarbonate resins (A) may be mixed and used.

  As the resin material containing the aromatic polycarbonate resin (A), an aromatic polycarbonate polymer alloy obtained by combining the aromatic polycarbonate resin (A) with other resins and / or elastomers described later may be used.

[Other resins and elastomers]
The aromatic polycarbonate resin composition does not impair the excellent transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc. inherent in the aromatic polycarbonate resin (A). Specifically, in the range of 50 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (A), other resins and / or elastomers may be blended as necessary.

  Other resins include polystyrene (PSt), styrene random copolymers (acrylonitrile-styrene resin (AS resin), etc.), alternating copolymers of styrene and maleic anhydride, and graft copolymers (acrylonitrile-butadiene-). Styrene resins such as styrene resin (ABS resin), acrylonitrile-ethylene propylene rubber-styrene resin (AES resin), acrylonitrile-acrylate-styrene resin (AAS resin), high impact polystyrene (HIPS), etc .; polyethylene terephthalate (PET) , Polyesters such as polybutylene terephthalate (PBT) and copolymers thereof; acrylic resins such as polymethyl methacrylate (PMMA) and copolymers having methyl methacrylate units; polypropylene (PP) and polyethylene (PE), olefin resins such as ethylene- (meth) acrylic acid copolymer; polyurethane; silicone resin; syndiotactic PS; polyamide such as 6-nylon and 6,6-nylon; polyarylate; polyphenylene sulfide; Examples include various general-purpose resins or engineering plastics such as ether ketone; polysulfone; polyethersulfone polyamideimide; polyacetal.

  Examples of the elastomer include isobutylene-isoprene rubber; polyester-based elastomer; styrene-butadiene rubber, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-polyisoprene-polystyrene (SIS). Styrene elastomers such as polystyrene-poly (ethylene-propylene) -polystyrene (SEPS); polyolefin elastomers such as ethylene-propylene rubber; polyamide elastomers; acrylic elastomers; diene rubbers, acrylic rubbers, silicone rubbers, etc. Containing methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-styrene resin (MAS tree) ) Impact modifiers such as core-shell type represented by like.

[Flowability improver (B)]
The fluidity improver (B) is an aromatic vinyl monomer (b1) 0.5 to 99.5% by mass, and a monomer (b2) 0.5 to 99.5 represented by the following formula (I). And a monomer mixture composed of 0 to 40% by mass of the other monomer (b3) [provided that the total of the monomers (b1) to (b3) is 100% by mass. ] Is a polymer obtained by polymerizing.

(In formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted phenyl group.)
The fluidity improver (B) is a fragrance that exhibits phase separation behavior with the aromatic polycarbonate resin (A) during melt molding and has a good level of peel resistance in the use temperature range of the molded product. Because it exhibits compatibility (affinity) with the aromatic polycarbonate resin (A), it does not impair the properties (heat resistance, impact resistance, etc.) of the aromatic polycarbonate resin (A), and has an unprecedented melt fluidity. (Formability) and chemical resistance are improved.

  The fluidity improver (B) includes a mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization, and a content (% by mass) of each monomer constituent unit in the polymer after polymerization. ) Is preferably the same. In order to obtain such a polymer, the polymerization rate of the monomer mixture is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 97% by mass or more. . When the polymerization rate is 90% by mass or more, the mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization and the content (mass of each monomer constituent unit in the polymer after polymerization) %) Is almost the same. When the polymerization rate is less than 90% by mass, the mixing ratio (% by mass) of each monomer in the monomer mixture and the content (mass of monomer constituent units contained in the polymer after polymerization) %) May be different.

  Examples of the aromatic vinyl monomer (b1) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, Examples include chlorostyrene, bromostyrene, vinyl toluene, vinyl naphthalene, vinyl anthracene and the like. These may be used alone or in combination of two or more. Of these, styrene, α-methylstyrene, and pt-butylstyrene are preferable.

Content of an aromatic vinyl monomer (b1) is 0.5-99.5 mass% in a monomer mixture (100 mass%). When the content of the aromatic vinyl monomer (b1) is within this range, the fluidity improver (B) exhibits an excellent effect of improving melt fluidity and chemical resistance.
When the content of the aromatic vinyl monomer (b1) exceeds 99.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes insufficient, and as a result, the molded product causes delamination, and the appearance And may damage the mechanical properties. If the content of the aromatic vinyl monomer (b1) is less than 0.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes too good, so that the phase separation behavior is fully exhibited during melting. It cannot be done, and the effect of improving the melt fluidity tends to decrease and the effect of improving the chemical resistance tends to decrease.

  Considering the balance between appearance and mechanical properties, melt fluidity and chemical resistance, the content of the aromatic vinyl monomer (b1) is preferably 98% by mass or less, more preferably 96% by mass or less, and 93 The mass% or less is further preferable, and 90 mass% or less is particularly preferable. Further, the content of the aromatic vinyl monomer (b1) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 50% by mass or more, and particularly preferably 70% by mass or more.

  As the monomer (b2) represented by the formula (I), phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromo (meth) acrylate Examples include phenyl, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. Of these, phenyl (meth) acrylate is particularly preferred. In the present invention, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

Content of a monomer (b2) is 0.5-99.5 mass% in a monomer mixture (100 mass%). If content of a monomer (b2) exists in this range, a fluidity improver (B) will express the improvement effect of the outstanding compatibility (peeling resistance).
When the content of the monomer (b2) is less than 0.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes insufficient, and as a result, the molded product causes delamination, and the appearance and machine The characteristics may be impaired. When the content of the monomer (b2) exceeds 99.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes too good, so that the phase separation behavior can be sufficiently exhibited during melting. However, the effect of improving the melt fluidity tends to decrease and the effect of improving the chemical resistance tends to decrease.

  Considering the balance between appearance and mechanical properties, melt fluidity and chemical resistance, the content of the monomer (b2) is preferably 90% by mass or less, more preferably 80% by mass or less, and 50% by mass or less. Is more preferable, and 30% by mass or less is particularly preferable. Moreover, 2 mass% or more is preferable, as for content of a monomer (b2), 4 mass% or more is more preferable, 7 mass% or more is further more preferable, and 10 mass% or more is especially preferable.

  The polymer constituting the fluidity improver (B) can be copolymerized with the aromatic vinyl monomer (b1) and the monomer (b2), if necessary, within a range not impairing the above-mentioned characteristics. The monomer (b3) may be contained in an amount of 0 to 40% by mass.

  The other monomer (b3) is an α, β-unsaturated monomer. Such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid t-butyl, (meth) acrylic acid isobornyl, (meth) acrylic acid t-butylcyclohexyl; Reactive functional groups such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl phthalate, allyl (meth) acrylate, 1,3-butylene dimethacrylate (Meth) acrylic acid ester having vinyl benzoate, vinyl acetate, Water maleate, N- phenylmaleimide, cyclohexylmaleimide, divinylbenzene and the like. These may be used alone or in combination of two or more.

  Content of another monomer (b3) is 0-40 mass% in a monomer mixture (100 mass%). When the content of the monomer (b3) exceeds 40% by mass, the effect of improving the melt fluidity and chemical resistance of the aromatic polycarbonate resin composition tends to be lowered. The content of the other monomer (b3) is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

Since the fluidity improver (B) is excellent in compatibility with the aromatic polycarbonate resin (A), the transparency of the molded product made of the aromatic polycarbonate resin composition containing the fluid polycarbonate resin is improved. The polymer constituting the fluidity improver (B) is a two-component system of an aromatic vinyl monomer (b1) and a monomer (b2) represented by the formula (I), and the content thereof is further increased. By making it within a specific range, it becomes possible to express extremely high transparency.
As a polymer which expresses extremely high transparency, a polymer comprising 0.5 to 40% by mass of an aromatic vinyl monomer (b1) and 60 to 99.5% by mass of a monomer (b2) ( B1) (total amount of both is 100% by mass), aromatic vinyl monomer (b1) 60-99.5% by mass and monomer (b2) 0.5-40% by mass There are two combinations (B2) (the total amount of both is 100% by mass).

  The mass average molecular weight of the polymer constituting the fluidity improver (B) is preferably 5,000 to 200,000. If the mass average molecular weight is less than 5,000, relatively low molecular weight substances are increased, which may reduce various properties such as heat resistance and rigidity. In addition, there is a possibility that problems such as smoke generation at the time of melt molding, mist, mechanical dirt, appearance defects of molded products such as fish eyes and silver may increase. When a molded article having good transparency at high temperature (molded article having a low haze temperature dependency) is required, the polymer should have a higher mass average molecular weight. Therefore, the weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 15,000 or more, further preferably 30000 or more, and particularly preferably 40000 or more.

  Moreover, when the mass average molecular weight of the polymer exceeds 200,000, the melt viscosity of the aromatic polycarbonate resin composition becomes high, and there is a possibility that sufficient effect of improving melt fluidity cannot be obtained. In the case where it is desired to improve only the chemical resistance, there is no particular problem even if the mass average molecular weight of the polymer exceeds 200,000. If a significant effect of improving melt fluidity is required, the polymer should have a lower mass average molecular weight. Therefore, the weight average molecular weight of the polymer is preferably 170000 or less, more preferably 150,000 or less, further preferably 120,000 or less, and particularly preferably 100,000 or less.

  The molecular weight distribution of the polymer constituting the fluidity improver (B), that is, the mass average molecular weight (Mw) / number average molecular weight (Mn) is preferably smaller. The molecular weight distribution is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. If the molecular weight distribution exceeds 4.0, the melt viscosity of the aromatic polycarbonate resin composition also increases, and there is a possibility that sufficient effect of improving melt fluidity cannot be obtained.

  Examples of the method for producing the polymer constituting the fluidity improver (B) include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. Among these, the suspension polymerization method and the emulsion polymerization method are preferable because the recovery method is easy. In the case of the emulsion polymerization method, residual salts in the polymer may cause thermal decomposition of the aromatic polycarbonate resin. Therefore, at the time of emulsion polymerization, a carboxylate emulsifier or the like is used, and the polymer is recovered by acid precipitation coagulation or the like, or a nonionic anionic emulsifier such as a phosphate ester is used, and the polymer is calcium acetate salt or the like. It is preferable to recover by salting out coagulation using

  What is necessary is just to determine the compounding quantity of a fluid improvement agent (B) suitably according to a desired physical property. In order to obtain an effective effect of improving melt fluidity without deteriorating the properties (transparency, heat resistance, impact resistance, etc.) of the aromatic polycarbonate resin (A), the blending of the fluidity improver (B) The amount is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resins and / or elastomers. If the blending amount of the fluidity improver (B) is less than 0.1 parts by mass, a sufficient effect of improving melt fluidity may not be obtained. If the blending amount of the fluidity improver (B) exceeds 30 parts by mass, the excellent mechanical properties of the aromatic polycarbonate resin (A) may be impaired. The blending amount of the fluidity improver (B) is preferably 1 part by mass or more and more preferably 2 parts by mass or more with respect to a total of 100 parts by mass of the aromatic polycarbonate resin (A) and other resins and / or elastomers. It is preferably 3 parts by mass or more. Further, the blending amount of the fluidity improver (B) is preferably 25 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resins and / or elastomers. Is more preferable, and 10 parts by mass or less is particularly preferable.

〔Additive〕
In the aromatic polycarbonate resin composition, an ultraviolet absorber, light, etc., as necessary, as long as the excellent characteristics (transparency, heat resistance, impact resistance, etc.) of the aromatic polycarbonate resin (A) are not impaired. Stabilizers, antioxidants, heat stabilizers and other stabilizers; inorganic fillers, flame retardants, non-drip agents, antistatic agents, mold release agents, light diffusing agents, bluing agents, dyes, infrared absorbers, resistance You may mix | blend well-known various additives, such as an impact modifier.

[Aromatic polycarbonate resin composition]
The aromatic polycarbonate-based resin composition includes, for example, an aromatic polycarbonate-based resin (A) and a fluidity improver (B), and if necessary, other resins and / or elastomers, various additives, a tumbler, and a V-type blender. , A super mixer, a nauter mixer, a Banbury mixer, a kneading roll, an extruder and the like.

  The blending of various additives may be carried out in one step or in two or more steps. As a method to be carried out in two stages, for example, after various additives are blended in advance, this is blended with the aromatic polycarbonate resin (A) and the fluidity improver (B); A part of the resin-based resin (A) and various additives and fluidity improver (B) are blended, that is, the various additives are diluted with the aromatic polycarbonate-based resin (A) to obtain a master batch of various additives. Then, the method of blending this masterbatch and aromatic polycarbonate resin (A) is mentioned.

The aromatic polycarbonate resin composition in the present invention can provide a molded article having excellent transparency. More specifically, it is possible to provide a molded product having transparency in which the haze of a molded product having a thickness of 2 mm is in the range of 0.1 to 5%. Moreover, when the above-mentioned polymer (B1) or polymer (B2) is used as the fluidity improver (B), the haze of the molded product having a thickness of 3 mm is excellent in the range of 0.1 to 2%. It is possible to provide a molded product having high transparency.
Moreover, the aromatic polycarbonate-type resin composition in this invention can provide the molded article with which transparency was maintained within the temperature range for experiment (room temperature-high temperature). High temperature here is the range of 60-100 degreeC.

〔Molding〕
The molded article in the present invention is the above-mentioned aromatic polycarbonate resin composition as it is or after being once pelletized with a melt extruder, and then an injection molding method, extrusion molding method, compression molding method, blow molding method, cast molding. It can be obtained by melt molding by a known melt molding method such as a method.

  As the melt molding method, an injection molding method is preferable. Examples of the injection molding method include not only a normal injection molding method but also an injection compression molding method, an injection press molding method, a heat insulating mold molding method, a rapid heating / cooling mold molding method, an ultra-high speed injection molding method, and the like. Among these, injection press molding is a molding method capable of reducing the molding temperature, and is preferable because a molded product having a good appearance and hue can be obtained.

  In addition, a hard coat layer is provided on a polycarbonate sheet or film made of the above-mentioned aromatic polycarbonate resin composition prepared in advance by an extrusion molding method or the like, and the polycarbonate sheet or film having the hard coat layer is mounted in a mold. After that, a method of injecting the aromatic polycarbonate resin composition into the mold and integrating the polycarbonate sheet or film having the hard coat layer with the molded product may be used.

[Hard coat product]
The hard coat product of the present invention is one in which a hard coat layer is provided on the surface of a molded product formed by molding the above-mentioned aromatic polycarbonate resin composition.

The hard coat layer is formed by applying and curing a hard coat agent on the surface of a molded product formed by molding an aromatic polycarbonate resin composition, or on the surface of a polycarbonate sheet or film as a skin material of the molded product. Is done.
Examples of the hard coating agent include a silicone resin hard coating agent and other organic resin hard coating agents.

  The silicone resin hard coat agent forms a cured resin layer having a siloxane bond. Examples of the silicone resin hard coat agent include partially hydrolyzed condensates of compounds mainly composed of compounds corresponding to trifunctional siloxane units (trialkoxysilane compounds, etc.) and compounds corresponding to trifunctional siloxane units and tetrafunctional. Examples include partial hydrolysis condensates of compounds containing compounds corresponding to siloxane units (tetraalkoxysilane compounds, etc.), partial hydrolysis condensates obtained by filling these partial hydrolysis condensates with metal oxide fine particles such as colloidal silica, and the like. It is done. These partial hydrolysis-condensation products may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These partial hydrolysis-condensation products include alcohols generated during the condensation reaction (in the case of partial hydrolysis-condensation products of alkoxysilanes) and the like.

  These partial hydrolysis-condensation products may be dissolved or dispersed in an arbitrary organic solvent, water, or a mixture thereof as necessary. The organic solvent is preferably one that does not react with the molded product or does not dissolve the molded product, and examples thereof include lower fatty acid alcohols, polyhydric alcohols, ethers, and esters. Further, in order to smooth the surface of the hard coat layer, various surfactants such as a siloxane surfactant and a fluoroalkyl surfactant may be added to the silicone resin hard coat agent. . When a hard coat layer with excellent long-term weather resistance and relatively high surface hardness is required, a silicone resin hard coat agent is preferred.

  Examples of other organic resin hard coat agents include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Among these, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, monofunctionality such as organic-inorganic hybrid (meth) acrylate obtained by condensing colloidal silica and (meth) acryloylalkoxysilane ( Preferred are monomers or oligomers such as (meth) acrylates or polyfunctional (meth) acrylates; organic-inorganic hybrid vinyl compounds. In the present invention, (meth) acrylate means acrylate and / or methacrylate.

These other organic resin hard coat agents may be appropriately selected according to the required performance of the obtained hard coat layer. Moreover, these may be used individually by 1 type and may use 2 or more types together. Since it is easy to adjust the required performance of the obtained hard coat layer, it is preferable to use two or more kinds in combination.
Among other organic resin hard coat agents, a hard coat layer having excellent heat resistance, chemical resistance, weather resistance, and adhesion to a molded product can be obtained. A composition containing a polyfunctional acrylate and urethane poly (meth) acrylate having at least two radically polymerizable unsaturated double bonds in one molecule is preferable.

The hard coat layer may have a primer layer (first layer) made of various resins and a top layer (second layer) made of a silicone resin hard coat agent formed on the primer layer. Good.
As the resin forming the primer layer (first layer), urethane resin, acrylic resin, polyester resin, epoxy resin, melamine resin, amino resin composed of various block isocyanate components and polyol components; polyester acrylate, urethane acrylate, epoxy acrylate, Examples include various polyfunctional acrylic resins such as phosphazene acrylate, melamine acrylate, and amino acrylate. These may be used alone or in combination of two or more. Among these, those containing 50% by mass, preferably 60% by mass or more of acrylic resin or polyfunctional acrylic resin are preferred, and those comprising acrylic resin and urethane acrylate are particularly preferred.

Hard coating agents include light stabilizers, UV absorbers, antioxidants, catalysts, thermal / photopolymerization initiators, polymerization inhibitors, antifoaming agents, viscosity modifiers, leveling agents, thickeners, precipitation inhibitors, Various additives such as sagging inhibitors, flame retardants, organic / inorganic pigments / dyes, antistatic agents, or additive aids may be added.
As the viscosity modifier, any material that does not impair the properties of the hard coating agent and does not react with the molded product or dissolve the molded product, for example, those having low viscosity of various resins used in the hard coating agent, Examples include various organic solvents. Examples of the organic solvent include alcohols such as n-butanol and i-butanol, and esters such as n-butyl acetate and diethylene glycol acetate. These are preferably used in appropriate combination.

The hard coat agent is applied to the molded product according to the shape of the molded product from known coating methods such as bar coating, dip coating, flow coating, spray coating, spin coating, and roller coating. An application method can be selected as appropriate. Among these, the dip coating method, the flow coating method, and the spray coating method are preferable from the viewpoints of easily dealing with complicated shapes and easy film thickness control.
When the organic solvent is used, the hard coating agent can be cured by volatilizing the organic solvent, and then irradiating and / or heating it with active energy rays such as ultraviolet rays and electron beams.

  Since the hard coat product of the present invention is excellent in transparency, heat resistance, impact resistance and appearance, various electronic / electric equipment, OA equipment, vehicle parts, machine parts, agricultural materials, fishery materials, transport containers, packaging containers It is useful for various uses such as playground equipment and miscellaneous goods. In addition, because it can be made larger, lighter and thinner, more complicated in shape, and higher in performance, it can be used for glazing materials for vehicles, window glass for construction machinery, windows for buildings, houses, greenhouses, garages, arcade roofs, etc. Games such as lighting lenses, traffic light lenses, optical equipment lenses, mirrors, glasses, goggles, noise barriers, motorcycle windshields, nameplates, solar cell covers, solar cell substrates, display device covers, touch panels, pachinko machines, etc. It is useful for a wide range of applications such as machine parts (circuit covers, chassis, pachinko ball conveyance guides, etc.). In particular, various optical information recording media such as CDs, CD-Rs, DVDs, and MDs; various lamp covers for automobiles such as headlamps, inner lenses, and rear lamps; front door windows (windshields), rear door windows, quarter windows, and back windows It is suitable for glazing materials for buildings and vehicles such as back door windows, sunroofs, roof panels and various window materials.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

(Production Example 1)
Production of fluidity improver (B-1):
In a separable flask equipped with a condenser and a stirrer, anionic emulsifier ("Latemul ASK", manufactured by Kao Corporation) (solid content 28%) 1.0 part (solid content), 295 parts distilled water, Heated to 80 ° C. in a water bath under nitrogen atmosphere. Then, in a separable flask, 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were added in 5 parts of distilled water, and then 80 parts of styrene. Then, a mixture of 20 parts of phenyl methacrylate, 0.2 part of t-butyl hydroperoxide and 0.5 part of n-octyl mercaptan was added dropwise over 180 minutes. Thereafter, the mixture was stirred at 80 ° C. for 60 minutes to obtain a polymer emulsion (polymerization rate: 98%).

  While stirring, 300 parts of an aqueous solution in which sulfuric acid was dissolved at a ratio of 0.7% was heated to 70 ° C., and the polymer emulsion obtained therein was gradually added dropwise to solidify the polymer. The precipitate was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (fluidity improver (B-1)). The weight average molecular weight (Mw) was 49000, and the molecular weight distribution (Mw / Mn) was 2.1.

(Production Example 2)
Production of fluidity improver (B-2):
A polymer (fluidity) was obtained in the same manner as in Production Example 1 except that 87.5 parts of styrene, 12.5 parts of phenyl methacrylate, and the amount of n-octyl mercaptan were changed from 0.5 part to 0.2 part. An improver (B-2)) was obtained (polymerization rate was 98%). The weight average molecular weight (Mw) was 97000, and the molecular weight distribution (Mw / Mn) was 2.0.

(Production Example 3)
Production of fluidity improver (B-3):
A polymer (flowability improver (B-3) was prepared in the same manner as in Production Example 1 except that 20 parts of styrene, 80 parts of phenyl methacrylate, and the amount of n-octyl mercaptan were changed from 0.5 part to 2 parts. )) Was obtained (polymerization rate 99%). The weight average molecular weight (Mw) was 27000, and the molecular weight distribution (Mw / Mn) was 1.9.

(Production Example 4)
Production of fluidity improver (B′-4):
A separable flask equipped with a condenser and a stirrer was charged with 0.4 parts of calcium phosphate and 150 parts of distilled water, and then 96 parts of styrene, 4 parts of n-butyl methacrylate and 1.2 parts of benzoyl peroxide were dissolved. After stirring for a while, nitrogen bubbling was performed for 30 minutes. The mixture was stirred at 80 ° C. for 4 hours under a nitrogen atmosphere, and further stirred at 90 ° C. for 1 hour. The precipitate was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (flowability improver (B′-4)) (polymerization rate was 97%). The mass average molecular weight (Mw) was 150,000, and the molecular weight distribution (Mw / Mn) was 3.3.

  Table 1 shows the charged amount (parts) of each component, the polymerization mode, the polymerization rate, the mass average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the obtained polymer in Production Examples 1 to 4. In the table, St is styrene, PhMA is phenyl methacrylate, BA is n-butyl acrylate, and BPO is benzoyl peroxide. Moreover, the polymerization rate was computed by conversion of the mass of the obtained polymer solid. Moreover, the mass average molecular weight (Mw) and the number average molecular weight (Mn) were measured by GPC method (eluent: chloroform).

(Examples 1-4, Comparative Examples 1-3)
The following were prepared as aromatic polycarbonate resins.
PC1: Aromatic polycarbonate resin, “Panlite L1225WS”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 21,000.
PC2: Aromatic polycarbonate resin, “Panlite L1225ZL”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 18,000.

  A fluidity improver and an aromatic polycarbonate resin were mixed in the formulation shown in Table 2 (100 parts in total), and an ultraviolet absorber (“Tinuvin 329”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 Part, 0.1 part of antioxidant ("Irganox 1076", manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.1 part of heat stabilizer ("Adeka Stub 2112", manufactured by Asahi Denka Kogyo Co., Ltd.) The mixture was supplied to a twin screw extruder (model name “TEM-35”, manufactured by Toshiba Machine Co., Ltd.) and melt kneaded at 280 ° C. to obtain an aromatic polycarbonate resin composition.

Using the obtained aromatic polycarbonate resin composition, a 2 mm thick, 10 cm square flat plate molded product was obtained by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
On one side of the molded product, a hard coat agent (UV curable paint for hard coat, “UV-7605B”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is applied by spray coating so that the film thickness after curing is 8 μm. N-butanol solution) was applied. After standing for 1 minute, the molded product was placed in a heating furnace at 60 ° C., and the organic solvent was volatilized from the coating film by heating for 90 seconds. Then, using a high-pressure mercury lamp in an air atmosphere, ultraviolet rays with a wavelength of 340 to 380 nm are irradiated so that the integrated light amount is 3000 mJ / cm ² to cure the coating film, and a hard coat layer is formed on the surface of the molded product Then, a hard coat product was obtained.
The obtained aromatic polycarbonate resin composition and hard coat product were evaluated in the following (1) to (9). The results are shown in Table 2.

(Evaluation methods)
(1) Melt fluidity:
The spiral flow length (SFL) of the aromatic polycarbonate resin composition was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The molding temperature was 280 ° C., the mold temperature was 80 ° C., and the injection pressure was 98 MPa. The thickness of the molded product was 2 mm and the width was 15 mm.

(2) Chemical resistance:
Using an aromatic polycarbonate resin composition, a 2 mm thick, 15 cm square flat plate was produced by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.), and this was cut to a thickness of 2 mm. A molded product of 15 cm × 2.5 cm was obtained. After the test piece was annealed at 120 ° C. for 2 hours, a cantilever test was performed, and the breaking time of the test piece by chemical application was measured. The measurement was performed at a test temperature: 23 ° C., a load: 20 MPa, and a solvent: toluene / isooctane = 1/1 vol ratio.

(3) Surface peelability (peeling resistance):
The protruding pin mark of the molded product obtained in (2) was cut with a cutter, and the peeled state was visually observed. The evaluation criteria are as follows.
○: Good without peeling.
X: Surface layer peeling is seen.

(4) Deflection temperature under load (heat resistance):
Using the aromatic polycarbonate resin composition, a molded article having a thickness of ¼ inch was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The deflection temperature under load of the molded product was measured according to ASTM D648. The annealing treatment was performed at 120 ° C. for 1 hour, and the load was 1.82 MPa.

(5) Hard coat layer adhesion:
In accordance with the method of cross-cut peel test described in JIS K-5400, a test piece in which a hard coat layer of a hard coat product is cut with a grid cut is produced, and Cellotape (registered trademark) (Nichiban Co., Ltd.) The product is attached to the test piece, and then the tape is quickly pulled in a direction of 90 degrees to peel off, and the number of grids remaining on the surface of the hard coat product is counted. As an index, evaluation was made with no peeling (◯) and with partial peeling (x).

(6) Appearance:
The surface of the hard coat layer of the hard coat product was observed with the naked eye under sunlight to evaluate the presence or absence of silver and cracks. The evaluation criteria are as follows.
○: No occurrence of silver or cracks.
Δ: Silver or crack occurred.
X: Silver and cracks are generated.

(7) Haze:
The haze of the hard coat product was measured at 23 ° C. according to ASTM D1003.

(8) Surface impact test:
Using a graphic impact tester (manufactured by Toyo Seiki Kogyo Co., Ltd.), a surface impact test of the hard coat layer of the hard coat product was performed, and the total absorbed energy (J) was measured. The measurement conditions were as follows: hitting core diameter: 1/2 inch, cradle diameter: 3 inches, drop height: 60 cm, weight mass: 14.5 kg.

(9) Destruction mode:
The fracture form of the hard coat product after the test of (8) was visually evaluated. The evaluation criteria are as follows.
○: Ductile and similar destruction.
X: Brittle and similar fracture.

As is apparent from the results in Table 2, in Examples 1 to 4, the melt fluidity of the aromatic polycarbonate resin composition and the molded product were obtained without impairing the heat resistance, peel resistance, and transparency of the molded product. Significant improvement in chemical resistance was observed, and the hard coat product obtained therefrom had good adhesion, appearance and impact resistance of the hard coat layer.
On the other hand, in Comparative Example 1, since the compatibility of the aromatic polycarbonate resin composition was insufficient, good peeling resistance was not obtained, and improvement in melt fluidity and chemical resistance was not obtained. And the hard-coat goods obtained from this were inferior to the adhesiveness of a hard-coat layer, an external appearance, and impact resistance.

  In Comparative Examples 2 and 3, the aromatic polycarbonate resin composition did not contain the fluidity improver (B), and sufficient fluidity and chemical resistance could not be obtained. In particular, in Comparative Example 2, the melt flowability of the aromatic polycarbonate resin composition is insufficient, and in Comparative Example 3, the chemical resistance of the molded product is reduced. The appearance and impact resistance were greatly reduced.

The hard coat product of the present invention is large, thin (light weight), and complex in shape without impairing the excellent properties (transparency, heat resistance, impact resistance, etc.) of molded products made of aromatic polycarbonate resin. It is possible to improve the performance and performance, and it has excellent appearance, such as various electronic / electric equipment, OA equipment, vehicle parts, machine parts, agricultural materials, fishery materials, transport containers, packaging containers, playground equipment, miscellaneous goods, etc. Useful for various applications. In particular, it is suitable for optical information recording media, automotive lamp covers, and glazing materials for buildings and vehicles because it can cope with large size, light weight, thin shape, complicated shape, and high performance. It is exceptional.

Claims (1)

A hard coat product in which a hard coat layer is provided on the surface of a molded product formed by molding an aromatic polycarbonate resin composition containing an aromatic polycarbonate resin (A) and a fluidity improver (B),
The fluidity improver (B) is an aromatic vinyl monomer (b1) 0.5 to 99.5% by mass, a monomer (b2) represented by the following formula (I) 0.5 to 99.99. Monomer mixture consisting of 5% by mass and other monomers (b3) 0 to 40% by mass [wherein the total of the monomers (b1) to (b3) is 100% by mass. ] Is a polymer obtained by polymerizing].

(In formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted phenyl group.)