WO2016035516A1

WO2016035516A1 - Unsaturated polyester resin composition, lamp reflector and method for producing same

Info

Publication number: WO2016035516A1
Application number: PCT/JP2015/072645
Authority: WO
Inventors: 審史田村; 俊直三木; 慎太郎山内
Original assignee: 昭和電工株式会社
Priority date: 2014-09-04
Filing date: 2015-08-10
Publication date: 2016-03-10
Also published as: MY186790A; CN106795252A; CN106795252B; JP6590342B2; JPWO2016035516A1

Abstract

This unsaturated polyester resin composition contains (a) an unsaturated polyester resin, (b) a metal soap, (c) a carboxylic acid, (d) an inorganic filler, (e) a shrinkage reducing agent, (f) a fiber reinforcing material and (g) a curing agent. In this unsaturated polyester resin composition, 1-3 parts by mass of the component (b), 5-15 parts by mass of the component (c), 350-550 parts by mass of the component (d), 10-30 parts by mass of the component (e) and 70-120 parts by mass of the component (f) are contained per 100 parts by mass of the component (a). An unsaturated polyester resin composition having the above-described composition is capable of providing a molded body which exhibits excellent coatability of an undercoating agent, mold releasability and fogging properties without performing a removal process of a mold release agent, while having excellent dimensional accuracy and mechanical characteristics.

Description

Unsaturated polyester resin composition, lamp reflector and method for producing the same

The present invention relates to an unsaturated polyester resin composition, a lamp reflector and a method for producing the same. Specifically, the present invention relates to an unsaturated polyester resin composition, a lamp reflector, and a method for producing the same, which are used in the manufacture of a lamp reflector used for an automotive headlamp or the like.

An unsaturated polyester resin composition in which a fiber reinforcement or an inorganic filler is blended with an unsaturated polyester resin has a good moldability and is a cured product with excellent surface smoothness, dimensional accuracy, heat resistance and mechanical strength. Therefore, it is widely used in the manufacture of OA equipment, office equipment chassis, automotive headlamp lamp reflectors and the like.

Among them, in the manufacture of the lamp reflector, after forming an undercoat layer by applying and curing an undercoat agent on the surface of a molded body (base material) obtained by molding and curing an unsaturated polyester resin composition, A metal coating layer (reflection layer) such as aluminum or zinc is formed on the undercoat layer by vapor deposition or the like. Therefore, in addition to the above characteristics, the unsaturated polyester resin composition used for the manufacture of the lamp reflector is also required to give a cured product excellent in the coatability of the undercoat agent.

However, from the viewpoint of releasability, a release agent such as metal soap is generally blended with the unsaturated polyester resin composition. This mold release agent can make the molded body easy to be demolded by bleeding on the surface of the molded body. On the other hand, when applying the undercoat agent to the surface of the molded body, the “repel” of the undercoat agent is removed. There is a problem that the undercoat agent cannot be uniformly applied to the surface of the molded body.
As a means for solving this problem, there is known a method of removing the release agent bleed on the surface of the molded body by cleaning treatment, heat treatment, frame treatment, etc., but such release agent removal treatment is performed by a lamp reflector. This leads to a decrease in manufacturing efficiency and an increase in manufacturing cost.

Therefore, the present applicants previously described an unsaturated polyester resin composition (see Patent Document 1) in which an unsaturated polyester, a specific crosslinking agent, and a low shrinkage agent are blended in a predetermined ratio, and an unsaturated polyester resin. The unsaturated polyester resin composition (refer patent document 2) which mix | blended polybutadiene with predetermined ratio was proposed.

JP 2010-49918 A JP 2011-162748 A

Since the lamp reflector is used under high-temperature conditions near the lamp (heat source), the mold release agent contained in the molded body may sublimate due to the heat of the lamp and may adhere to the lens and cause fogging. . In order to prevent fogging, it is considered necessary to reduce the amount of the release agent contained in the unsaturated polyester resin composition that gives the molded product, but when the amount of the release agent is reduced, the mold release property of the molded product Will fall. Actually, the unsaturated polyester resin compositions of

Patent Documents

1 and 2 contain a release agent to the extent that a desired release property can be obtained. In order to prevent fogging, the molded body is washed. The release agent must be removed by performing removal treatment such as treatment, heat treatment, and frame treatment.
However, since the release agent removal treatment leads to a decrease in the manufacturing efficiency of the lamp reflector and an increase in production cost, not only the paintability of the undercoat agent but also the release properties and There is a need for an unsaturated polyester resin composition that provides a molded article with excellent fogging properties.

The present invention has been made to solve the above-described problems. In addition to the dimensional accuracy and mechanical characteristics, the coating properties of the undercoat agent and the mold release can be achieved without performing the removal treatment of the mold release agent. It aims at providing the unsaturated polyester resin composition which gives the molded object excellent in the property and fogging property. Another object of the present invention is to provide a lamp reflector and a method for manufacturing the same that can increase manufacturing efficiency and reduce manufacturing costs.

As a result of diligent research to solve the above problems, the present inventors have formulated a carboxylic acid instead of reducing the amount of metal soap generally used as a release agent in unsaturated polyester resin compositions. The inventors have found that it is possible to form a molded article having excellent paintability, releasability and fogging properties of the undercoat agent without performing the removal agent removal treatment, and have completed the present invention.
That is, the present invention includes the following (1) to (6).

(1) (a) unsaturated polyester resin, (b) metal soap, (c) carboxylic acid, (d) inorganic filler, (e) low shrinkage agent, (f) fiber reinforcement and (g) curing agent. An unsaturated polyester resin composition comprising (a) component of 100 parts by mass, component (b) of 1 to 3 parts by mass, component (c) of 5 to 15 parts by mass, and component (d) of 350 An unsaturated polyester resin composition characterized in that it is ˜550 parts by mass, component (e) is 10-30 parts by mass, and component (f) is 70-120 parts by mass.
(2) The unsaturated polyester resin composition according to item (1), wherein the (c) carboxylic acid has 10 to 18 carbon atoms.
(3) The (c) carboxylic acid is at least one selected from the group consisting of capric acid, lauric acid, myristic acid, palmitic acid and stearic acid. The unsaturated polyester resin composition according to item 2).
(4) The (b) metal soap is at least one selected from the group consisting of calcium stearate, zinc stearate, aluminum stearate and magnesium stearate, The unsaturated polyester resin composition according to any one of items 3).

(5) A molded body obtained by molding and curing the unsaturated polyester resin composition according to any one of items (1) to (4), and an underlayer formed on the molded body A lamp reflector comprising: a coat layer; and a metal reflective layer formed on the undercoat layer.
(6) forming and curing the unsaturated polyester resin composition according to any one of items (1) to (4) to obtain a molded product;
(B) a step of forming an undercoat layer by applying and curing an undercoat agent on the molded body without performing a metal soap removal treatment;
And a step of forming a metal reflective layer on the undercoat layer.

According to the present invention, in addition to dimensional accuracy and mechanical properties, an unsaturated polyester that provides a molded article excellent in undercoat coating, releasability, and fogging properties without performing a removal agent removal treatment. A resin composition can be provided. Furthermore, according to the present invention, it is possible to provide a lamp reflector and a method for manufacturing the same that can increase productivity and reduce manufacturing costs.

It is sectional drawing of the lamp | ramp provided with the lamp reflector of this invention. It is an expanded sectional view of the aa 'line of FIG. 1a.

The unsaturated polyester resin composition of the present invention comprises (a) an unsaturated polyester resin, (b) a metal soap, (c) a carboxylic acid, (d) an inorganic filler, (e) a low shrinkage agent, and (f) fiber reinforcement. Material and (g) a curing agent. A preferred coating composition in the present invention consists essentially of the components (a) to (g). Here, “essentially” in this specification includes components (a) to (g) as essential components, and can include optional components other than the essential components within a range that does not impair the effects of the present invention. Means.
Hereinafter, each component will be described.

(A) An unsaturated polyester resin generally comprises a condensation product (unsaturated polyester) obtained by an esterification reaction of a polyhydric alcohol, an unsaturated polybasic acid and an arbitrary saturated polybasic acid with a crosslinking agent (“reactive dilution”). It is also referred to as “agent”. Such unsaturated polyester resins are generally known in the art, and include, for example, “Polyester Resin Handbook” (published by Nikkan Kogyo Shimbun, 1988) and “Paint Glossary of Terms” (Edited by Color Material Association, 1993). ) Etc.

The polyhydric alcohol used for the synthesis of the unsaturated polyester is not particularly limited, and those known in the technical field 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, and glycerin. Etc. Among these, propylene glycol, neopentyl glycol, and bisphenol A or hydrogenated bisphenol A are preferable from the viewpoints of heat resistance, mechanical strength, and moldability. These polyhydric alcohols can be used alone or in combination.

It does not specifically limit as unsaturated polybasic acid used for the synthesis | combination of unsaturated polyester, A well-known thing can be used in the said technical field. 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. Among these, maleic anhydride and fumaric acid are more preferable from the viewpoints of heat resistance, mechanical strength, moldability, and the like.
It does not specifically limit as a saturated polybasic acid used for the synthesis | combination of unsaturated polyester, A well-known thing can be used. Examples of saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, het acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endomethylenetetrahydrophthalic anhydride, etc. Can be mentioned. These can be used alone or in combination.

The unsaturated polyester can be synthesized by a known method using the above raw materials. Various conditions in this synthesis need to be set as appropriate according to the raw material used and the amount thereof. In general, the pressure is increased or decreased at a temperature of 140 to 230 ° C. in an inert gas stream such as nitrogen gas. What is necessary is just to esterify below. In this esterification reaction, an esterification catalyst can be used as needed. Examples of the catalyst include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate. These can be used alone or in combination.

The weight average molecular weight (MW) of the unsaturated polyester is not particularly limited, but is preferably 5,000 to 20,000. In this specification, “weight average molecular weight” is measured at normal temperature (23 ° C.) under the following conditions using gel permeation chromatography (Shodex GPC-101, Showa Denko KK), and a standard polystyrene calibration curve. It means the value obtained using.
Column: Showa Denko LF-804
Column temperature: 40 ° C
Sample: 0.2% by mass tetrahydrofuran solution of copolymer Flow rate: 1 mL / min Eluent: Tetrahydrofuran Detector: RI-71S

(A) The crosslinking agent used in the unsaturated polyester resin is not particularly limited as long as it has an ethylenic double bond polymerizable with the unsaturated polyester, and those known in the technical field are used. be able to. 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.
(A) Although the compounding quantity of the crosslinking agent in unsaturated polyester resin is not specifically limited, From a viewpoint of workability | operativity, polymerizability, the shrinkage | contraction property of a molded object, and the freedom degree of quantity adjustment, it is the sum total of unsaturated polyester and a crosslinking agent. On the other hand, it is preferably 25 to 70% by mass, more preferably 35 to 65% by mass.

(B) Metal soap is a component generally used as a release agent in the technical field. (B) It does not specifically limit as a metal soap, A well-known thing can be used in the said technical field. (B) Examples of the metal soap include calcium stearate, zinc stearate, aluminum stearate, magnesium stearate and the like. These can be used alone or in combination.

(B) The blending amount of the metal soap is 1 to 3 parts by mass, preferably 1 to 2.5 parts by mass, more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. By using a combination of a predetermined amount of (c) carboxylic acid together with such a smaller blending amount of (b) metal soap than in the past, mold release properties and fogging properties can be obtained without removing the release agent. It is possible to produce an unsaturated polyester resin composition that gives a molded article having both the coatability of the undercoat agent. (B) When the compounding amount of the metal soap is less than 1 part by mass, the component as a release agent is insufficient, and the mold release property of the molded article is lowered. On the other hand, if the blending amount of (b) metal soap exceeds 3 parts by mass, the amount of the component as a mold release agent is too much, and (b) metal soap bleeds on the surface of the molded body. Therefore, in order to obtain a molded article having desired fogging properties and paintability of the undercoat agent, (b) metal soap must be removed.

(C) Carboxylic acid is a component blended instead of reducing the blending amount of (b) metal soap. (C) By blending carboxylic acid, the releasability does not decrease even if the blending amount of (b) metal soap is reduced, and the coatability of the undercoat agent is not required even if the release agent is not removed. In addition, a molded article excellent in fogging property can be obtained.
(C) As the carboxylic acid, an aliphatic carboxylic acid is preferable from the viewpoint of stably obtaining the above effects. Further, (c) the carboxylic acid preferably has 10 to 18 carbon atoms. (C) Examples of carboxylic acids include capric acid (10 carbon atoms), undecyl acid (11 carbon atoms), lauric acid (12 carbon atoms), tridecyl acid (13 carbon atoms), myristic acid (14 carbon atoms), Examples include pentadecylic acid (15 carbon atoms), palmitic acid (16 carbon atoms), margaric acid (17 carbon atoms), and stearic acid (18 carbon atoms). Among these, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid are preferable from the viewpoint of releasability, fogging properties, and undercoat coating properties. These can be used alone or in combination.

(C) The blending amount of the carboxylic acid is 5 to 15 parts by mass, preferably 6 to 13 parts by mass, more preferably 8 to 12 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. By using a combination of (c) carboxylic acid in such a blending amount and (b) a metal soap in a blending amount smaller than that in the past, mold release properties and fogging properties can be obtained without performing a release agent removal treatment. It is possible to produce an unsaturated polyester resin composition that gives a molded article having both the coatability of the undercoat agent. When the blending amount of (c) carboxylic acid is less than 5 masses, the amount of (c) carboxylic acid is insufficient, and the mold releasability of the molded product is lowered. On the other hand, when the compounding amount of (c) carboxylic acid exceeds 15 parts by mass, the mechanical properties of the molded article deteriorate.

(D) The inorganic filler is not particularly limited, and those known in the technical field can be used. (D) Examples of the inorganic filler include silica, alumina, calcium carbonate, aluminum hydroxide, barium sulfate, wollastonite, clay, talc, mica, gypsum, anhydrous silicic acid, glass powder and the like. In addition, from the viewpoint of reducing the specific gravity of the molded body, a hollow filler such as a glass balloon, a silica balloon, or an alumina balloon may be used as the inorganic filler (d). These can be used alone or in combination.

(D) The average particle size of the inorganic filler is not particularly limited, but is preferably 0.5 μm to 15 μm or less, more preferably 0.7 μm to 10 μm. (D) When the average particle diameter of the inorganic filler is less than 0.5 μm, the viscosity of the unsaturated polyester resin composition may increase and the moldability may decrease. On the other hand, when the average particle diameter of (d) inorganic filler exceeds 15 μm, the surface smoothness and mechanical strength of the molded product are remarkably lowered, or the fluidity of the unsaturated polyester resin composition is lowered, and the moldability is reduced. May decrease.
Here, in the present specification, (d) “average particle diameter” of the inorganic filler means a particle diameter obtained by calculation from a specific surface area obtained by an air permeation method.
Average particle diameter = (6 × 10000) / (true specific gravity × specific surface area)

(D) The blending amount of the inorganic filler is 350 to 550 parts by mass, preferably 370 to 530 parts by mass, more preferably 400 to 500 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (D) When the compounding amount of the inorganic filler is less than 350 parts by mass, the mechanical properties of the molded article are deteriorated. On the other hand, if the blending amount of (d) inorganic filler exceeds 550 parts by mass, (d) inorganic filler is not uniformly dispersed in the unsaturated polyester resin composition, and a homogeneous molded body cannot be produced. .

(E) The low shrinkage agent is not particularly limited, and those known in the technical field 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, and styrene-butadiene rubber. These can be used alone or in combination of two or more.

(E) The compounding amount of the low shrinkage agent is 10 to 30 parts by mass, preferably 12 to 28 parts by mass, more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (E) When the blending amount of the low shrinkage agent is less than 10 parts by mass, the shrinkage rate of the molded body increases, and desired dimensional accuracy cannot be obtained. On the other hand, when the compounding amount of (e) the low shrinkage agent exceeds 30 parts by mass, the mechanical properties of the molded article deteriorate.

(F) The fiber reinforcing material is not particularly limited, and those known in the technical field can be used. (F) Examples of the fiber reinforcement include various organic fibers and inorganic fibers such as glass fiber, pulp fiber, polyethylene terephthalate fiber, vinylon fiber, carbon fiber, aramid fiber, and wollastonite. Among them, it is preferable to use chopped strand glass cut to a fiber length of about 1.5 to 25 mm.

(F) The compounding amount of the fiber reinforcement is 70 to 120 parts by mass, preferably 75 to 115 parts by mass, more preferably 70 to 110 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. (F) When the compounding amount of the fiber reinforcing material is less than 70 parts by mass, the mechanical properties of the molded article deteriorate. On the other hand, when the blending amount of (f) fiber reinforcement exceeds 120 parts by mass, (f) fiber reinforcement is not uniformly dispersed in the unsaturated polyester resin composition, and a homogeneous molded body cannot be produced. .

(G) The curing agent is not particularly limited, and those known in the technical field can be used. (G) Examples of curing agents include t-butyl peroxy octoate, benzoyl peroxide, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane, t-butyl peroxyisopropyl carbonate Organic peroxides such as t-butyl peroxybenzoate, dicumyl peroxide, and di-t-butyl peroxide. These can be used alone or in combination of two or more.

(G) The blending 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 (g) is preferably 0.5 to 10 parts by mass, more preferably 0.7 to 7 parts by mass, and further preferably 1 to 5 parts per 100 parts by mass of the (a) unsaturated polyester resin. Part by mass.

The unsaturated polyester resin composition of the present invention may contain, in addition to the above-described components, components known in the art such as thickeners, pigments, and thickeners in a range that does not impair the effects of the present invention. it can.
Although it does not specifically limit as a thickener, For example, metal oxides, such as magnesium oxide, magnesium hydroxide, calcium hydroxide, calcium oxide, an isocyanate compound, etc. are mentioned. These can be used alone or in combination of two or more.

The unsaturated polyester resin composition of the present invention containing the above components can be produced by kneading using a method usually performed in the technical field, for example, a kneader.

The unsaturated polyester resin composition of the present invention produced as described above has a reduced amount of (b) metal soap generally used as a release agent in the unsaturated polyester resin composition. ) Since a predetermined amount of carboxylic acid is blended, the mold release property is good, and it is possible to give a molded article excellent in the coatability and fogging property of the undercoat agent without performing the removal treatment of the mold release agent. it can. In addition, the unsaturated polyester resin composition of the present invention contains (d) an inorganic filler, (e) a low shrinkage agent, and (f) a fiber reinforcement in a predetermined ratio, so that dimensional accuracy and mechanical properties are obtained. It is possible to provide an excellent molded product.

The unsaturated polyester resin composition of the present invention can be molded into a desired shape and cured to produce a molded product. The molding and curing method is not particularly limited, and a method usually performed in the technical field, for example, compression molding, transfer molding, injection molding, or the like can be used.

The molded product obtained from the unsaturated polyester resin composition of the present invention is suitable for use as a base material for a lamp reflector.
The lamp reflector generally includes a molded body (base material) obtained by molding and curing an unsaturated polyester resin composition, an undercoat layer formed on the molded body, and a metal formed on the undercoat layer. And a reflective layer.
Hereinafter, a preferred embodiment of a lamp reflector will be described with reference to the drawings.
FIG. 1 a is a cross-sectional view of a lamp provided with the lamp reflector of the present embodiment. FIG. 1b is an enlarged cross-sectional view taken along the line aa ′ of FIG. 1a.
In FIG. 1a, a lamp generally includes a lamp reflector, a light source 4 provided at a predetermined position of the lamp reflector, and a lens 5 provided at an opening of the lamp reflector. Here, as shown in FIG. 1b, the lamp reflector includes a molded body 1 obtained by molding and curing an unsaturated polyester resin composition, an undercoat layer 2 formed on the molded body 1, and an undercoat. And a metal reflective layer 3 formed on the layer 2. In this lamp, the light generated from the light source 4 is reflected by the metal reflection layer 3.

The lamp reflector having such a configuration can be manufactured as follows.
First, the unsaturated polyester resin composition of the present invention is molded and cured to obtain a molded body 1. Here, the molded body 1 can be obtained by molding and curing the unsaturated polyester resin composition of the present invention into a predetermined shape using a known molding method such as compression molding, transfer molding, or injection molding. The molded body 1 thus obtained is excellent in the coating properties and fogging properties of the undercoat agent without performing the release agent removal treatment.

Next, an undercoat layer 2 is formed by applying and curing an undercoat agent on the molded body 1 without performing a removing agent removal treatment. Here, in the conventional lamp reflector manufacturing method, it is necessary to remove the release agent bleed on the surface of the molded body 1 in order to solve the problem of “repellency” of the undercoat agent and fogging property. On the other hand, in the present invention, since the amount of the release agent that bleeds to the surface of the molded body 1 is reduced by reducing the amount of the release agent, There is no need to perform removal processing. As a result, the manufacturing efficiency of the lamp reflector can be increased and the manufacturing cost of the lamp reflector can be reduced.

The undercoat agent that gives the undercoat layer 2 is not particularly limited, and those known in the technical field 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 UV curable resins and thermosetting resins include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate. Examples include acrylic resins obtained by homopolymerization or copolymerization of functional monomers. The resin composition may also contain a polyester resin such as an unsaturated polyester resin, a vinyl-modified polyester resin, a phenol-modified polyester resin, an oil-modified polyester resin, or a silicone-modified polyester resin, a curing agent, a solvent, and the like.

The method for applying the undercoat agent onto the molded body 1 is not particularly limited, and for example, a known method such as an air spray method or an airless spray method can be used. Also, the curing method is not particularly limited, and may be appropriately selected according to the type of the undercoat agent.
The thickness of the undercoat layer 2 may be appropriately set in accordance with the required size of the lamp reflector, but is generally 10 to 50 μm.

Next, the metal reflective layer 3 is formed on the undercoat layer 2. It does not specifically limit as a material of the metal reflective layer 3, A well-known thing can be used in the said technical field. Examples of the material of the metal reflection layer 3 include aluminum, silver, zinc, an alloy mainly composed of silver and zinc, and the like.
The method for forming the metal reflective layer 3 on the undercoat layer 2 is not particularly limited, and for example, a known method such as a vacuum deposition method can be used.
The thickness of the metal reflective layer 3 may be appropriately set according to the required size of the lamp reflector, but is generally 800 to 2,000 mm.

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 can be used. The method of providing the light source 4 and the lens 5 is not particularly limited, and can be performed according to a known method.
The lamp reflector of this embodiment manufactured in this way has high manufacturing efficiency and low manufacturing cost.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these.
(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 an acid value of 20 mgKOH / The reaction was continued until 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 so that it might become 30 mass% in unsaturated polyester resin. Moreover, it was 15,000 when the weight average molecular weight (MW) of unsaturated polyester was measured on said conditions.

(Examples 1 to 13)
Each component was charged with the composition shown in Table 1, and an unsaturated polyester resin composition was obtained by kneading using a double-type kneader. In addition, (a) unsaturated polyester resin shown in Table 1 and 2 contains 30 mass% of styrene monomers.
(Comparative Examples 1 to 10)
Each component was charged with the composition shown in Table 2, and an unsaturated polyester resin composition was obtained by kneading using a double-type kneader.
In the above Examples and Comparative Examples, (b) (b-1) zinc stearate and (b-2) calcium stearate as metal soap, (c) carboxylic acid (c-1) lauric acid, (c-2) ) Capric acid and (c-3) stearic acid, (d) calcium carbonate (average particle size 10 μm) as inorganic filler, (e) polystyrene as low shrinkage agent, (f) chopped strand glass (fiber length) 6 mm), (g) t-butyl peroxybenzoate as a curing agent, and magnesium oxide as a thickener.
The unsaturated polyester resin compositions of Examples and Comparative Examples obtained as described above were evaluated for kneading property, mold release property, undercoat agent coating property, fogging property, molding shrinkage rate and bending elastic modulus. It was. These evaluation methods are as follows.

(1) Kneadability When an unsaturated polyester resin composition is prepared by kneading using a double-type kneader, whether or not a uniform unsaturated polyester resin composition having no poor dispersion is obtained is visually evaluated. did. In this evaluation, the case where the unsaturated polyester resin composition is uniform is represented by ◯, and the case where the unsaturated polyester resin composition has poor dispersion is represented by x.

(2) Releasability Transfer molding was carried out under conditions of a molding temperature of 150 ° C., an injection pressure of 20 MPa, and a molding time of 1 minute to produce a transfer molded body (φ117 mm, thickness 3 mm). At this time, it was visually evaluated whether or not the transfer molded body remained in the mold and the transfer molded body could be smoothly removed from the mold. In this evaluation, the case where the transfer molded body did not remain and the transfer molded body could be smoothly removed from the mold was ○, and the transfer molded body remained and the transfer molded body could not be removed smoothly from the mold. The case is represented as x.

(3) Paintability of undercoat agent Transfer molding was carried out under the conditions of a molding temperature of 150 ° C., an injection pressure of 20 MPa, and a molding time of 1 minute to produce a transfer molded body (φ117 mm, thickness 3 mm). Next, an undercoat layer (resin composition containing a UV curable resin) was applied to the surface of the transfer molded body so as to have a thickness of 10 μm and cured to form an undercoat layer. At this time, a portion with good coating (portion without repelling) in the entire coating portion of the undercoat agent was visually confirmed, and the ratio of the area was determined. In this evaluation, the case where the area ratio of the part with good coating is 95% or more is represented by ◯, and the case where the area ratio of the part with good coating is less than 95% is represented by x.

(4) Fogging property Transfer molding was carried out under conditions of a molding temperature of 150 ° C., an injection pressure of 20 MPa, and a molding time of 1 minute to produce a transfer molded body (φ117 mm, thickness 3 mm). A 40 mm square sample was cut out from the transfer molded body and placed in a glass petri dish, and the mouth of the glass petri dish was covered with aluminum foil and rubber and completely sealed. Next, a glass petri dish was placed on a hot plate set at 180 ° C. with the aluminum foil side down, and heated for 12 hours. The haze value of the glass petri dish before and after this heat treatment was measured using a haze meter (Hazeguard II manufactured by Toyo Seiki Seisakusho), and the difference in haze values before and after this heat treatment (Δhaze value) was determined. A case where the Δhaze value is 1 or less is represented by “◯”, and a case where the Δhaze value is more than 1 are represented by “×”.

(5) Molding Shrinkage Ratio A shrinking disk specified in JIS K-6911 5.7 was produced by compression molding under conditions of a molding temperature of 150 ° C., a molding pressure of 10 MPa, and a molding time of 3 minutes, and JIS K-6911. The molding shrinkage was calculated according to 5.7.

(6) Bending elastic modulus A bending elastic modulus test piece specified in JIS K6911 is produced by compression molding under conditions of a molding temperature of 150 ° C., a molding pressure of 10 MPa, and a molding time of 3 minutes, and bent according to JIS K6911. The elastic modulus was measured.

Regarding the above evaluation results, the results of Examples are shown in Table 1, and the results of Comparative Examples are shown in Table 2, respectively. In addition, in the comparative example, about (1) kneading | mixing property or (2) releasability evaluation was x, subsequent evaluation was not performed.

As can be seen from the results in Tables 1 and 2, the unsaturated polyester resin compositions of Examples 1 to 13 containing the components (a) to (g) in a predetermined ratio are kneadable, mold release properties, and undercoat agents. The coating properties, fogging properties, molding shrinkage rate and flexural modulus were all excellent.
On the other hand, in the unsaturated polyester resin composition of Comparative Example 1 that does not contain the component (b), the releasability is lowered, and in the unsaturated polyester resin composition of Comparative Example 2 in which the proportion of the component (b) is large, fogging is performed. And paintability of the undercoat agent decreased. (C) In the unsaturated polyester resin composition of Comparative Example 3 with a small proportion of component, the releasability is lowered, and in the unsaturated polyester resin composition of Comparative Example 4 with a large proportion of (c) component, the flexural modulus is lowered. did. In the unsaturated polyester resin composition of Comparative Example 5 having a small proportion of the component (d), the flexural modulus was lowered, and in the unsaturated polyester resin composition of Comparative Example 6 having a large proportion of the component (d), the kneadability was lowered. . In the unsaturated polyester resin composition of Comparative Example 7 in which the proportion of component (e) is small, the molding shrinkage is reduced, and in the unsaturated polyester resin composition of Comparative Example 8 in which the proportion of component (e) is large, the flexural modulus is lowered. did. The flexural modulus decreased in the unsaturated polyester resin composition of Comparative Example 9 having a small proportion of the component (f), and the kneadability decreased in the unsaturated polyester resin composition of Comparative Example 10 having a large proportion of the component (f). .

Considering the above results, in order to improve all of kneadability, mold release property, undercoat agent coating property, fogging property, molding shrinkage rate and bending elastic modulus, the components (a) to (g) are added. It is considered necessary to control to a predetermined ratio.

As can be seen from the above results, according to the present invention, in addition to the dimensional accuracy and mechanical properties, the undercoat agent is excellent in paintability, releasability and fogging properties without performing the removal agent removal treatment. It is possible to provide an unsaturated polyester resin composition that gives a molded product. Furthermore, according to the present invention, it is possible to provide a lamp reflector and a method for manufacturing the same that can increase productivity and reduce manufacturing costs.

Note that this international application claims priority based on Japanese Patent Application No. 2014-180303 filed on September 4, 2014, and the entire contents of this Japanese patent application are incorporated herein by reference. To do.

1 molded body, 2 undercoat layer, 3 metal reflective layer, 4 light source, 5 lens.

Claims

Unsaturation comprising (a) unsaturated polyester resin, (b) metal soap, (c) carboxylic acid, (d) inorganic filler, (e) low shrinkage agent, (f) fiber reinforcement and (g) curing agent. A polyester resin composition comprising:
(A) 1 to 3 parts by mass of component (b), 5 to 15 parts by mass of component (c), 350 to 550 parts by mass of component (d), and 10 parts of component (e) with respect to 100 parts by mass of component (a) An unsaturated polyester resin composition, characterized in that it is ˜30 parts by mass and the component (f) is 70 to 120 parts by mass.
2. The unsaturated polyester resin composition according to claim 1, wherein the (c) carboxylic acid has 10 to 18 carbon atoms.
The unsaturated polyester according to claim 1 or 2, wherein the (c) carboxylic acid is at least one selected from the group consisting of capric acid, lauric acid, myristic acid, palmitic acid and stearic acid. Resin composition.
The metal soap (b) is at least one selected from the group consisting of calcium stearate, zinc stearate, aluminum stearate, and magnesium stearate, according to any one of claims 1 to 3. The unsaturated polyester resin composition as described.
A molded body obtained by molding and curing the unsaturated polyester resin composition according to any one of claims 1 to 4, an undercoat layer formed on the molded body, and the undercoat layer And a metal reflecting layer formed on the lamp reflector.
Molding and curing the unsaturated polyester resin composition according to any one of claims 1 to 4 to obtain a molded body;
(B) a step of forming an undercoat layer by applying and curing an undercoat agent on the molded body without performing a metal soap removal treatment;
And a step of forming a metal reflective layer on the undercoat layer.