WO2019116691A1 - Unsaturated polyester resin composition, molded article containing cured product thereof, and lamp reflector including said molded article - Google Patents

Unsaturated polyester resin composition, molded article containing cured product thereof, and lamp reflector including said molded article Download PDF

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Publication number
WO2019116691A1
WO2019116691A1 PCT/JP2018/037262 JP2018037262W WO2019116691A1 WO 2019116691 A1 WO2019116691 A1 WO 2019116691A1 JP 2018037262 W JP2018037262 W JP 2018037262W WO 2019116691 A1 WO2019116691 A1 WO 2019116691A1
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Prior art keywords
unsaturated polyester
polyester resin
resin composition
inorganic filler
mass
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PCT/JP2018/037262
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French (fr)
Japanese (ja)
Inventor
審史 田村
正太郎 板見
隆仁 石内
和正 中条
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昭和電工株式会社
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Priority to JP2019558930A priority Critical patent/JPWO2019116691A1/en
Priority to CN201880065135.2A priority patent/CN111201280A/en
Publication of WO2019116691A1 publication Critical patent/WO2019116691A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V7/00—Reflectors for light sources
    • F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
    • F21V7/28—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors characterised by coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors

Definitions

  • the present invention relates to an unsaturated polyester resin composition, a molded article containing the cured product thereof, and a lamp reflector containing the molded article.
  • the present invention relates to an unsaturated polyester resin composition used in the production of a lamp reflector used for an automobile headlamp and the like, a molded article containing the cured product thereof, and a lamp reflector containing the molded article.
  • An unsaturated polyester resin composition in which a fiber reinforcing material and an inorganic filler are mixed with an unsaturated polyester resin has good resin flowability at the time of molding and a cured product excellent in dimensional accuracy, heat resistance and mechanical strength. It is widely used in the manufacture of office automation equipment, office equipment chassis, automobile headlamp lamp reflectors, etc.
  • the lamp reflector reflects and illuminates the light of the lamp at a certain angle, which may cause deviation of light distribution if the surface smoothness of the reflective layer is not sufficient.
  • an undercoat agent is applied and cured on the surface of a molded article (base material) obtained by molding and curing an unsaturated polyester resin composition to form an undercoat layer, and then an undercoat layer is formed.
  • a metal coating layer (reflection layer) of aluminum, zinc or the like is formed thereon by vapor deposition or the like.
  • it may be considered to increase the thickness of the undercoat layer, but the thickness of the undercoat layer leads to an increase in manufacturing cost.
  • the unsaturated polyester resin composition used for the production of the lamp reflector has a surface which is excellent in resin flowability at the time of molding and gives a cured product excellent in dimensional accuracy, heat resistance and mechanical strength. It is also required to provide a cured product with excellent smoothness.
  • An inorganic filler is generally blended in the unsaturated polyester resin composition from the viewpoint of mechanical strength and cost (Patent Documents 1 and 2).
  • the mechanical strength of the unsaturated polyester resin composition can be improved by increasing the amount of the inorganic filler to be blended, while the resin flowability at the time of molding of the unsaturated polyester resin composition and the surface smoothness of the molded article Sex tends to decline.
  • the present invention has been made to solve the problems as described above, and has a good resin flowability at the time of molding, and a molded article having excellent surface smoothness in addition to dimensional accuracy and mechanical properties. It is an object of the present invention to provide an unsaturated polyester resin composition which gives
  • the present inventors have blended a predetermined amount of inorganic filler in the unsaturated polyester resin composition, and used two types of average particle sizes as the inorganic filler.
  • inorganic fillers By using different inorganic fillers, it has been found that resin flowability at the time of molding is good and that a molded article having excellent surface smoothness can be formed, and the present invention has been completed.
  • the present invention relates to the following [1] to [6].
  • Unsaturated polyester resin composition comprising (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcement and (f) curing agent
  • the inorganic filler (b) is 250 to 600 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a),
  • As the inorganic filler (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 ⁇ m and (b2) an inorganic filler having an average particle diameter of 8.0 to 50.0 ⁇ m
  • an unsaturated polyester resin composition which gives a molded article excellent in surface smoothness in addition to dimensional accuracy and mechanical properties, as well as resin flowability at the time of molding. .
  • One embodiment of the present invention comprises (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcement and (f) curing agent. It is an unsaturated polyester resin composition.
  • (A) unsaturated polyester resin generally contains a condensation product (unsaturated polyester) obtained by the esterification reaction of a polyhydric alcohol with an unsaturated polybasic acid and an optional saturated polybasic acid as a crosslinking agent (“reactivity It is also dissolved in “diluent”.
  • An unsaturated polybasic acid is a polybasic acid having a polymerizable ethylenic double bond
  • a saturated polybasic acid is a polybasic acid having no polymerizable ethylenic double bond.
  • polyester resin handbook (Nikkan Kogyo Shimbun, published in 1988) and "Coating glossary” (coloring materials association ed., 1993) Yearly issue etc.).
  • the polyhydric alcohol used for the synthesis of the unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used.
  • polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentanediol, hydrogenated bisphenol A, bisphenol A, glycerin Etc.
  • propylene glycol, neopentyl glycol, bisphenol A and hydrogenated bisphenol A are preferable from the viewpoints of heat resistance, mechanical strength and resin fluidity at the time of molding. These can be used alone or in combination of two or more.
  • the unsaturated polybasic acid used for the synthesis of the unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used.
  • unsaturated polybasic acids include maleic anhydride, fumaric acid, citraconic acid, itaconic acid and the like. These can be used alone or in combination of two or more. Among these, maleic anhydride and fumaric acid are preferable from the viewpoints of heat resistance, mechanical strength, resin fluidity at the time of molding, and the like.
  • the saturated polybasic acid used for the synthesis of the unsaturated polyester is not particularly limited, and known ones can be used.
  • saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endo methylene tetrahydrophthalic anhydride, hetic acid, etc. It can be mentioned. These can be used alone or in combination of two or more.
  • Unsaturated polyester can be synthesized by known methods using raw materials as described above. Although various conditions in this synthesis need to be set appropriately according to the raw materials used and the amount thereof, generally, pressurization or pressure reduction is carried out at a temperature of 140 to 230 ° C. in an inert gas stream such as nitrogen gas. It may be esterified below. In this esterification reaction, an esterification catalyst can be used as needed. Examples of catalysts include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate and cobalt acetate. These can be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of the unsaturated polyester is not particularly limited, but is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and still more preferably 7,000 to 18 , 000.
  • “weight average molecular weight” is measured at room temperature (23 ° C.) under the following conditions using gel permeation chromatography (Shodex (registered trademark) GPC-101 manufactured by Showa Denko KK). The value determined using a standard polystyrene calibration curve is meant.
  • the crosslinking agent used for the unsaturated polyester resin is not particularly limited as long as it has an ethylenic double bond that can be polymerized with the unsaturated polyester, and known crosslinking agents in the technical field of the present invention Can be used.
  • the crosslinking agent include styrene monomer, diallyl phthalate monomer, diallyl phthalate prepolymer, methyl methacrylate, triallyl isocyanurate and the like. These can be used alone or in combination of two or more.
  • the compounding amount of the crosslinking agent in the unsaturated polyester resin is not particularly limited, but from the viewpoint of workability, polymerizability, shrinkage of molded articles and freedom in adjusting the amount, the total amount of unsaturated polyester and crosslinking agent On the other hand, it is preferably 25 to 70% by mass, more preferably 30 to 68% by mass, and still more preferably 35 to 65% by mass.
  • the unsaturated polyester resin can also contain a polymerization inhibitor such as hydroquinone, if necessary.
  • the inorganic filler (b) As the inorganic filler (b), those known in the technical field of the present invention can be used.
  • the inorganic filler (b) include calcium carbonate, silica, alumina, aluminum hydroxide, barium sulfate, wollastonite, clay, talc, mica, gypsum, anhydrous silicic acid, glass powder and the like. These can be used alone or in combination of two or more.
  • the true specific gravity of the inorganic filler (b) is preferably 1 to 10 g / cm 3 , more preferably 1.5 to 8 g / cm 3 , and still more preferably 2 to 5 g / cm 3 . If the true specific gravity of the inorganic filler is 1 g / cm 3 or more, the mechanical properties of the molded article are better, and if the true specific gravity of the inorganic filler is 10 g / cm 3 or less, the kneadability is better is there.
  • the shape of the inorganic filler (b) is not particularly limited, and examples thereof include approximately a true sphere, an ellipsoid, a scaly shape, and an amorphous shape.
  • the blending amount of the (b) inorganic filler is 250 to 600 parts by mass, more preferably 300 to 550 parts by mass, and still more preferably 350 to 500 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. Parts, in particular 350 to 450 parts by weight.
  • the inorganic filler includes (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 ⁇ m, and (b2) an inorganic filler having an average particle diameter of 8.0 to 50.0 ⁇ m.
  • the "average particle size" of the inorganic filler (b) means a particle size determined according to the following equation from the specific surface area determined by an air permeation method using a constant pressure powder specific surface area measuring device.
  • a constant pressure powder specific surface area measuring device SS-100 manufactured by Shimadzu Corporation can be used.
  • Average particle size [ ⁇ m] (6 ⁇ 10000) / (true specific gravity [g / cm 3 ] ⁇ specific surface area [cm 2 / g])
  • the average particle diameter of (b1) is more preferably 0.7 to 4.0 ⁇ m, still more preferably 0.8 to 3.0 ⁇ m.
  • the average particle diameter of (b2) is more preferably 9.0 to 40.0 ⁇ m, and still more preferably 10.0 to 30.0 ⁇ m. If the average particle diameter of (b1) is 0.5 ⁇ m or more, the viscosity of the unsaturated polyester resin composition is appropriate and good resin fluidity is obtained at the time of molding, and if it is 5.0 ⁇ m or less, the surface of the molded article is smooth. It is possible to improve the quality.
  • the average particle diameter of (b2) is 8.0 ⁇ m or more, the resin flowability at molding and the mechanical strength of the molded product are better, and if it is 50.0 ⁇ m or less, the surface smoothness of the molded product It is possible to keep the sex better.
  • the mass ratio of (b1) to (b2) is 25:75 to 75:25. From the viewpoint of surface smoothness, it is preferably 30:70 to 70:30, and more preferably 40:60 to 60:40.
  • (C) metal soap is a component generally used as a mold release agent in the technical field of the present invention.
  • the metal soap (c) is not particularly limited, and those known in the technical field of the present invention can be used.
  • Examples of (c) metal soaps include calcium stearate, zinc stearate, aluminum stearate, magnesium stearate and the like. These can be used alone or in combination of two or more.
  • the blending amount of the (c) metal soap is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (C) If the compounding quantity of metal soap is 1 mass part or more, the releasability of a molded object will be more favorable. On the other hand, if the blending amount of (c) metal soap is 15 parts by mass or less, it is possible to prevent (c) the metal soap from bleeding on the surface of the molded product, so desired fogging properties and paintability of the undercoat agent Can be obtained.
  • the low-shrinkage agent (d) is not particularly limited, and those known in the technical field of the present invention can be used.
  • the low shrinkage agent include thermoplastic polymers generally used as a low shrinkage agent such as polystyrene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, styrene-butadiene rubber and the like. These can be used alone or in combination of two or more.
  • the blending amount of the (d) low-shrinkage agent is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (D) If the blending amount of the low-shrinkage agent is 10 parts by mass or more, the shrinkage rate of the molded product becomes small, and desired dimensional accuracy can be obtained. On the other hand, if the blending amount of the (d) low shrinkage agent is 40 parts by mass or less, the mechanical properties of the molded article are more favorable.
  • the fiber reinforcing material is a fibrous material having an aspect ratio of 3 or more.
  • the aspect ratio can be measured by the microscopic method described in Japanese Industrial Standard JIS R-8900-1: 2008 "Particle for measuring particle size measuring device".
  • the fiber reinforcing material (e) is not particularly limited, and those known in the technical field of the present invention can be used.
  • Examples of the fiber reinforcement include various organic fibers and inorganic fibers such as glass fibers, pulp, polyethylene terephthalate fibers, vinylon fibers, carbon fibers, aramid fibers, wollastonite and the like. Among them, glass fiber is preferable, and chopped strand glass cut to a fiber length of about 1.5 to 25 mm is more preferable.
  • the compounding amount of the (e) fiber reinforcing material is preferably 70 to 120 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (E) If the compounding quantity of a fiber reinforcement is 70 mass parts or more, the mechanical characteristic of a molded object will be more favorable. On the other hand, if the blending amount of (e) fiber reinforcing material is 120 parts by mass or less, (e) the fiber reinforcing material is more uniformly dispersed in the unsaturated polyester resin composition to produce a homogeneous molded article. it can.
  • the curing agent (f) is not particularly limited as long as it is a radical initiator capable of polymerizing an ethylenically unsaturated bond, and those known in the technical field of the present invention can be used.
  • curing agents include t-butyl peroxy octoate, benzoyl peroxide, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane, t-butyl peroxy isopropyl carbonate And organic peroxides such as t-butylperoxybenzoate, dicumyl peroxide, di-t-butyl peroxide and the like. These can be used alone or in combination of two or more.
  • the compounding amount of the curing agent may be appropriately set according to the raw material to be used, and is not particularly limited.
  • the amount of the curing agent (f) is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, still more preferably 1 to 5 parts by mass per 100 parts by mass of the unsaturated polyester resin (a). It is a mass part.
  • the unsaturated polyester resin composition of the present invention includes, in addition to the above components, components known in the technical field of the present invention, such as thickeners, pigments, viscosity reducing agents, etc., within the range not to inhibit the effects of the present invention. be able to.
  • metal oxides other than (b) inorganic fillers such as magnesium oxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and an isocyanate compound etc. are mentioned. These can be used alone or in combination of two or more.
  • the unsaturated polyester resin composition can be produced by a method which is usually carried out in the technical field of the present invention, for example, by kneading each component using a kneader or the like.
  • a molded object can be manufactured by shape
  • the molding and curing method is not particularly limited, and methods commonly used in the technical field of the present invention, for example, compression molding, transfer molding, injection molding and the like can be used.
  • the molded article of the unsaturated polyester resin composition is suitable for use as a substrate of a lamp reflector. Since the molded article of the unsaturated polyester resin composition containing the inorganic filler having the above two specific average particle sizes is excellent in surface smoothness, the thickness of the undercoat layer necessary to prevent the deviation of the light distribution Is small. Therefore, it is possible to reduce the manufacturing cost.
  • the lamp reflector generally includes a molded article (base material) of the unsaturated polyester resin composition, an undercoat layer located on the molded article, and a metal reflective layer located on the undercoat layer.
  • FIG. 1a is a cross-sectional view of a lamp with a lamp reflector of one embodiment.
  • FIG. 1b is an enlarged cross-sectional view of the line aa 'of FIG. 1a.
  • the lamp generally comprises a lamp reflector, a light source 4 provided at a predetermined position of the lamp reflector, and a lens 5 provided at the opening of the lamp reflector.
  • the lamp reflector includes a molded body 1 of the unsaturated polyester resin composition, an undercoat layer 2 positioned on the molded body 1, and a metal reflection layer positioned on the undercoat layer 2. And three. In this lamp, the light generated from the light source 4 is reflected by the metal reflection layer 3.
  • the thickness of the undercoat layer 2 can be appropriately set in accordance with the required size of the lamp reflector, but is generally 10 to 50 ⁇ m.
  • the undercoat agent for giving the undercoat layer 2 is not particularly limited, and those known in the technical field of the present invention can be used.
  • This undercoat agent is also called a primer composition, and is generally a resin composition containing a UV curable resin or a thermosetting resin.
  • the UV curable resin and the thermosetting resin include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.
  • the undercoat agent may contain a polyester resin such as unsaturated polyester resin, vinyl-modified polyester resin, phenol-modified polyester resin, oil-modified polyester resin, silicone-modified polyester resin, curing agent, solvent and the like.
  • the thickness of the metal reflection layer 3 can be appropriately set in accordance with the required size of the lamp reflector and the like, but is generally 800 to 2,000 ⁇ .
  • the material for providing the metal reflective layer 3 is not particularly limited, and materials known in the technical field of the present invention can be used.
  • Examples of the material of the metal reflective layer 3 include aluminum, silver, zinc, an alloy composed mainly of silver and zinc, and the like.
  • the light source 4 and the lens 5 provided at predetermined positions of the lamp body are not particularly limited, and those known in the technical field of the present invention can be used.
  • a lamp reflector having such a configuration can be manufactured as follows.
  • the unsaturated polyester resin composition is molded and cured to obtain a molded body 1.
  • the molded body 1 can be obtained by molding and curing the unsaturated polyester resin composition into a predetermined shape using a known molding method such as compression molding, transfer molding, injection molding and the like.
  • the release agent is removed if necessary.
  • the removal of the release agent can be carried out by washing treatment, heat treatment, flame treatment or the like.
  • an undercoat agent is applied onto the molded body 1 and cured to form an undercoat layer 2. It does not specifically limit as method to apply
  • well-known methods such as an air spray system and an airless spray system, can be used.
  • the curing method is also not particularly limited, and can be appropriately selected according to the type of undercoat agent.
  • the metal reflective layer 3 is formed on the undercoat layer 2. It does not specifically limit as method to form the metal reflection layer 3 on the undercoat layer 2, For example, well-known methods, such as a vacuum evaporation method, can be used.
  • the light source 4 and the lens 5 are attached to predetermined positions of the lamp body.
  • the method of attaching the light source 4 and the lens 5 is not particularly limited, and can be performed according to a known method.
  • Examples 1 to 13 Each component was charged according to the composition shown in Table 1 and kneaded for 30 minutes at 25 ° C. using a double-arm type kneader to obtain an unsaturated polyester resin composition.
  • the unsaturated polyester resin (a) shown in Tables 1 and 2 contains 30% by mass of a styrene monomer.
  • the unsaturated polyester resin composition was obtained by preparing each component with the composition shown in Table 2 and kneading it for 30 minutes at 25 ° C. using a double-arm type kneader.
  • calcium carbonate (average particle diameter 0.5 ⁇ m, 1.0 ⁇ m, 2.0 ⁇ m, 5.0 ⁇ m, 8.0 ⁇ m, 10.0 ⁇ m, 20.0 ⁇ m, and the like) as the inorganic filler (b) And 8 types of 50.0 ⁇ m, each having a true specific gravity of 2.7 g / cm 3 ), (c) zinc stearate as a metal soap, (d) polystyrene as a low-shrinkage agent (weight average molecular weight 200,000), (e) Chopped strand glass (fiber length 6 mm) was used as a fiber reinforcement, and (f) t-butylperoxybenzoate was used as a curing agent.
  • Molding shrinkage ratio Compression molding of a shrinking disk ( ⁇ 90 mm ⁇ 11 mm) defined in JIS K-6911 5.7 under the conditions of a molding temperature of 160 ° C., a molding pressure of 10 MPa and a molding time of 3 minutes (Techno Marushichi Co., Ltd. Manufactured by using a compression molding machine), and the molding shrinkage ratio is calculated in accordance with JIS K-6911 5.7.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Provided is an unsaturated polyester resin composition which ensures good resin flowability and from which a molded article having excellent surface smoothness as well as dimensional accuracy and mechanical properties is provided. This unsaturated polyester resin composition comprises (a) an unsaturated polyester resin, (b) an inorganic filler, (c) a metal soap, (d) a low shrinking agent, (e) a fiber reinforcing material, and (f) a curing agent, wherein (b) the inorganic filler is 250-600 parts by mass with respect to 100 parts by mass of (a) the unsaturated polyester resin, and (b) the inorganic filler contains (b1) an inorganic filler having an average particle size of 0.5-5.0 μm and (b2) an inorganic filler having an average particle diameter of 8.0-50.0 μm at a mass ratio of (b1):(b2)=25:75-75:25.

Description

不飽和ポリエステル樹脂組成物、その硬化物を含む成形体、及び該成形体を含むランプリフレクターUnsaturated polyester resin composition, molded article containing the cured product thereof, and lamp reflector containing the molded article
　本発明は、不飽和ポリエステル樹脂組成物、その硬化物を含む成形体、及び該成形体を含むランプリフレクターに関する。詳細には、本発明は、自動車用ヘッドランプ等に用いられるランプリフレクターの製造で使用される不飽和ポリエステル樹脂組成物、その硬化物を含む成形体、及び該成形体を含むランプリフレクターに関する。 The present invention relates to an unsaturated polyester resin composition, a molded article containing the cured product thereof, and a lamp reflector containing the molded article. In particular, the present invention relates to an unsaturated polyester resin composition used in the production of a lamp reflector used for an automobile headlamp and the like, a molded article containing the cured product thereof, and a lamp reflector containing the molded article.
　不飽和ポリエステル樹脂に繊維強化材や無機充填材を配合した不飽和ポリエステル樹脂組成物は、成形時の樹脂流動性が良好であると共に、寸法精度、耐熱性及び機械的強度に優れた硬化物を与えるため、ＯＡ機器、事務機器のシャーシ、自動車用ヘッドランプのランプリフレクター等の製造において広く使用されている。 An unsaturated polyester resin composition in which a fiber reinforcing material and an inorganic filler are mixed with an unsaturated polyester resin has good resin flowability at the time of molding and a cured product excellent in dimensional accuracy, heat resistance and mechanical strength. It is widely used in the manufacture of office automation equipment, office equipment chassis, automobile headlamp lamp reflectors, etc.
　ランプリフレクターは、ランプの光を一定の角度で反射し前照させるため、反射層の表面平滑性が十分でない場合、配光のずれを引き起こすことがある。 The lamp reflector reflects and illuminates the light of the lamp at a certain angle, which may cause deviation of light distribution if the surface smoothness of the reflective layer is not sufficient.
　ランプリフレクターの製造では、不飽和ポリエステル樹脂組成物を成形及び硬化して得られた成形体（基材）の表面にアンダーコート剤を塗布及び硬化してアンダーコート層を形成した後、アンダーコート層上にアルミニウムや亜鉛等の金属コーティング層（反射層）を蒸着等によって形成する。配光のずれを防止するためには、アンダーコート層の厚さを厚くすればよいと考えられるが、アンダーコート層の厚さは製造コストの増大につながる。 In the production of a lamp reflector, an undercoat agent is applied and cured on the surface of a molded article (base material) obtained by molding and curing an unsaturated polyester resin composition to form an undercoat layer, and then an undercoat layer is formed. A metal coating layer (reflection layer) of aluminum, zinc or the like is formed thereon by vapor deposition or the like. In order to prevent the deviation of light distribution, it may be considered to increase the thickness of the undercoat layer, but the thickness of the undercoat layer leads to an increase in manufacturing cost.
　そのため、ランプリフレクターの製造に使用される不飽和ポリエステル樹脂組成物には、成形時の樹脂流動性に優れ、寸法精度、耐熱性及び機械的強度に優れる硬化物を与えるという特性に加えて、表面平滑性に優れた硬化物を与えることも要求される。 Therefore, the unsaturated polyester resin composition used for the production of the lamp reflector has a surface which is excellent in resin flowability at the time of molding and gives a cured product excellent in dimensional accuracy, heat resistance and mechanical strength. It is also required to provide a cured product with excellent smoothness.
　不飽和ポリエステル樹脂組成物には、機械的強度及びコストの観点から、無機充填材が一般に配合されている（特許文献１～２）。 An inorganic filler is generally blended in the unsaturated polyester resin composition from the viewpoint of mechanical strength and cost (Patent Documents 1 and 2).
国際公開第２０１６／０３５５１６号International Publication No. 2016/035516 国際公開第２００５／１０３１５２号WO 2005/103152
　しかし、配合する無機充填材の量を増やすと、不飽和ポリエステル樹脂組成物の機械的強度を向上させることができる一方、不飽和ポリエステル樹脂組成物の成形時の樹脂流動性及び成形品の表面平滑性は低下する傾向にある。 However, the mechanical strength of the unsaturated polyester resin composition can be improved by increasing the amount of the inorganic filler to be blended, while the resin flowability at the time of molding of the unsaturated polyester resin composition and the surface smoothness of the molded article Sex tends to decline.
　本発明は、上記のような問題を解決するためになされたものであり、成形時の樹脂流動性が良好であると共に、寸法精度及び機械的特性に加えて、表面平滑性に優れた成形体を与える不飽和ポリエステル樹脂組成物を提供することを目的とする。 The present invention has been made to solve the problems as described above, and has a good resin flowability at the time of molding, and a molded article having excellent surface smoothness in addition to dimensional accuracy and mechanical properties. It is an object of the present invention to provide an unsaturated polyester resin composition which gives
　本発明者らは、上記のような問題を解すべく鋭意研究した結果、不飽和ポリエステル樹脂組成物において所定量の無機充填材を配合し、かつ、該無機充填材として２種類の平均粒子径の異なる無機充填材を使用することで、成形時の樹脂流動性が良好であると共に、表面平滑性に優れた成形体を形成し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the problems as described above, the present inventors have blended a predetermined amount of inorganic filler in the unsaturated polyester resin composition, and used two types of average particle sizes as the inorganic filler. By using different inorganic fillers, it has been found that resin flowability at the time of molding is good and that a molded article having excellent surface smoothness can be formed, and the present invention has been completed.
　すなわち、本発明は、以下の［１］～［６］に関する。
［１］（ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物であって、
　前記（ｂ）無機充填材が前記（ａ）不飽和ポリエステル樹脂１００質量部に対して２５０～６００質量部であり、
　前記（ｂ）無機充填材として、（ｂ１）０．５～５．０μｍの平均粒子径を有する無機充填材と（ｂ２）８．０～５０．０μｍの平均粒子径を有する無機充填材とを、質量比が（ｂ１）：（ｂ２）＝２５：７５～７５：２５となる割合で含む、不飽和ポリエステル樹脂組成物。
［２］前記（ｂ）無機充填材が前記（ａ）不飽和ポリエステル樹脂１００質量部に対して３５０～４５０質量部である、［１］に記載の不飽和ポリエステル樹脂組成物。
［３］前記（ｂ）無機充填材が炭酸カルシウムを含む、［１］又は［２］のいずれかに記載の不飽和ポリエステル樹脂組成物。
［４］前記（ｅ）繊維強化材が（ａ）不飽和ポリエステル樹脂１００質量部に対して７０～１２０質量部である、［１］～［３］のいずれかに記載の不飽和ポリエステル樹脂組成物。
［５］［１］～［４］のいずれかに記載の不飽和ポリエステル樹脂組成物の硬化物を含む成形体。
［６］［５］に記載の成形体と、前記成形体上に位置するアンダーコート層と、前記アンダーコート層上に位置する金属反射層とを含むランプリフレクター。 That is, the present invention relates to the following [1] to [6].
[1] Unsaturated polyester resin composition comprising (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcement and (f) curing agent The object,
The inorganic filler (b) is 250 to 600 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a),
(B) As the inorganic filler, (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 μm and (b2) an inorganic filler having an average particle diameter of 8.0 to 50.0 μm And an unsaturated polyester resin composition containing a mass ratio of (b1) :( b2) = 25: 75 to 75:25.
[2] The unsaturated polyester resin composition according to [1], wherein the (b) inorganic filler is 350 to 450 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
[3] The unsaturated polyester resin composition according to [1] or [2], wherein the inorganic filler (b) contains calcium carbonate.
[4] The unsaturated polyester resin composition according to any one of [1] to [3], wherein the (e) fiber reinforcing material is 70 to 120 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin object.
[5] A molded article comprising a cured product of the unsaturated polyester resin composition according to any one of [1] to [4].
[6] A lamp reflector comprising the molded body according to [5], an undercoat layer located on the molded body, and a metal reflection layer located on the undercoat layer.
　本発明によれば、成形時の樹脂流動性が良好であると共に、寸法精度及び機械的特性に加えて、表面平滑性に優れた成形体を与える不飽和ポリエステル樹脂組成物を提供することができる。 According to the present invention, it is possible to provide an unsaturated polyester resin composition which gives a molded article excellent in surface smoothness in addition to dimensional accuracy and mechanical properties, as well as resin flowability at the time of molding. .
ランプリフレクターを備えたランプの断面図である。It is a sectional view of a lamp provided with a lamp reflector. 図１ａのａ－ａ’線の拡大断面図である。It is an expanded sectional view of the a-a 'line | wire of FIG. 1 a.
　本発明の一実施態様は、（ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物である。 One embodiment of the present invention comprises (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcement and (f) curing agent. It is an unsaturated polyester resin composition.
　以下、各成分について説明する。 Each component will be described below.
［（ａ）不飽和ポリエステル樹脂］
　（ａ）不飽和ポリエステル樹脂は、一般に、多価アルコールと不飽和多塩基酸及び任意成分の飽和多塩基酸とのエステル化反応による縮合生成物（不飽和ポリエステル）を、架橋剤（「反応性希釈剤」ともいう。）に溶解したものである。不飽和多塩基酸とは、重合可能なエチレン性二重結合を有する多塩基酸であり、飽和多塩基酸とは、重合可能なエチレン性二重結合を有さない多塩基酸である。このような不飽和ポリエステル樹脂は、本発明の技術分野において一般に公知であり、例えば、「ポリエステル樹脂ハンドブック」（日刊工業新聞社、１９８８年発行）や「塗料用語辞典」（色材協会編、１９９３年発行）等に記載されている。 [(A) unsaturated polyester resin]
(A) Unsaturated polyester resin generally contains a condensation product (unsaturated polyester) obtained by the esterification reaction of a polyhydric alcohol with an unsaturated polybasic acid and an optional saturated polybasic acid as a crosslinking agent (“reactivity It is also dissolved in “diluent”. An unsaturated polybasic acid is a polybasic acid having a polymerizable ethylenic double bond, and a saturated polybasic acid is a polybasic acid having no polymerizable ethylenic double bond. Such unsaturated polyester resins are generally known in the technical field of the present invention, and, for example, "Polyester resin handbook" (Nikkan Kogyo Shimbun, published in 1988) and "Coating glossary" (coloring materials association ed., 1993) Yearly issue etc.).
　不飽和ポリエステルの合成に用いられる多価アルコールとしては、特に限定されず、本発明の技術分野において公知のものを用いることができる。多価アルコールの例としては、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ペンタンジオール、ヘキサンジオール、ネオペンタンジオール、水素化ビスフェノールＡ、ビスフェノールＡ、グリセリン等が挙げられる。これらの中でも、耐熱性、機械的強度及び成形時の樹脂流動性の観点から、プロピレングリコール、ネオペンチルグリコール、ビスフェノールＡ及び水素化ビスフェノールＡが好ましい。これらは、単独又は複数を組み合わせて用いることができる。 The polyhydric alcohol used for the synthesis of the unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentanediol, hydrogenated bisphenol A, bisphenol A, glycerin Etc. Among these, propylene glycol, neopentyl glycol, bisphenol A and hydrogenated bisphenol A are preferable from the viewpoints of heat resistance, mechanical strength and resin fluidity at the time of molding. These can be used alone or in combination of two or more.
　不飽和ポリエステルの合成に用いられる不飽和多塩基酸としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。不飽和多塩基酸の例としては、無水マレイン酸、フマル酸、シトラコン酸、イタコン酸等が挙げられる。これらは、単独又は複数を組み合わせて用いることができる。これらの中でも、耐熱性、機械的強度及び成形時の樹脂流動性等の観点から、無水マレイン酸及びフマル酸が好ましい。 The unsaturated polybasic acid used for the synthesis of the unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used. Examples of unsaturated polybasic acids include maleic anhydride, fumaric acid, citraconic acid, itaconic acid and the like. These can be used alone or in combination of two or more. Among these, maleic anhydride and fumaric acid are preferable from the viewpoints of heat resistance, mechanical strength, resin fluidity at the time of molding, and the like.
　不飽和ポリエステルの合成に用いられる飽和多塩基酸としては、特に限定されず、公知のものを用いることができる。飽和多塩基酸の例としては、無水フタル酸、イソフタル酸、テレフタル酸、コハク酸、アジピン酸、セバシン酸、テトラクロロ無水フタル酸、テトラブロモ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、ヘット酸等が挙げられる。これらは、単独又は複数を組み合わせて用いることができる。 The saturated polybasic acid used for the synthesis of the unsaturated polyester is not particularly limited, and known ones can be used. Examples of saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endo methylene tetrahydrophthalic anhydride, hetic acid, etc. It can be mentioned. These can be used alone or in combination of two or more.
　不飽和ポリエステルは、上記のような原料を用いて公知の方法で合成することができる。この合成における各種条件は、使用する原料やその量に応じて適宜設定する必要があるが、一般的に、窒素ガス等の不活性ガス気流中、１４０～２３０℃の温度にて加圧又は減圧下でエステル化させればよい。このエステル化反応では、必要に応じてエステル化触媒を使用することができる。触媒の例としては、酢酸マンガン、ジブチル錫オキサイド、シュウ酸第一錫、酢酸亜鉛、及び酢酸コバルト等の公知の触媒が挙げられる。これらは、単独又は複数を組み合わせて用いることができる。 Unsaturated polyester can be synthesized by known methods using raw materials as described above. Although various conditions in this synthesis need to be set appropriately according to the raw materials used and the amount thereof, generally, pressurization or pressure reduction is carried out at a temperature of 140 to 230 ° C. in an inert gas stream such as nitrogen gas. It may be esterified below. In this esterification reaction, an esterification catalyst can be used as needed. Examples of catalysts include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate and cobalt acetate. These can be used alone or in combination of two or more.
　不飽和ポリエステルの重量平均分子量（Ｍｗ）は、特に限定されないが、好ましくは３，０００～２５，０００であり、より好ましくは５，０００～２０，０００であり、さらに好ましくは７，０００～１８，０００である。なお、本明細書において「重量平均分子量」とは、ゲルパーミエーションクロマトグラフィー（昭和電工株式会社製Ｓｈｏｄｅｘ（登録商標）ＧＰＣ－１０１）を用いて下記条件にて常温（２３℃）で測定し、標準ポリスチレン検量線を用いて求めた値を意味する。
　カラム：昭和電工株式会社製ＬＦ－８０４
　カラム温度：４０℃
　試料：不飽和ポリエステルの０．２質量％テトラヒドロフラン溶液
　流量：１ｍＬ／分
　溶離液：テトラヒドロフラン
　検出器：ＲＩ－７１Ｓ The weight average molecular weight (Mw) of the unsaturated polyester is not particularly limited, but is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and still more preferably 7,000 to 18 , 000. In the present specification, “weight average molecular weight” is measured at room temperature (23 ° C.) under the following conditions using gel permeation chromatography (Shodex (registered trademark) GPC-101 manufactured by Showa Denko KK). The value determined using a standard polystyrene calibration curve is meant.
Column: Showa Denko KK LF-804
Column temperature: 40 ° C
Sample: 0.2 wt% tetrahydrofuran solution of unsaturated polyester Flow rate: 1 mL / min Eluent: tetrahydrofuran Detector: RI-71S
　（ａ）不飽和ポリエステル樹脂に用いられる架橋剤としては、不飽和ポリエステルと重合可能なエチレン性二重結合を有しているものであれば特に限定されず、本発明の技術分野において公知のものを用いることができる。架橋剤の例としては、スチレンモノマー、ジアリルフタレートモノマー、ジアリルフタレートプレポリマー、メタクリル酸メチル、トリアリルイソシアヌレート等が挙げられる。これらは、単独又は複数を組み合わせて用いることができる。 (A) The crosslinking agent used for the unsaturated polyester resin is not particularly limited as long as it has an ethylenic double bond that can be polymerized with the unsaturated polyester, and known crosslinking agents in the technical field of the present invention Can be used. Examples of the crosslinking agent include styrene monomer, diallyl phthalate monomer, diallyl phthalate prepolymer, methyl methacrylate, triallyl isocyanurate and the like. These can be used alone or in combination of two or more.
　（ａ）不飽和ポリエステル樹脂における架橋剤の配合量は、特に限定されないが、作業性、重合性、成形体の収縮性及び量調整の自由度の観点から、不飽和ポリエステル及び架橋剤の合計に対して、好ましくは２５～７０質量％、より好ましくは３０～６８質量％、さらに好ましくは３５～６５質量％である。 (A) The compounding amount of the crosslinking agent in the unsaturated polyester resin is not particularly limited, but from the viewpoint of workability, polymerizability, shrinkage of molded articles and freedom in adjusting the amount, the total amount of unsaturated polyester and crosslinking agent On the other hand, it is preferably 25 to 70% by mass, more preferably 30 to 68% by mass, and still more preferably 35 to 65% by mass.
　（ａ）不飽和ポリエステル樹脂は、必要に応じてハイドロキノン等の重合禁止剤を含むこともできる。 (A) The unsaturated polyester resin can also contain a polymerization inhibitor such as hydroquinone, if necessary.
［（ｂ）無機充填材］
　（ｂ）無機充填材としては、本発明の技術分野において公知のものを用いることができる。（ｂ）無機充填材の例としては、炭酸カルシウム、シリカ、アルミナ、水酸化アルミニウム、硫酸バリウム、ワラストナイト、クレー、タルク、マイカ、石膏、無水ケイ酸、ガラス粉末等が挙げられる。これらは、単独又は複数を組み合わせて用いることができる。 [(B) inorganic filler]
As the inorganic filler (b), those known in the technical field of the present invention can be used. Examples of the inorganic filler (b) include calcium carbonate, silica, alumina, aluminum hydroxide, barium sulfate, wollastonite, clay, talc, mica, gypsum, anhydrous silicic acid, glass powder and the like. These can be used alone or in combination of two or more.
　（ｂ）無機充填材の真比重は、好ましくは１～１０ｇ／ｃｍ３であり、より好ましくは１．５～８ｇ／ｃｍ３であり、さらに好ましくは２～５ｇ／ｃｍ３である。無機充填材の真比重が１ｇ／ｃｍ３以上であれば、成形体の機械的特性がより良好であり、無機充填材の真比重が１０ｇ／ｃｍ３以下であれば、混練性がより良好である。 The true specific gravity of the inorganic filler (b) is preferably 1 to 10 g / cm 3 , more preferably 1.5 to 8 g / cm 3 , and still more preferably 2 to 5 g / cm 3 . If the true specific gravity of the inorganic filler is 1 g / cm 3 or more, the mechanical properties of the molded article are better, and if the true specific gravity of the inorganic filler is 10 g / cm 3 or less, the kneadability is better is there.
　（ｂ）無機充填材の形状としては、特に制限されるものではないが、略真球、楕円体、鱗片状、無定形等が挙げられる。 The shape of the inorganic filler (b) is not particularly limited, and examples thereof include approximately a true sphere, an ellipsoid, a scaly shape, and an amorphous shape.
　（ｂ）無機充填材の配合量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して２５０～６００質量部であり、より好ましくは３００～５５０質量部であり、さらに好ましくは３５０～５００質量部であり、特に３５０～４５０質量部である。（ｂ）無機充填材の配合量が２５０質量部以上であれば、成形体の機械的特性がより良好である。また、（ｂ）無機充填材の配合量が６００質量部以下であれば、不飽和ポリエステル樹脂組成物中で（ｂ）無機充填材がより均一に分散するため均質な成形体を製造することができる。 The blending amount of the (b) inorganic filler is 250 to 600 parts by mass, more preferably 300 to 550 parts by mass, and still more preferably 350 to 500 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. Parts, in particular 350 to 450 parts by weight. (B) If the compounding quantity of an inorganic filler is 250 mass parts or more, the mechanical characteristic of a molded object will be more favorable. Moreover, if the compounding quantity of (b) inorganic filler is 600 mass parts or less, in order to disperse | distribute the (b) inorganic filler more uniformly in an unsaturated polyester resin composition, a homogeneous molded object may be manufactured. it can.
［（ｂ１）及び（ｂ２）特定の平均粒子径を有する無機充填材］
　無機充填材は、（ｂ１）０．５～５．０μｍの平均粒子径を有する無機充填材、及び（ｂ２）８．０～５０．０μｍの平均粒子径を有する無機充填材を含む。 [(B1) and (b2) inorganic filler having a specific average particle size]
The inorganic filler includes (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 μm, and (b2) an inorganic filler having an average particle diameter of 8.0 to 50.0 μm.
　本明細書において（ｂ）無機充填材の「平均粒子径」とは、恒圧粉体比表面積測定装置による空気透過法によって求めた比表面積から以下の式にしたがって求めた粒子径を意味する。恒圧粉体比表面積測定装置としては、株式会社島津製作所製のＳＳ－１００を用いることができる。
　平均粒子径［μｍ］＝（６×１００００）／（真比重［ｇ／ｃｍ３］×比表面積［ｃｍ２／ｇ］） In the present specification, the "average particle size" of the inorganic filler (b) means a particle size determined according to the following equation from the specific surface area determined by an air permeation method using a constant pressure powder specific surface area measuring device. As a constant pressure powder specific surface area measuring device, SS-100 manufactured by Shimadzu Corporation can be used.
Average particle size [μm] = (6 × 10000) / (true specific gravity [g / cm 3 ] × specific surface area [cm 2 / g])
　（ｂ１）の平均粒子径は０．７～４．０μｍがより好ましく、さらに好ましくは０．８～３．０μｍである。一方、（ｂ２）の平均粒子径は９．０～４０．０μｍがより好ましく、さらに好ましくは１０．０～３０．０μｍである。（ｂ１）の平均粒子径が０．５μｍ以上であれば、不飽和ポリエステル樹脂組成物の粘度が適切であり成形時に良好な樹脂流動性となり、５．０μｍ以下であれば、成形体の表面平滑性を向上させることができる。また、（ｂ２）の平均粒子径が８．０μｍ以上であれば、成形時の樹脂流動性及び成形体の機械的強度がより良好であり、５０．０μｍ以下であれば、成形体の表面平滑性をより良好に保持することができる。 The average particle diameter of (b1) is more preferably 0.7 to 4.0 μm, still more preferably 0.8 to 3.0 μm. On the other hand, the average particle diameter of (b2) is more preferably 9.0 to 40.0 μm, and still more preferably 10.0 to 30.0 μm. If the average particle diameter of (b1) is 0.5 μm or more, the viscosity of the unsaturated polyester resin composition is appropriate and good resin fluidity is obtained at the time of molding, and if it is 5.0 μm or less, the surface of the molded article is smooth. It is possible to improve the quality. Further, if the average particle diameter of (b2) is 8.0 μm or more, the resin flowability at molding and the mechanical strength of the molded product are better, and if it is 50.0 μm or less, the surface smoothness of the molded product It is possible to keep the sex better.
　（ｂ１）と（ｂ２）との質量比は２５：７５～７５：２５である。表面平滑性の面から、好ましくは３０：７０～７０：３０であり、より好ましくは４０：６０～６０：４０である。 The mass ratio of (b1) to (b2) is 25:75 to 75:25. From the viewpoint of surface smoothness, it is preferably 30:70 to 70:30, and more preferably 40:60 to 60:40.
［（ｃ）金属石鹸］
　（ｃ）金属石鹸は、本発明の技術分野において離型剤として一般に用いられている成分である。（ｃ）金属石鹸としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｃ）金属石鹸の例としては、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸マグネシウム等が挙げられる。これらは、単独又は複数を組み合わせて用いることができる。 [(C) metal soap]
(C) Metal soap is a component generally used as a mold release agent in the technical field of the present invention. The metal soap (c) is not particularly limited, and those known in the technical field of the present invention can be used. Examples of (c) metal soaps include calcium stearate, zinc stearate, aluminum stearate, magnesium stearate and the like. These can be used alone or in combination of two or more.
　（ｃ）金属石鹸の配合量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して１～１５質量部であることが好ましい。（ｃ）金属石鹸の配合量が１質量部以上であれば成形体の離型性がより良好である。一方、（ｃ）金属石鹸の配合量が１５質量部以下であれば成形体の表面に（ｃ）金属石鹸がブリードすることを防ぐことができるため、所望のフォギング性及びアンダーコート剤の塗装性を有する成形体を得ることができる。 The blending amount of the (c) metal soap is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (C) If the compounding quantity of metal soap is 1 mass part or more, the releasability of a molded object will be more favorable. On the other hand, if the blending amount of (c) metal soap is 15 parts by mass or less, it is possible to prevent (c) the metal soap from bleeding on the surface of the molded product, so desired fogging properties and paintability of the undercoat agent Can be obtained.
［（ｄ）低収縮剤］
　（ｄ）低収縮剤としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。低収縮剤の例としては、ポリスチレン、ポリメチルメタクリレート、ポリ酢酸ビニル、飽和ポリエステル、スチレン－ブタジエン系ゴム等の低収縮剤として一般に使用されている熱可塑性ポリマーが挙げられる。これらは、単独又は２種以上を組み合わせて用いることができる。 [(D) Low-shrinkage agent]
The low-shrinkage agent (d) is not particularly limited, and those known in the technical field of the present invention can be used. Examples of the low shrinkage agent include thermoplastic polymers generally used as a low shrinkage agent such as polystyrene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, styrene-butadiene rubber and the like. These can be used alone or in combination of two or more.
　（ｄ）低収縮剤の配合量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して１０～４０質量部であることが好ましい。（ｄ）低収縮剤の配合量が１０質量部以上であれば成形体の収縮率が小さくなり、所望の寸法精度を得ることができる。一方、（ｄ）低収縮剤の配合量が４０質量部以下であれば、成形体の機械的特性がより良好である。 The blending amount of the (d) low-shrinkage agent is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (D) If the blending amount of the low-shrinkage agent is 10 parts by mass or more, the shrinkage rate of the molded product becomes small, and desired dimensional accuracy can be obtained. On the other hand, if the blending amount of the (d) low shrinkage agent is 40 parts by mass or less, the mechanical properties of the molded article are more favorable.
［（ｅ）繊維強化材］
　（ｅ）繊維強化材は、アスペクト比が３以上の繊維状物質である。アスペクト比は、日本工業規格ＪＩＳ　Ｒ－８９００－１：２００８「粒子径測定装置検定用粒子」に記載されている顕微鏡法によって測定することができる。 [(E) fiber reinforcement]
(E) The fiber reinforcing material is a fibrous material having an aspect ratio of 3 or more. The aspect ratio can be measured by the microscopic method described in Japanese Industrial Standard JIS R-8900-1: 2008 "Particle for measuring particle size measuring device".
　（ｅ）繊維強化材としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｅ）繊維強化材の例としては、ガラス繊維、パルプ、ポリエチレンテレフタレート繊維、ビニロン繊維、カーボン繊維、アラミド繊維、ワラストナイト等の様々な有機繊維及び無機繊維を挙げることができる。その中でもガラス繊維が好ましく、より好ましくは繊維長１．５～２５ｍｍ程度に切断したチョップドストランドガラスである。 The fiber reinforcing material (e) is not particularly limited, and those known in the technical field of the present invention can be used. (E) Examples of the fiber reinforcement include various organic fibers and inorganic fibers such as glass fibers, pulp, polyethylene terephthalate fibers, vinylon fibers, carbon fibers, aramid fibers, wollastonite and the like. Among them, glass fiber is preferable, and chopped strand glass cut to a fiber length of about 1.5 to 25 mm is more preferable.
　（ｅ）繊維強化材の配合量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して７０～１２０質量部であることが好ましい。（ｅ）繊維強化材の配合量が７０質量部以上であれば、成形体の機械的特性がより良好である。一方、（ｅ）繊維強化材の配合量が１２０質量部以下であれば、不飽和ポリエステル樹脂組成物中で（ｅ）繊維強化材がより均一に分散し、均質な成形体を製造することができる。 The compounding amount of the (e) fiber reinforcing material is preferably 70 to 120 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (E) If the compounding quantity of a fiber reinforcement is 70 mass parts or more, the mechanical characteristic of a molded object will be more favorable. On the other hand, if the blending amount of (e) fiber reinforcing material is 120 parts by mass or less, (e) the fiber reinforcing material is more uniformly dispersed in the unsaturated polyester resin composition to produce a homogeneous molded article. it can.
［（ｆ）硬化剤］
　（ｆ）硬化剤としては、エチレン性不飽和結合を重合できるラジカル開始剤であれば特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｆ）硬化剤の例としては、ｔ－ブチルパーオキシオクトエート、ベンゾイルパーオキサイド、１，１－ジ－ｔ－ブチルパーオキシ－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシベンゾエート、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド等の有機過酸化物が挙げられる。これらは、単独又は２種以上を組み合わせて用いることができる。 [(F) curing agent]
The curing agent (f) is not particularly limited as long as it is a radical initiator capable of polymerizing an ethylenically unsaturated bond, and those known in the technical field of the present invention can be used. (F) Examples of curing agents include t-butyl peroxy octoate, benzoyl peroxide, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane, t-butyl peroxy isopropyl carbonate And organic peroxides such as t-butylperoxybenzoate, dicumyl peroxide, di-t-butyl peroxide and the like. These can be used alone or in combination of two or more.
　（ｆ）硬化剤の配合量は、使用する原料に応じて適宜設定すればよく、特に限定されない。（ｆ）硬化剤の配合量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して好ましくは１～１０質量部であり、より好ましくは１～８質量部であり、さらに好ましくは１～５質量部である。 (F) The compounding amount of the curing agent may be appropriately set according to the raw material to be used, and is not particularly limited. The amount of the curing agent (f) is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, still more preferably 1 to 5 parts by mass per 100 parts by mass of the unsaturated polyester resin (a). It is a mass part.
［その他の成分］
　本発明の不飽和ポリエステル樹脂組成物は、上記の成分に加えて、増粘剤、顔料、減粘剤等の本発明の技術分野において公知の成分を、本発明の効果を阻害しない範囲において含むことができる。 [Other ingredients]
The unsaturated polyester resin composition of the present invention includes, in addition to the above components, components known in the technical field of the present invention, such as thickeners, pigments, viscosity reducing agents, etc., within the range not to inhibit the effects of the present invention. be able to.
　増粘剤としては、特に限定されないが、例えば、酸化マグネシウム、水酸化マグネシウム、水酸化カルシウム、酸化カルシウム等の（ｂ）無機充填材以外の金属酸化物、及びイソシアネート化合物等が挙げられる。これらは、単独又は２種以上を組み合わせて用いることができる。 Although it does not specifically limit as a thickener, For example, metal oxides other than (b) inorganic fillers, such as magnesium oxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and an isocyanate compound etc. are mentioned. These can be used alone or in combination of two or more.
［不飽和ポリエステル樹脂組成物の製造方法］
　不飽和ポリエステル樹脂組成物は、本発明の技術分野において通常行われる方法、例えば、ニーダー等を用いて各成分を混練することによって製造することができる。 [Method for producing unsaturated polyester resin composition]
The unsaturated polyester resin composition can be produced by a method which is usually carried out in the technical field of the present invention, for example, by kneading each component using a kneader or the like.
［不飽和ポリエステル樹脂組成物の成形体の製造方法］
　不飽和ポリエステル樹脂組成物を、所望の形状に成形して硬化することによって成形体を製造することができる。成形及び硬化方法としては、特に限定されず、本発明の技術分野において通常行われる方法、例えば、圧縮成形、トランスファー成形、射出成形等を用いることができる。 [Method of producing molded article of unsaturated polyester resin composition]
A molded object can be manufactured by shape | molding and hardening an unsaturated polyester resin composition to a desired shape. The molding and curing method is not particularly limited, and methods commonly used in the technical field of the present invention, for example, compression molding, transfer molding, injection molding and the like can be used.
［ランプリフレクター］
　不飽和ポリエステル樹脂組成物の成形体は、ランプリフレクターの基材として用いるのに適している。上記２種類の特定の平均粒子径を有する無機充填材を含む不飽和ポリエステル樹脂組成物の成形体は表面平滑性に優れるため、配光のずれを防止するのに必要なアンダーコート層の厚さが小さい。したがって製造コストを低減することが可能である。 [Lamp reflector]
The molded article of the unsaturated polyester resin composition is suitable for use as a substrate of a lamp reflector. Since the molded article of the unsaturated polyester resin composition containing the inorganic filler having the above two specific average particle sizes is excellent in surface smoothness, the thickness of the undercoat layer necessary to prevent the deviation of the light distribution Is small. Therefore, it is possible to reduce the manufacturing cost.
　ランプリフレクターは、一般に、不飽和ポリエステル樹脂組成物の成形体（基材）と、成形体上に位置するアンダーコート層と、アンダーコート層上に位置する金属反射層とを含む。 The lamp reflector generally includes a molded article (base material) of the unsaturated polyester resin composition, an undercoat layer located on the molded article, and a metal reflective layer located on the undercoat layer.
　以下、ランプリフレクターの好適な実施形態につき図面を用いて説明する。 Hereinafter, preferred embodiments of the lamp reflector will be described with reference to the drawings.
　図１ａは、一実施形態のランプリフレクターを備えたランプの断面図である。また、図１ｂは、図１ａのａ－ａ'線の拡大断面図である。 FIG. 1a is a cross-sectional view of a lamp with a lamp reflector of one embodiment. FIG. 1b is an enlarged cross-sectional view of the line aa 'of FIG. 1a.
　図１ａにおいて、ランプは、一般に、ランプリフレクターと、ランプリフレクターの所定の位置に設けられた光源４と、ランプリフレクターの開口部に設けられたレンズ５とを備えている。ここで、ランプリフレクターは、図１ｂに示すように、不飽和ポリエステル樹脂組成物の成形体１と、成形体１上に位置するアンダーコート層２と、アンダーコート層２上に位置する金属反射層３とを有する。このランプでは、光源４から生じる光を金属反射層３によって反射させる。 In FIG. 1a, the lamp generally comprises a lamp reflector, a light source 4 provided at a predetermined position of the lamp reflector, and a lens 5 provided at the opening of the lamp reflector. Here, as shown in FIG. 1 b, the lamp reflector includes a molded body 1 of the unsaturated polyester resin composition, an undercoat layer 2 positioned on the molded body 1, and a metal reflection layer positioned on the undercoat layer 2. And three. In this lamp, the light generated from the light source 4 is reflected by the metal reflection layer 3.
　アンダーコート層２の厚さは、要求されるランプリフレクターの大きさにあわせて適宜設定することができるが、一般に１０～５０μｍである。 The thickness of the undercoat layer 2 can be appropriately set in accordance with the required size of the lamp reflector, but is generally 10 to 50 μm.
　アンダーコート層２を与えるアンダーコート剤としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。このアンダーコート剤は、プライマー組成物とも呼ばれ、一般にＵＶ硬化性樹脂又は熱硬化性樹脂を含む樹脂組成物である。ＵＶ硬化性樹脂及び熱硬化性樹脂の例としては、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等の多官能性モノマーの単独重合又は共重合によって得られるアクリル樹脂等が挙げられる。アンダーコート剤は、不飽和ポリエステル樹脂、ビニル変性ポリエステル樹脂、フェノール変性ポリエステル樹脂、油脂変性ポリエステル樹脂、シリコーン変性ポリエステル樹脂等のポリエステル樹脂、硬化剤、溶剤等を含んでいてもよい。 The undercoat agent for giving the undercoat layer 2 is not particularly limited, and those known in the technical field of the present invention can be used. This undercoat agent is also called a primer composition, and is generally a resin composition containing a UV curable resin or a thermosetting resin. Examples of the UV curable resin and the thermosetting resin include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like. The acrylic resin etc. which are obtained by the homopolymerization or copolymerization of a functional monomer are mentioned. The undercoat agent may contain a polyester resin such as unsaturated polyester resin, vinyl-modified polyester resin, phenol-modified polyester resin, oil-modified polyester resin, silicone-modified polyester resin, curing agent, solvent and the like.
　金属反射層３の厚さは、要求されるランプリフレクターの大きさなどにあわせて適宜設定することができるが、一般に８００～２，０００Åである。 The thickness of the metal reflection layer 3 can be appropriately set in accordance with the required size of the lamp reflector and the like, but is generally 800 to 2,000 Å.
　金属反射層３を与える材料としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。金属反射層３の材料の例としては、アルミニウム、銀、亜鉛、銀及び亜鉛を主体とした合金等が挙げられる。 The material for providing the metal reflective layer 3 is not particularly limited, and materials known in the technical field of the present invention can be used. Examples of the material of the metal reflective layer 3 include aluminum, silver, zinc, an alloy composed mainly of silver and zinc, and the like.
　ランプボディの所定の位置に設けられる光源４及びレンズ５としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。 The light source 4 and the lens 5 provided at predetermined positions of the lamp body are not particularly limited, and those known in the technical field of the present invention can be used.
［ランプリフレクターの製造方法］
　このような構成を有するランプリフレクターは、次のようにして製造することができる。 [Method of manufacturing lamp reflector]
A lamp reflector having such a configuration can be manufactured as follows.
　まず、不飽和ポリエステル樹脂組成物を成形及び硬化して成形体１を得る。成形体１は、不飽和ポリエステル樹脂組成物を圧縮成形、トランスファー成形、射出成形等の公知の成形法を用いて所定の形状に成形及び硬化することによって得ることができる。 First, the unsaturated polyester resin composition is molded and cured to obtain a molded body 1. The molded body 1 can be obtained by molding and curing the unsaturated polyester resin composition into a predetermined shape using a known molding method such as compression molding, transfer molding, injection molding and the like.
　次に、必要に応じて離型剤の除去処理を行う。離型剤の除去は、洗浄処理、熱処理、フレーム処理等によって行うことができる。 Next, the release agent is removed if necessary. The removal of the release agent can be carried out by washing treatment, heat treatment, flame treatment or the like.
　続いて、成形体１上にアンダーコート剤を塗布して硬化させてアンダーコート層２を形成する。アンダーコート剤を成形体１上に塗布する方法としては、特に限定されず、例えば、エアースプレー方式やエアレススプレー方式等の公知の方法を用いることができる。硬化方法も、特に限定されず、アンダーコート剤の種類に応じて適宜選択することができる。 Subsequently, an undercoat agent is applied onto the molded body 1 and cured to form an undercoat layer 2. It does not specifically limit as method to apply | coat an undercoat agent on the molded object 1, For example, well-known methods, such as an air spray system and an airless spray system, can be used. The curing method is also not particularly limited, and can be appropriately selected according to the type of undercoat agent.
　その後、アンダーコート層２上に金属反射層３を形成する。金属反射層３をアンダーコート層２上に形成する方法としては、特に限定されず、例えば、真空蒸着法等の公知の方法を用いることができる。 Thereafter, the metal reflective layer 3 is formed on the undercoat layer 2. It does not specifically limit as method to form the metal reflection layer 3 on the undercoat layer 2, For example, well-known methods, such as a vacuum evaporation method, can be used.
　さらに、光源４及びレンズ５をランプボディの所定の位置に取り付ける。光源４及びレンズ５を取り付ける方法は、特に限定されず、公知の方法に準じて行うことができる。 Furthermore, the light source 4 and the lens 5 are attached to predetermined positions of the lamp body. The method of attaching the light source 4 and the lens 5 is not particularly limited, and can be performed according to a known method.
　以下、実施例及び比較例によって本発明を詳細に説明するが、これらによって本発明が限定されるものではない。 Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited thereto.
（不飽和ポリエステル樹脂の合成）
　攪拌機、還流冷却器、窒素ガス導入管及び温度計を備えた反応容器中に、プロピレングリコール１００モル、無水フタル酸３０モル、無水マレイン酸７０モルを仕込み、定法に従い２１０℃で酸価が２０ｍｇＫＯＨ／ｇになるまで反応させた。次に、反応物１００質量部に対してハイドロキノンを０．０１５質量部添加して１６０℃に冷却した後、スチレンモノマーをさらに添加して不飽和ポリエステル樹脂を得た。ここで、スチレンモノマーは、不飽和ポリエステル樹脂中で３０質量％となるように添加した。また、不飽和ポリエステルの重量平均分子量（Ｍｗ）を上記の条件にて測定したところ、１５，０００であった。 (Synthesis of unsaturated polyester resin)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a thermometer, 100 mol of propylene glycol, 30 mol of phthalic anhydride and 70 mol of maleic anhydride are charged, and according to a conventional method, the acid value is 20 mg KOH / It was made to react until it became g. Next, 0.015 parts by mass of hydroquinone was added to 100 parts by mass of the reaction product and cooled to 160 ° C., and then a styrene monomer was further added to obtain an unsaturated polyester resin. Here, the styrene monomer was added to be 30% by mass in the unsaturated polyester resin. Moreover, it was 15,000 when the weight average molecular weight (Mw) of unsaturated polyester was measured on said conditions.
（実施例１～１３）
　表１に示す配合組成で各成分を仕込み、双腕型ニーダーを用いて２５℃にて３０分間混練することで不飽和ポリエステル樹脂組成物を得た。なお、表１及び２に示す（ａ）不飽和ポリエステル樹脂は、スチレンモノマーを３０質量％含有する。 (Examples 1 to 13)
Each component was charged according to the composition shown in Table 1 and kneaded for 30 minutes at 25 ° C. using a double-arm type kneader to obtain an unsaturated polyester resin composition. The unsaturated polyester resin (a) shown in Tables 1 and 2 contains 30% by mass of a styrene monomer.
（比較例１～１０）
　表２に示す配合組成で各成分を仕込み、双腕型ニーダーを用いて２５℃にて３０分間混練することで不飽和ポリエステル樹脂組成物を得た。 (Comparative Examples 1 to 10)
The unsaturated polyester resin composition was obtained by preparing each component with the composition shown in Table 2 and kneading it for 30 minutes at 25 ° C. using a double-arm type kneader.
　上記の実施例及び比較例において、（ｂ）無機充填材として炭酸カルシウム（平均粒子径０．５μｍ、１．０μｍ、２．０μｍ、５．０μｍ、８．０μｍ、１０．０μｍ、２０．０μｍ、及び５０．０μｍの８種類、いずれも真比重２．７ｇ／ｃｍ３）、（ｃ）金属石鹸としてステアリン酸亜鉛、（ｄ）低収縮剤としてポリスチレン（重量平均分子量２００，０００）、（ｅ）繊維強化材としてチョップドストランドガラス（繊維長６ｍｍ）、（ｆ）硬化剤としてｔ－ブチルパーオキシベンゾエートを用いた。 In the above Examples and Comparative Examples, calcium carbonate (average particle diameter 0.5 μm, 1.0 μm, 2.0 μm, 5.0 μm, 8.0 μm, 10.0 μm, 20.0 μm, and the like) as the inorganic filler (b) And 8 types of 50.0 μm, each having a true specific gravity of 2.7 g / cm 3 ), (c) zinc stearate as a metal soap, (d) polystyrene as a low-shrinkage agent (weight average molecular weight 200,000), (e) Chopped strand glass (fiber length 6 mm) was used as a fiber reinforcement, and (f) t-butylperoxybenzoate was used as a curing agent.
　上記のようにして得られた実施例及び比較例の不飽和ポリエステル樹脂組成物について、混練性、樹脂組成物の型内流動性、成形品表面平滑性、成形収縮率及び曲げ弾性率の評価を行った。なお、混練性評価が不良であった不飽和ポリエステル樹脂組成物については、その他の評価を行わなかった。これらの評価の方法は次のとおりである。結果を表１及び２に示す。 With respect to the unsaturated polyester resin compositions of the Examples and Comparative Examples obtained as described above, evaluation of the kneadability, in-mold fluidity of the resin composition, molded article surface smoothness, molding shrinkage and flexural modulus went. In addition, about the unsaturated polyester resin composition in which the kneadability evaluation was unsatisfactory, other evaluation was not performed. The method of these evaluations is as follows. The results are shown in Tables 1 and 2.
（１）混練性
　双腕型ニーダーを用いて２５℃にて３０分間混練して不飽和ポリエステル樹脂組成物を調製する際に、分散不良がない均一な不飽和ポリエステル樹脂組成物が得られるか否かを目視にて評価する。この評価において、不飽和ポリエステル樹脂組成物が均一であった場合を良、不飽和ポリエステル樹脂組成物に分散不良があった場合を不良と表す。 (1) Kneadability When preparing an unsaturated polyester resin composition by kneading at 25 ° C. for 30 minutes using a double-arm type kneader, it is possible to obtain a uniform unsaturated polyester resin composition free from poor dispersion. Evaluate the scale visually. In this evaluation, the case where the unsaturated polyester resin composition is uniform is referred to as good, and the case where the unsaturated polyester resin composition has poor dispersion is referred to as a defect.
（２）樹脂組成物の型内流動性
　トランスファー成形機（株式会社テクノマルシチ製）にスパイラルフロー金型（断面形状が上辺６ｍｍ、底辺８ｍｍ、高さ２ｍｍの台形状）を取り付けて金型温度１６０℃、注入圧力１０ＭＰａの条件下でスパイラルフロー試験を行い、流動長を測定する。この評価において、流動長が４０ｃｍ以上であると樹脂組成物の型内流動性が良好である。 (2) In-mold fluidity of resin composition A spiral flow mold (cross-sectional shape 6 mm on top, 8 mm on bottom, trapezoidal 2 mm in height) is attached to a transfer molding machine (manufactured by Techno Marsichi Co., Ltd.) and mold temperature 160 Conduct a spiral flow test under the conditions of ° C and injection pressure of 10 MPa to measure the flow length. In this evaluation, when the flow length is 40 cm or more, the in-mold flowability of the resin composition is good.
（３）成形品表面平滑性
　成形温度１６０℃、射出圧力２０ＭＰａ、成形時間１分の条件下にてトランスファー成形（株式会社テクノマルシチ製トランスファー成形機）を行い、トランスファー成形体（φ１１７ｍｍ、厚さ３ｍｍ）を作製する。このトランスファー成形体の外観を目視で確認し、全体にツヤがありなお且つ全体にヒケがない場合を良、全体若しくは部分的にツヤがない又は全体若しくは部分的にヒケがある場合を不良と表す。 (3) Molded Product Surface Smoothness Transfer molding (transfer molding machine manufactured by Technomarsity Co., Ltd.) under conditions of molding temperature 160 ° C., injection pressure 20 MPa, molding time 1 minute, transfer molded body (φ 117 mm, thickness 3 mm) )). The appearance of the transfer molded product is visually confirmed, and the case where there is gloss throughout and no sinking throughout is indicated as good, and the case where there is gloss entirely or partially or the entire or partial sinking is represented as poor .
（４）成形収縮率
　ＪＩＳ　Ｋ－６９１１　５．７に規定される収縮円盤（φ９０ｍｍ×１１ｍｍ）を、成形温度１６０℃、成形圧力１０ＭＰａ、成形時間３分の条件下で圧縮成形（株式会社テクノマルシチ製コンプレッション成形機）することによって作製し、ＪＩＳ　Ｋ－６９１１　５．７に準拠して成形収縮率を算出する。 (4) Molding shrinkage ratio Compression molding of a shrinking disk (φ 90 mm × 11 mm) defined in JIS K-6911 5.7 under the conditions of a molding temperature of 160 ° C., a molding pressure of 10 MPa and a molding time of 3 minutes (Techno Marushichi Co., Ltd. Manufactured by using a compression molding machine), and the molding shrinkage ratio is calculated in accordance with JIS K-6911 5.7.
（５）曲げ弾性率
　ＪＩＳ　Ｋ－６９１１　５．１７に規定される曲げ弾性率試験片（９０ｍｍ×１０ｍｍ×４ｍｍ）を、成形温度１６０℃、成形圧力１０ＭＰａ、成形時間３分の条件下で圧縮成形（株式会社テクノマルシチ製コンプレッション成形機）することによって作製し、ＪＩＳ　Ｋ－６９１１　５．１７に準拠して曲げ弾性率を測定する。 (5) Flexural modulus The flexural modulus test piece (90 mm × 10 mm × 4 mm) defined in JIS K-6911 5.17 is compression molded at a molding temperature of 160 ° C., a molding pressure of 10 MPa and a molding time of 3 minutes. The compression elastic modulus is measured in accordance with JIS K-6911 5.17.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　１　　成形体
　２　　アンダーコート層
　３　　金属反射層
　４　　光源
　５　　レンズ 1 molded body 2 undercoat layer 3 metal reflective layer 4 light source 5 lens

Claims (6)

  1. 　（ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物であって、
    　前記（ｂ）無機充填材が前記（ａ）不飽和ポリエステル樹脂１００質量部に対して２５０～６００質量部であり、
    　前記（ｂ）無機充填材として、（ｂ１）０．５～５．０μｍの平均粒子径を有する無機充填材と（ｂ２）８．０～５０．０μｍの平均粒子径を有する無機充填材とを、質量比が（ｂ１）：（ｂ２）＝２５：７５～７５：２５となる割合で含む、不飽和ポリエステル樹脂組成物。     An unsaturated polyester resin composition comprising (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcement and (f) curing agent. ,
    The inorganic filler (b) is 250 to 600 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a),
    (B) As the inorganic filler, (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 μm and (b2) an inorganic filler having an average particle diameter of 8.0 to 50.0 μm And an unsaturated polyester resin composition containing a mass ratio of (b1) :( b2) = 25: 75 to 75:25.
  2. 　前記（ｂ）無機充填材が前記（ａ）不飽和ポリエステル樹脂１００質量部に対して３５０～４５０質量部である、請求項１に記載の不飽和ポリエステル樹脂組成物。 The unsaturated polyester resin composition according to claim 1, wherein the (b) inorganic filler is 350 to 450 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
  3. 　前記（ｂ）無機充填材が炭酸カルシウムを含む、請求項１又は２のいずれかに記載の不飽和ポリエステル樹脂組成物。 The unsaturated polyester resin composition according to any one of claims 1 or 2, wherein the inorganic filler (b) contains calcium carbonate.
  4. 　前記（ｅ）繊維強化材が（ａ）不飽和ポリエステル樹脂１００質量部に対して７０～１２０質量部である、請求項１～３のいずれか一項に記載の不飽和ポリエステル樹脂組成物。 The unsaturated polyester resin composition according to any one of claims 1 to 3, wherein the (e) fiber reinforcing material is 70 to 120 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
  5. 　請求項１～４のいずれか一項に記載の不飽和ポリエステル樹脂組成物の硬化物を含む成形体。 A molded article comprising a cured product of the unsaturated polyester resin composition according to any one of claims 1 to 4.
  6. 　請求項５に記載の成形体と、前記成形体上に位置するアンダーコート層と、前記アンダーコート層上に位置する金属反射層とを含むランプリフレクター。 A lamp reflector comprising the molded body according to claim 5, an undercoat layer located on the molded body, and a metal reflection layer located on the undercoat layer.
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