JP2020131585A - Decorative molding - Google Patents

Abstract

To provide a decorative molding having good chemical resistance to a thermosetting resin and excellent surface hardness and appearance.SOLUTION: There is provided a decorative molding in which a layer composed of a polycarbonate resin (A) including a unit represented by the following formula (1) and a thermosetting resin (B) are laminated.SELECTED DRAWING: None

Description

The present invention relates to a decorative molded body in which a polycarbonate resin and a thermosetting resin are laminated.

The fiber-reinforced composite material, which is a composite of fiber and resin, has excellent features such as advanced mechanical properties, light weight, and easy workability, and is used for various industrial materials such as automobiles, aircraft, personal computers, and digital cameras. It is used as. For example, carbon fiber reinforced composite materials are being increasingly adopted as interior and exterior materials for automobiles and aircraft because they are lightweight and have strength and elastic modulus comparable to those of metals.

When a fiber-reinforced composite material is used as a surface material, it is necessary to cover the surface by painting. However, there is a problem that surface defects due to the unevenness of the texture of the fiber are likely to occur and the productivity is inferior.

Under these circumstances, a method of decorating and molding a fiber-reinforced composite material using a resin film has been developed. Patent Document 1 discloses a method of laminating an acrylic resin film on an uncured fiber-reinforced thermosetting resin and performing decorative molding. However, the acrylic resin film has a problem that it has poor chemical resistance to a thermosetting resin and is inferior in adhesion and appearance. In order to decorate and mold the fiber-reinforced composite material as described above, it is necessary to use a resin film having both chemical resistance and adhesion to a thermosetting resin.

Japanese Unexamined Patent Publication No. 9-174547

Therefore, an object of the present invention is to provide a decorative molded article having good adhesion to a thermosetting resin and having excellent surface hardness and appearance.

As a result of diligent research, the present inventors have obtained a decorative molded product having good adhesion to a thermosetting resin and having excellent surface hardness and appearance by using a polycarbonate resin containing isosorbide. After investigating this, the present invention was completed.
That is, according to the present invention, the subject of the invention is achieved by the following.

1. 1. A decorative molded body in which a layer made of a polycarbonate resin (A) containing a unit represented by the following formula (1) and a thermosetting resin (B) are laminated.

2. 2. The decorative molded article according to item 1 above, wherein the polycarbonate resin (A) has a glass transition temperature of 90 ° C to 160 ° C.
3. 3. The decorative molded product according to any one of items 1 and 2 above, wherein the surface hardness of the polycarbonate resin (A) is HB or higher.
4. The decorative molded product according to any one of items 1 to 3 above, wherein the thermosetting resin (B) is any of an epoxy resin, a phenol resin, and a polyimide resin.
5. The decorative molded product according to any one of items 1 to 4 above, wherein the thermosetting resin (B) is a fiber-reinforced thermosetting resin.

According to the present invention, by using a polycarbonate resin containing isosorbide, it has become possible to provide a decorative molded article having good adhesion to a thermosetting resin and having excellent surface hardness and appearance. Therefore, the industrial effect it produces is exceptional.

Hereinafter, the present invention will be described in detail.
<Polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention contains a unit represented by the above formula (1). The content ratio of the repeating unit represented by the formula (1) is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 55 mol% or more in all the repeating units. As mentioned above, it is particularly preferably 60 mol% or more, and most preferably 65 mol% or more. Further, it is preferably 100 mol% or less, more preferably 98 mol% or less, still more preferably 95 mol% or less, and particularly preferably 90 mol% or less. Such a molar ratio is preferable because it has good adhesion to a thermosetting resin, has a high surface hardness, and has a good appearance.

Further, it is preferable to include many units represented by the formula (1) because the chemical resistance is improved. For chemical resistance, refer to the literature (“2013 Decorative Film-related Market Outlook and Manufacturer Strategy”, pp. 118-122, Fuji Keizai), and refer to the commercially available tanning cream (Mentholatum Skin Aqua manufactured by Rohto Pharmaceutical Co., Ltd.). SPF45) was uniformly applied to the surface of the decorative molded product sample (first layer; polycarbonate resin (A) film layer side), heat-treated at 80 ° C. for 4 hours, and then wiped off with a cloth to visually check the surface appearance. By doing so, it can be determined by the wiping condition and the presence or absence of whitening.

Further, when the molar ratio of the unit represented by the formula (1) is smaller than the lower limit, the surface hardness may be low. The molar ratio can be measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL Ltd.
Examples of the repeating unit represented by the formula (1) include repeating units (1-1), (1-2) and (1-3) represented by the following formulas having a stereoisomeric relationship.

These are sugar-derived ether diols, which are also obtained from natural biomass, and are one of the so-called renewable resources. The repeating units (1-1), (1-2) and (1-3) are called isosorbide, isomannide and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting material.

Among isosorbide, isomannide, and isoidide, the repeating unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because it is easy to manufacture and has excellent heat resistance.

The diol compound (diol monomer) that induces a repeating unit other than the repeating unit represented by the formula (1) may be any of an aliphatic diol compound, an alicyclic diol compound, and an aromatic dihydroxy compound, and is published internationally. Examples thereof include diol compounds described in Pamphlet No. 2004/11106 and Pamphlet No. 2011/021720, and oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. These may be used alone or in combination of two or more. Representative specific examples of the diol component are shown below, but the diol component is not limited thereto.

Examples of the aliphatic diol compound include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1.9-nonanediol. 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl- 1,3-Propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexaneglycol, 1,2-octylglycol, 2-ethyl -1,3-Hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc. Can be mentioned.

Examples of the alicyclic diol compound include cyclohexanedimethanol, tricyclodecanedimethanol, adamantandiol, pentacyclopentadecanedimethanol, and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4. 8,10-Tetraoxaspiro [5.5] undecane, 2,2,4,4-tetramethylcyclopentanediol, 1,1'-spirobiindane-6,6'-diol, decalin-2,6-dimethanol, Norbornane dimethanol, cyclopentane-1,3-dimethanol, and the like can be mentioned.

Examples of the aromatic dihydroxy compound include α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis (4). -Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, bisphenol A, 2,2-bis (4-hydroxy-3-methylphenyl) propane ( Bisphenol C), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF), biphenol, 1,1-bis (4-hydroxyphenyl) decane , Bis (2-hydroxyethoxy) naphthalene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -1,8-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3) -Methylphenyl) -1,8-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -1,8-diphenylfluorene, 9,9-bis (4- (2) -Hydroxyethoxy) -1-naphthyl) -1,8-diphenylfluorene, 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) -1,8-diphenylfluorene, 9,9-bis ( 4-Hydroxyphenyl) -1,8-diphenylfluorene, 9,9-bis (4-hydroxy-3-methylphenyl) -1,8-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) ) -1,8-Diphenylfluorene, 9,9-bis (4-hydroxy-1-naphthyl) -1,8-diphenylfluorene, 9,9-bis (6-hydroxy-2-naphthyl) -1,8- Diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2,7-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -2, 7-Diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -2,7-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -1- Naftyl) -2,7-diphenylfluorene, 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) -2,7-diphenylfluorene, 9,9-bis (4-hydroxyphenyl) -2 , 7-Diphenylfluorene, 9,9-bis (4-hydroxy-3-methylphenyl) -2,7-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) -2,7-diphenyl Fluorene, 9,9-bis (4-hydroxy-1-naphthyl) -2,7-diphenylfluorene, 9,9-bis (6-hydroxy-2-naphthyl) -2,7-diphenylfluorene, 9,9- Bis (4- (2-hydroxyethoxy) phenyl) -3,6-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -3,6-diphenylfluorene, 9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -3,6-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -1-naphthyl) -3,6- Diphenylfluorene, 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) -3,6-diphenylfluorene, 9,9-bis (4-hydroxyphenyl) -3,6-diphenylfluorene, 9 , 9-bis (4-hydroxy-3-methylphenyl) -3,6-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) -3,6-diphenylfluorene, 9,9-bis (4-Hydroxy-1-naphthyl) -3,6-diphenylfluorene, 9,9-bis (6-hydroxy-2-naphthyl) -3,6-diphenylfluorene, 9,9-bis (4- (2-) Hydroxyethoxy) phenyl) -4,5-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -4,5-diphenylfluorene, 9,9-bis (4-( 2-Hydroxyethoxy) -3-phenylphenyl) -4,5-diphenylfluorene, 9,9-bis (4- (2-hydroxyethoxy) -1-naphthyl) -4,5-diphenylfluorene, 9,9- Bis (6- (2-hydroxyethoxy) -2-naphthyl) -4,5-diphenylfluorene, 9,9-bis (4-hydroxyphenyl) -4,5-diphenylfluorene, 9,9-bis (4-) Hydroxy-3-methylphenyl) -4,5-diphenylfluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) -4,5-diphenylfluorene, 9,9-bis (4-hydroxy-1- Naftil) -4,5-diphenylfluorene, 9,9-bis (6-bis) Hydroxy-2-naphthyl) -4,5-diphenylfluorene, 2,2'-bis (2-hydroxyethoxy) -3,3'-diphenyl-1,1'-binaphthyl, 2,2'-bis (2-) Hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis (2-hydroxyethoxy) -7,7'-diphenyl-1,1'-binaphthyl, 2,2'- Bis (2-hydroxyethoxy) -3,3'-dimethyl-1,1'-binaphthyl, 2,2'-bis (2-hydroxyethoxy) -6,6'-dimethyl-1,1'-binaphthyl, 2 , 2'-bis (2-hydroxyethoxy) -7,7'-dimethyl-1,1'-binaphthyl, 1,1'-bi-2-naphthol, dihydroxynaphthalene and the like.

The content ratio of the other repeating units is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, still more preferably 45 mol% or less, and particularly preferably 40, in all the repeating units. It is mol% or less, most preferably 35 mol% or less. Further, it is preferably 2 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more.

(Production method)
The polycarbonate resin (A) is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a diol component with a carbonic acid precursor such as a carbonic acid diester. Next, the basic means for these manufacturing methods will be briefly described.

The transesterification reaction using a carbonic acid diester as a carbonic acid precursor is carried out by a method in which a predetermined proportion of the diol component is stirred with the carbonic acid diester while heating in an inert gas atmosphere to distill out the produced alcohol or phenols. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. Further, a terminal terminator, an antioxidant and the like may be added as needed.

Examples of the carbonic acid diester used in the transesterification reaction include esters such as an aryl group and an aralkyl group having 6 to 12 carbon atoms which may be substituted. Specific examples thereof include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferable. The amount of the diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, based on 1 mol of the total dihydroxy compound.

Further, in the melt polymerization method, a polymerization catalyst can be used in order to increase the polymerization rate, and examples of such a polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides and the like of alkali metals and alkaline earth metals are preferably used, and these compounds are used. It can be used alone or in combination.

Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, etc. Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples thereof include 2 lithium hydrogen acid, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium phenol salt, potassium salt, cesium salt, lithium salt and the like.

Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and diacetic acid. Examples include barium and barium stearate.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having alkyl and aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide. Can be mentioned. Examples thereof include tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole. Further, bases such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like, or basic salts and the like are exemplified.

Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. These compounds may be used alone or in combination of two or more.

The amount of these polymerization catalysts used is preferably 1 × 10 ^-9 to 1 × 10 ⁻² equivalents, preferably 1 × 10 ^-8 to 1 × 10 ⁻⁵ equivalents, and more preferably 1 × 10 to 1 mol of the diol component. It is selected in the range of ^10-7 to 1 × 10 ^-3 equivalents.

It is also possible to add a catalyst deactivating agent in the latter stage of the reaction. As the catalyst deactivating agent to be used, known catalyst deactivating agents are effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acids are preferable. Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

As esters of sulfonic acid, methyl benzenesulfonic acid, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenylbenzenesulfonic acid, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are preferably used. Of these, the tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is most preferably used.

The amount of these catalyst deactivators used is preferably 0.5 to 50 mol per mol of the catalyst when at least one polymerization catalyst selected from the alkali metal compound and / or the alkaline earth metal compound is used. It can be used in proportions, more preferably 0.5 to 10 mol, and even more preferably 0.8 to 5 mol.

(Specific viscosity: η _SP )
The specific viscosity (η _SP ) of the polycarbonate resin (A) is preferably 0.2 to 1.5. It is more preferably 0.22 to 1.2, further preferably 0.25 to 1.0, particularly preferably 0.28 to 0.5, and most preferably 0.3 to 0.4. is there. When the specific viscosity is in the above range, the strength and moldability of the molded product are good.
The specific viscosity referred to in the present invention was determined from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
The specific specific viscosity can be measured, for example, as follows. First, the polycarbonate resin is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and sufficiently dried to obtain a solid of methylene chloride soluble component. The specific viscosity at 20 ° C. of a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride is determined using an Ostwald viscometer.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polycarbonate resin (A) is preferably 90 to 160 ° C, more preferably 92 to 150 ° C, still more preferably 95 to 140 ° C, and particularly preferably 100 to 130 ° C. .. When Tg is within the above range, heat stability and moldability are good, which is preferable.
The glass transition temperature (Tg) is measured at a heating rate of 20 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd.

(Pencil hardness)
The layer made of the polycarbonate resin (A) preferably has a pencil hardness of HB or higher. It is more preferably F or more in that it is more excellent in scratch resistance. The pencil hardness of 4H or less has a sufficient function. In the present invention, the pencil hardness is the hardness at which no scratch marks remain even when the resin of the present invention is rubbed with a pencil having a specific pencil hardness, and is measured according to JIS K-5600. It is preferable to use the pencil hardness used for the surface hardness test of the resulting coating film as an index. Pencil hardness is 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, and the hardest is 9H, the hardest. The soft one is 6B.

The layer made of the polycarbonate resin (A) may contain other components in addition to the polycarbonate resin (A) as long as the effects of the present invention are not significantly impaired. Examples of other components include aromatic polycarbonate resins, resins other than polycarbonate resins, and thermoplastic elastomers. In addition, 1 type may be contained in the other component, and 2 or more types may be contained in arbitrary combinations and ratios. Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); polystyrene resin (PS resin) and high-impact polystyrene. Resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-polyethylene propylene rubber- Polystyrene resin such as styrene copolymer (AES resin); polyolefin such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin Resin; Polyethylene resin (PA resin); Polystyrene resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); and the like. Among the above, ABS resin, PP resin, PET resin, PBT resin, PPS resin, and PMMA resin are preferable, ABS resin, PET resin, and PMMA resin are more preferable, and PMMA resin is particularly preferable.

The thermoplastic elastomer is not particularly limited, and examples thereof include polystyrene-based elastomers, polyolefin-based elastomers, polyester-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, and fluoropolymer-based elastomers. Among the above, polyester-based elastomers are preferable.

The ratio of the polycarbonate resin (A) to the layer made of the polycarbonate resin (A) is preferably 30% by weight or more, more preferably 50% by weight or more, further preferably 70% by weight or more, particularly preferably 80% by weight or more, 90% by weight or more. Most preferably by weight% or more.

The ratio of the components other than the polycarbonate resin (A) to the layer made of the polycarbonate resin (A) is preferably 70% by weight or less, more preferably 50% by weight or less, further preferably 30% by weight or less, and 20% by weight. The following is particularly preferable, and 10% by weight or less is most preferable. If the proportion of the components other than the polycarbonate resin (A) is too high, the adhesiveness of the decorative molded product tends to decrease.

(Additive)
The polycarbonate resin (A) used in the present invention includes a heat stabilizer, a plasticizer, a light stabilizer, a polymer metal inactivating agent, a flame retardant, a lubricant, an antistatic agent, and a surfactant, if necessary. , Antibacterial agents, UV absorbers, mold release agents, fillers, compatibilizers and other additives can be added.

(Heat stabilizer)
The polycarbonate resin (A) used in the present invention preferably contains a heat stabilizer in order to suppress a decrease in molecular weight and deterioration of hue during extrusion and molding. Examples of the heat stabilizer include phosphorus-based heat stabilizers, phenol-based heat stabilizers, and sulfur-based heat stabilizers, and one of these can be used alone or in combination of two or more. In particular, since the ether diol residue of the unit (a-1) is deteriorated by heat and oxygen and easily colored, it is preferable to contain a phosphorus-based heat stabilizer as the heat stabilizer. As the phosphorus-based stabilizer, it is preferable to add a phosphite compound. Examples of the phosphite compound include a pentaerythritol-type phosphite compound, a phosphite compound that reacts with divalent phenols and has a cyclic structure, and a phosphite compound having another structure.

Specific examples of the above-mentioned pentaerythritol-type pentaerythritol compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6). -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosfite, and more preferably, distearylpentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) penta. Examples include erythritol diphosphite.

Examples of the phosphite compound having a cyclic structure that reacts with the above divalent phenols include 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl). ) Phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) Phosphite, 2,2'-methylenebis (4-methyl-6-) tert-Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) ) Phosphite, 2,2'-methylene-bis- (4,6-di-t-butylphenyl) octylphosphite, 6-tert-butyl-4- [3-[(2,4,8,10)) -Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl) oxy] propyl] -2-methylphenol and the like can be mentioned.

Examples of the phosphenyl compound having the above other structure include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, and didecylmonophenylphosphite. , Dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphos Fight, Tris (diethylphenyl) phosphite, Tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, And tris (2,6-di-tert-butylphenyl) phosphite and the like.

In addition to various phosphite compounds, for example, phosphate compounds, phosphonite compounds, and phosphonate compounds can be mentioned.

Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Phenylnite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phenylonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrax (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, Tetrax (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di) -N-Phenylphenyl) -3-Phenyl-Phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Among the above phosphorus-based heat stabilizers, trisnonylphenyl phosphite, trimethylphosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are preferably used.

The above phosphorus-based heat stabilizers can be used alone or in combination of two or more. The phosphorus-based heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin (A). Partially mixed.

The polycarbonate resin (A) used in the present invention is a hindered phenol-based heat stabilizer or a sulfur-based heat stabilizer as a heat stabilizer for the purpose of suppressing a decrease in molecular weight and deterioration of hue during extrusion / molding. Can also be added in combination with a phosphorus-based heat stabilizer.

The hindered phenol-based heat stabilizer is not particularly limited as long as it has an antioxidant function, and is, for example, n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-. Butylphenyl) propionate, tetrakis {methylene-3- (3', 5'-di-t-butyl-4-hydroxyphenyl) propionate} methane, distearyl (4-hydroxy-3-methyl-5-t-butylbenzyl) ) Malonate, triethireglycol-bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,2-thiodiethylenebis {3- (3,3) 5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3) , 5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis {(octylthio) methyl} -o -Cresol, Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl-2 (4', 8', 12'-trimethyltridecyl ) Chroman-6-ol, 3,3', 3 ", 5,5', 5" -hexa-t-butyl-a, a', a "-(mesitylen-2,4,6-triyl) tri- Examples thereof include p-cresol.

Among these, n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butylphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl) -4-Hydroxyphenyl) propionate}, 3,3', 3 ", 5,5', 5" -hexa-t-butyl-a, a', a'-(mesitylen-2,4,6-triyl) Tri-p-cresol, 2,2-thiodiethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} and the like are preferable.
One of these hindered phenolic heat stabilizers may be used alone, or two or more thereof may be used in combination.
The hindered phenolic heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and further preferably 0.01 to 0 part by weight per 100 parts by weight of the polycarbonate resin (A). It is blended in 3 parts by weight.

Examples of the sulfur-based heat stabilizer include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, and di-dipropionic acid ester. Stearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3) -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis (2-naphthol) and the like. .. Of the above, pentaerythritol tetrakis (3-laurylthiopropionate) is preferable.
One of these sulfur-based heat stabilizers may be used alone, or two or more thereof may be used in combination.
The sulfur-based heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and further preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin (A). Partially mixed.

When a phosphite-based heat stabilizer, a phenol-based heat stabilizer, and a sulfur-based heat stabilizer are used in combination, the total of these is preferably 0.001 to 1 part by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin (A). Is blended in 0.01 to 0.3 parts by weight.

(Release agent)
The polycarbonate resin (A) used in the present invention can be blended with a mold release agent within a range that does not impair the object of the present invention in order to further improve the mold release property from the mold during melt molding. is there.

Such release agents include higher fatty acid esters of monovalent or polyhydric alcohols, higher fatty acids, paraffin waxes, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic acid anhydride groups, silicone oils, etc. Organopolysiloxane and the like can be mentioned.

As the higher fatty acid ester, a partial ester or a total ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of the partial ester or total ester of such monovalent or polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, and behenic acid. Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene -To, sorbitan monostearate, 2-ethylhexyl stearate and the like.
Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenic behenate are preferably used.

As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

One of these release agents may be used alone, or two or more of them may be used in combination. The amount of the release agent to be blended is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A).

(UV absorber)
The polycarbonate resin (A) used in the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, etc. Agents are preferred.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, and 2- (2). '-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-bis (Α, α'-dimethylbenzyl) phenylbenzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetraphthalimidemethyl) -5'-methylphenyl] benzotriazole , 2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-Chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], methyl-3- [3 Examples thereof include benzotriazole-based ultraviolet absorbers typified by a condensate of −tert-butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol.

The ratio of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, still more preferably 0.2 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). It is a part by weight.

(Light stabilizer)
The polycarbonate resin (A) used in the present invention can contain a light stabilizer. The inclusion of a light stabilizer is good in terms of weather resistance, and has an advantage that cracks are less likely to occur in the molded product.

Examples of the light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis didecanoate (2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, and the like. Bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, 2,4- Bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-2-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (2,2,6,6- Tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4 -Benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-disulfonate, bis (2,2,6,6-tetramethyl) Hindered amines such as -4-piperidyl) phenylphosphite, nickel such as nickelbis (octylphenylsulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzylphosphate monoethylate, nickeldibutyldithiocarbamate) Examples thereof include a complex. These light stabilizers may be used alone or in combination of two or more. The content of the light stabilizer is preferably 0.001 to 1 weight based on 100 parts by weight of the polycarbonate resin (A). Parts, more preferably 0.01 to 0.5 parts by weight.

(Epoxy stabilizer)
In order to improve the hydrolyzability, the polycarbonate resin (A) used in the present invention can be blended with an epoxy compound as long as the object of the present invention is not impaired.

Epoxy stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allylglycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate. , 3,4-Epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3,4-Epoxy-5-methylcyclohexyl) Butyl-3', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy -6-Methylcyclohexylmethyl-6'-methylsilohexylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, bis-epoxy dicyclo Pentazienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadienediepoxide, tetraphenylethyleneepoxide, octylepoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3, 5-Dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2 , 2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, Octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3', 4'-epoxycyclohexylcarboxylate, 4,5-Epoxy Tetrahydrophthalic anhydride, 3-t-butyl-4,5-Epoxy Tetrahydrophthalic anhydride, Diethyl-4,5 -Epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate and the like can be mentioned. Bisphenol A diglycidyl ether is preferable from the viewpoint of compatibility and the like.

Such an epoxy-based stabilizer is 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate resin (A). It is desirable to mix in the range of parts.

(Bluing agent)
The polycarbonate resin (A) used in the present invention can contain a brewing agent in order to cancel the yellowness of the lens based on the polymer or the ultraviolet absorber. As the brewing agent, any brewing agent used for polycarbonate can be used without any particular problem. Generally, anthraquinone dyes are easily available and preferable.

Specific brewing agents include, for example, the generic name Solvent Violet 13 [CA. No (color index No) 60725], generic name Solvent Violet31 [CA. No 68210, generic name Solvent Violet33 [CA. No 60725], generic name Solvent Blue94 [CA. No 61500], generic name Solvent Violet36 [CA. No 68210], generic name Solvent Blue97 ["Macrolex Violet RR" manufactured by Bayer] and generic name Solvent Blue45 [CA. No61110] is a typical example.

One of these brewing agents may be used alone, or two or more thereof may be used in combination. These brewing agents are preferably blended in a ratio of 0.1 × 10 ^-4 to 2 × 10 ^-4 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A).

(Flame retardants)
A flame retardant can also be added to the polycarbonate resin (A) used in the present invention. Flame retardants include halogen-based flame retardants such as brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, and chlorinated polyethylene, and phosphate ester-based flame retardants such as monophosphate compounds and phosphate oligomeric compounds. Organic phosphorus flame retardants other than phosphoric acid ester flame retardants such as phosphinate compounds, phosphonate compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, organic sulfonic acid alkali (earth) metal salts, borate metal salt flame retardants, Includes organic metal salt flame retardants such as metal phosphate flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, triazine flame retardants and the like. Separately, a flame retardant aid (for example, sodium antimonyate, antimony trioxide, etc.), a drip inhibitor (polytetrafluoroethylene having a fibril-forming ability, etc.) and the like may be blended in combination with the flame retardant.

Among the above-mentioned flame retardants, compounds that do not contain chlorine atoms and bromine atoms are one of the features that reduce the environmental load because the factors that are considered unfavorable when incineration disposal or thermal recycling are reduced. It is more suitable as a flame retardant in the molded product of the present invention.

When the flame retardant is blended, the range is preferably 0.05 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (A). Within the above range, sufficient flame retardancy is exhibited, and the strength and heat resistance of the molded product are excellent.

(Elastic polymer)
An elastic polymer can be used as the impact improver in the polycarbonate resin (A) used in the present invention, and examples of the elastic polymer include natural rubber or a rubber component having a glass transition temperature of 10 ° C. or less. Examples of graft copolymers obtained by copolymerizing one or more of monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable with these. be able to. A more suitable elastic polymer is a core-shell type graft copolymer in which one or more shells of the monomer are graft-copolymerized on the core of the rubber component.

Further, a block copolymer of such a rubber component and the above-mentioned monomer can also be mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomer (hydrogenated styrene / isoprene / styrene elastomer) and hydrogenated styrene / butadiene / styrene elastomer. Further, various elastic polymers known as other thermoplastic elastomers, such as polyurethane elastomers, polyester elastomers, and polyetheramide elastomers, can also be used.

A more suitable impact improver is a core-shell type graft copolymer. In the core-shell type graft copolymer, the particle size of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and 0.1 to 0.5 μm in terms of weight average particle size. Is even more preferable. Better impact resistance is achieved in the range of 0.05 to 0.8 μm. The elastic polymer preferably contains 40% or more of a rubber component, and more preferably 60% or more.

As rubber components, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene- Acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bond portions can be mentioned, but they contain halogen atoms from the viewpoint of concern about the generation of harmful substances during combustion. A non-rubber component is preferable in terms of environmental load.

The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and the rubber component is particularly preferably butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, or acrylic-silicone composite rubber. The composite rubber refers to a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure in which they are intertwined with each other so as not to be separated.

Examples of aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene, and the like, and styrene is particularly preferable. Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate, and examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples thereof include butyl, cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in 100% by weight of the shell in the case of a core-shell type polymer), preferably 10% by weight or more, and more preferably 15% by weight or more. Will be done.

The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or lower may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method is as follows. It does not matter whether it is a one-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during production. Further, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-step swelling polymerization method. Further, in the suspension polymerization method, a method in which the aqueous phase and the monomer phase are individually held and both are accurately supplied to a continuous disperser, and the particle size is controlled by the rotation speed of the disperser, and continuous production. In the method, a method of controlling the particle size by supplying the monomer phase into an aqueous liquid having a dispersibility through a small-diameter orifice having a diameter of several to several tens of μm or a porous filter may be used. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

Such elastic polymers are commercially available and easily available. For example, as the rubber component, butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber is mainly used as Kaneace B series (for example, B-56) of Kanebuchi Chemical Industry Co., Ltd. and Metabren of Mitsubishi Rayon Co., Ltd. C series (eg C-223A etc.), W series (eg W-450A etc.), Kureha Chemical Industry Co., Ltd. Pararoid EXL series (eg EXL-2602 etc.), HIA series (eg HIA-15 etc.), BTA series (For example, BTA-III), KCA series, Rohm & Hearth's Pararoid EXL series, KM series (for example, KM-336P, KM-357P, etc.), and Ube Psycon Co., Ltd.'s UCL modifier resin series (UMG).・ UMG AXS resin series of ABS Co., Ltd.), etc., and those mainly composed of acrylic-silicone composite rubber as a rubber component are commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of Metabren S-2001 or SRK-200. Some are listed.

The composition ratio of the impact improver is preferably 0.2 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 1.5 to 20 parts by weight per 100 parts by weight of the polycarbonate resin (A). Such a composition range can give good impact resistance to the composition while suppressing a decrease in rigidity.

(filler)
The polycarbonate resin (A) used in the present invention can be blended with various fillers as a reinforcing filler as long as the effects of the present invention are exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, gas phase growth method ultrafine carbon fiber (fiber diameter 0.1 μm) Less than), carbon nanotubes (fiber diameter less than 0.1 μm, hollow), fullerene, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, metal oxide particles, Examples include metal oxide fibers, metal oxide balloons, and various whiskers (potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate, etc.). These reinforcing fillers may be contained alone or in combination of two or more.

The content of these fillers is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the layer containing the polycarbonate resin (A).

<Thermosetting resin (B)>
(Thermosetting resin)
Examples of the thermosetting resin (B) include epoxy resin, phenol resin, polyimide resin, melamine resin, polyurethane resin, silicon resin, vinyl ester resin, unsaturated polyester resin, maleimide resin, and epoxy ester resin. Among them, epoxy resin, phenol resin and polyimide resin are preferable, epoxy resin and phenol resin are more preferable, and epoxy resin is particularly preferable. These may be used alone or in combination of two or more.

Examples of the epoxy resin include a bifunctional epoxy resin and a trifunctional or higher functional epoxy resin. Examples of the bifunctional epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, and epoxy resin modified from these. Examples of the trifunctional or higher functional polyfunctional epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraglycidyl diaminodiphenylmethane, triglycidyl aminophenol, glycidyl amine type epoxy resin such as tetraglycidyl amine, and tetrakis. Examples thereof include glycidyl ether type epoxy resins such as (glycidyl oxyphenyl) ethane and tris (glycidyl oxymethane), modified epoxy resins thereof, and brominated epoxy resins obtained by bromizing these epoxy resins. One of these may be used alone, or two or more thereof may be used in combination.

(Hardener)
As the thermosetting resin (B) used in the present invention, a curing agent that cures the curable resin may be used, if necessary. Examples of the curing agent include amines, carboxylic acid anhydrides, phenols, mercaptans, amine Lewis acid complexes, onium salts, and imidazoles. Among these, amine-based and phenol-based curing agents are preferable. One of these may be used alone, or two or more thereof may be used in combination.

(Curing accelerator)
A curing accelerator may be used for the thermosetting resin (B) used in the present invention. Examples of the curing accelerator include tertiary amine compounds such as imidazole and dimethylaminopyridine, phosphorus compounds such as triphenylphosphine, and boron trifluoride amine complexes such as boron trifluoride and boron difluoride monoethylamine complex. Examples thereof include organic acid compounds such as thiodipropionic acid, benzoxazine compounds such as thiodiphenol benzoxazine and sulfonylbenzoxazine, and sulfonyl compounds. One of these may be used alone, or two or more thereof may be used in combination. The amount of these curing accelerators added is preferably 0.001 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin (B).

(filler)
The thermosetting resin (B) used in the present invention can be blended with various fillers as a reinforcing filler as long as the effects of the present invention are exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, gas phase growth method ultrafine carbon fiber (fiber diameter 0.1 μm) Less than), carbon nanotubes (fiber diameter less than 0.1 μm, hollow), fullerene, metal flakes, metal fibers, aramid fibers, silicon carbide fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, Examples thereof include silica, metal oxide particles, metal oxide fibers, metal oxide balloons, and various whiskers (potassium titanate whisker, aluminum borate whisker, and basic magnesium sulfate, etc.). Among them, it is preferable to use reinforcing fibers such as glass fiber, aramid fiber, and carbon fiber, and carbon fiber is more preferable from the viewpoint of light weight and strength. These reinforcing fillers may be contained alone or in combination of two or more.
The content of these fillers is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 80 parts by weight, based on 100 parts by weight of the thermosetting resin (B).

(Reinforcing fiber)
The reinforcing fiber to be blended in the thermosetting resin (B) used in the present invention is preferably formed in a sheet shape and used. Examples of the reinforcing fiber sheet include a sheet in which a large number of reinforcing fibers are arranged in one direction, a bidirectional woven fabric such as plain weave and twill weave, a multi-axis woven fabric, a non-woven fabric, a mat, a knit, a braid, and a paper made from reinforcing fibers. And so on.
When the reinforcing fiber is blended with the thermosetting resin (B), it is preferably contained in the thermosetting resin in a proportion of 40 to 80% by mass. By containing 40% by mass or more of the reinforcing fibers, the mechanical properties of the obtained molded product can be improved. On the other hand, by containing 80% by mass or less of the reinforcing fibers, it is possible to suppress a decrease in fluidity during molding, sufficiently impregnate the matrix resin component, and as a result, improve the mechanical properties.

(Prepreg)
As the thermosetting resin (B), a resin sheet "prepreg" in which a reinforced fiber woven fabric is impregnated with an uncured or semi-cured thermosetting resin can also be used. The thermosetting resin (B) may be composed of one prepreg, but usually has a structure in which a plurality of prepregs are laminated.

<Decorative molding>
The decorative molded product in the present invention is obtained by laminating a polycarbonate resin (A) and a thermosetting resin (B) and integrally molding them.

(Molding method)
As the molding method, a heat-press molding method such as a press molding method, an autoclave molding method, or a vacuum bag molding method can be adopted.
The molding temperature in the heat-press molding may be appropriately selected depending on the selected matrix resin. For example, in the case of an epoxy resin, the temperature is usually preferably 80 to 180 ° C., although it depends on the type of curing agent contained. If the molding temperature is too low, sufficient curability may not be obtained, and conversely, if it is too high, warpage due to thermal strain is likely to occur.

The pressure for molding by the heat-pressurizing molding method varies depending on the thickness of the thermosetting resin and the like, but is usually preferably 0.1 to 5 MPa. If the molding pressure is too low, heat may not be sufficiently transferred to the inside of the thermosetting resin, and the heat may be locally uncured or warped. On the other hand, if it is too high, it may flow out to the surroundings before the resin is cured, and voids may occur in the resin or poor appearance may occur.

(surface treatment)
In the decorative molded article of the present invention, various surface treatments can be applied to the layer made of the polycarbonate resin. Surface treatment here means a new layer on the surface layer of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. It is formed, and the method used for ordinary polycarbonate resins can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metallizing (evaporation, etc.). Hard coat is a particularly preferred and required surface treatment.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the examples, "part" means "part by weight". The resin and the evaluation method used in the examples are as follows.

(Evaluation of polycarbonate resin)
1. 1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR of JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.
2. 2. It was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at a specific viscosity of 20 ° C.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
3. 3. Glass transition temperature (Tg)
Using 8 mg of sample, using the thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd., in accordance with JIS K7121 under a nitrogen atmosphere (nitrogen flow rate: 40 ml / min), heating rate: It was measured under the condition of 20 ° C./min.

(Evaluation of decorative molded product)
1. 1. Appearance The appearance of the decorative molded product sample was visually observed. The surface appearance was judged according to the criteria described below.
"○": No discoloration, whitening, or wrinkles are confirmed on the surface film layer.
"X": Discoloration, whitening, and wrinkles are confirmed in the surface film layer.
2. 2. Adhesion Using a cutter knife on the surface (first layer: film layer side) of the laminated body sample, cross-cutting was performed so that 100 1 mm ² cuts (grind) could be made. Next, the cellophane adhesive tape was completely adhered onto the created grid, and one end of the tape was lifted and peeled upward. This peeling operation was performed three times at the same location. Then, the number of peeled grids was determined according to the criteria described below.
"○": No peeling.
"X": There is peeling.
3. 3. Pencil hardness Based on JIS K5400, a line is applied with a pencil under a load of 1 kg while maintaining an angle of 45 degrees with respect to the surface of the first layer (film layer) of the laminated sample in a thermostatic chamber with an ambient temperature of 23 ° C. Was drawn, and the surface condition was visually evaluated.

[Polycarbonate resin (A)]
[Reference example 1]
Production of Polycarbonate Resin (PC1) Isosorbide (hereinafter abbreviated as ISS) 376 parts, 1,6-hexanediol (hereinafter abbreviated as HD) 101 parts, diphenyl carbonate (hereinafter abbreviated as DPC) 750 parts, and tetramethylammonium hydroxy as a catalyst 3.0 × ^10-2 parts and 2.0 × 10 ^-3 parts of sodium hydroxide were heated to 170 ° C. in a nitrogen atmosphere to melt them. After confirming that it had melted, the EI reaction step was started. After the start of depressurization, the pressure was reduced while adjusting the final decompression degree to 13.4 kPa over 70 minutes, and the decompression degree was maintained after reaching 13.4 kPa. At the same time as the start of depressurization, the temperature was raised at a rate of 10 ° C./hr until the final resin temperature reached 190 ° C. After reaching 190 ° C., the mixture was kept at a reduced pressure of 13.4 kPa and a resin temperature of 190 ° C. for 10 minutes until 80% of the theoretical amount of phenol was distilled off. After confirming that 80% was distilled off, the PA reaction step (first step step) was started. The temperature was raised at a rate of 0.5 ° C./min so that the final resin temperature was 220 ° C. Further, in parallel with the temperature rise, the pressure was reduced over 60 minutes so that the final degree of pressure reduction was 3 kPa. Subsequently, the PA reaction step (late step) was started. In the latter step, the temperature was raised at a rate of 1 ° C./min so that the final resin temperature was 240 ° C. Further, in parallel with the temperature rise, the pressure was reduced over 20 minutes until the final degree of pressure reduction reached 134 Pa. The reaction is terminated when the predetermined stirring power value is reached, dodecylbenzenesulfonic acid tetrabutylphosphonium salt in an amount twice the amount of the catalyst is added, the catalyst is deactivated, and then discharged from the bottom of the reaction vessel under nitrogen pressure. , While cooling in a water tank, cut with a pelletizer to obtain pellets. The specific viscosity of the obtained polycarbonate copolymer was 0.32, and the glass transition temperature was 101 ° C.

[Reference example 2]
Production of Polycarbonate Resin (PC2) Except for the use of 441 parts of ISS, 66 parts of 1,9-nonanediol (hereinafter abbreviated as ND), and 750 parts of DPC, the same operation as in Reference Example 1 was carried out. The specific viscosity of the obtained polycarbonate copolymer was 0.34, and the glass transition temperature was 121 ° C.

[Reference example 3]
Production of Polycarbonate Resin (PC3) Except that 358 parts of ISS, 151 parts of 1,4-cyclohexanedimethanol (hereinafter abbreviated as CHDM), and 750 parts of DPC were used as raw materials, the same operation as in Reference Example 1 was performed, and the same evaluation was performed. Was done. The specific viscosity of the obtained polycarbonate copolymer was 0.35, and the glass transition temperature was 121 ° C.

[Reference example 4]
Production of Polycarbonate Resin (PC4) Except that 256 parts of ISS, 252 parts of CHDM, and 750 parts of DPC were used as raw materials, exactly the same operation as in Example 1 was carried out, and the same evaluation was performed. The specific viscosity of the obtained polycarbonate copolymer was 0.31, and the glass transition temperature was 100 ° C.
[PCA]
Teijin Limited Panlite "L-1225Y" Tg 145 ° C, viscosity average molecular weight 24,000
[PMMA]
Mitsubishi Rayon Acripet "VH001"
[Thermosetting resin (B)]
(Epoxy resin) Bisphenol A type epoxy resin "jER828" manufactured by Mitsubishi Chemical Corporation
(Hardener) Amine-based hardener "KAYAHARD AA" manufactured by Nippon Kayaku Co., Ltd.
(Carbon fiber reinforced prepreg)
Teijin Limited carbon fiber reinforced prepreg "Tenax" (registered trademark) W-3101 / Q-195 (carbon fiber impregnated with uncured epoxy resin)

[Example 1]
(Manufacturing of film)
The resin pellet (PC1) was melted by a twin-screw extruder having a screw diameter of 15 mm and extruded through a T-shaped die having a set temperature of 230 ° C., and the obtained sheet was cooled by a mirror-finished roll to obtain a film. Further, the discharge amount of the molten resin was adjusted so that the thickness was film = 0.1 (mm).
(Manufacturing of decorative molded products)
100 parts by weight of the epoxy resin "jER828" and 34 parts by weight of the amine-based curing agent "KAYAHARD AA" were mixed to obtain a uniform mixed solution. This mixed solution was placed on a Teflon plate, and a film of PC1 was further laminated on the Teflon plate. This laminate was cured in an oven (temperature: 110 ° C., pressure: normal pressure, time: 5 hours) to obtain a decorative molded product. Various evaluations were carried out on the obtained decorative molded product by the evaluation method described above. The evaluation results are shown in Table 1.

[Example 2]
Except for using PC2 as the resin pellet, the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 1.

[Example 3]
Except for using PC3 as the resin pellet, the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 1.

[Example 4]
Except for using PC4 as the resin pellet, the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 1.

[Comparative Example 1]
Except for using PCA as the resin pellet, the same operation as in Example 1 was performed, and the same evaluation was performed. The evaluation results are shown in Table 1. The obtained laminate had poor appearance and surface hardness, and could not achieve the original purpose.

[Comparative Example 2]
Except for using PMMA as the resin pellet, the same operation as in Example 1 was carried out, and the same evaluation was performed. The evaluation results are shown in Table 1. The obtained laminate had a poor appearance and could not achieve the original purpose.

[Example 5]
Five carbon fiber reinforced prepregs "Tenax" were laminated, and a film of PC1 was further laminated. This laminated body was cured by an autoclave (temperature: 130 ° C., pressure: 0.5 MPa, time: 2 hours) to obtain a decorative molded body. Various evaluations were carried out on the obtained decorative molded product by the evaluation method described above. The evaluation results are shown in Table 2.

[Example 6]
Except for using PC2 as the resin pellet, the same operation as in Example 5 was performed, and the same evaluation was performed. The evaluation results are shown in Table 2.

[Example 7]
Except for using PC3 as the resin pellet, the same operation as in Example 5 was performed, and the same evaluation was performed. The evaluation results are shown in Table 2.

[Example 8]
Except for using PC4 as the resin pellet, the same operation as in Example 5 was performed, and the same evaluation was performed. The evaluation results are shown in Table 2.

[Comparative Example 3]
Except for using PCA as the resin pellet, the same operation as in Example 5 was performed, and the same evaluation was performed. The evaluation results are shown in Table 2. The obtained laminate had poor appearance and surface hardness, and could not achieve the original purpose.

[Comparative Example 4]
Except for using PMMA as the resin pellet, the same operation as in Example 5 was carried out, and the same evaluation was performed. The evaluation results are shown in Table 2. The obtained laminate had a poor appearance and could not achieve the original purpose.

The decorative molded body of the present invention is excellent in high mechanical properties, light weight, heat resistance, surface characteristics such as surface hardness, and appearance. Therefore, sports equipment, automobiles, ships, aircraft parts, personal computers, digital cameras, etc. It can be widely used for various purposes such as housings for cameras, mobile phones, etc.

Claims (5)

A decorative molded body in which a layer made of a polycarbonate resin (A) containing a unit represented by the following formula (1) and a thermosetting resin (B) are laminated.

The decorative molded article according to claim 1, wherein the glass transition temperature of the polycarbonate resin (A) is 90 ° C to 160 ° C. The decorative molded article according to any one of claims 1 to 2, wherein the surface hardness of the layer made of the polycarbonate resin (A) is HB or more. The decorative molded article according to any one of claims 1 to 3, wherein the thermosetting resin (B) is any one of an epoxy resin, a phenol resin, and a polyimide resin. The decorative molded article according to any one of claims 1 to 4, wherein the thermosetting resin (B) is a fiber-reinforced thermosetting resin.