JP4934368B2 - Press molding material including phosphorescent material and press molded product thereof - Google Patents

Description

The present invention relates to a press molding material including a phosphorescent material and a press molded product thereof. More specifically, the present invention relates to a press molding material including a phosphorescent material suitably used in various fields such as transportation, buildings, furniture, and signs, and a press molded product thereof.

Molding material is a molding compound that is usually used for molding such as compression molding in a closed mold, and has excellent productivity, surface properties, strength, lightness, water resistance, corrosion resistance, and dimensional stability. Volatile organic compounds (VOC) are also reduced. Such molding materials are widely used in various fields such as floor pans, waterproof pans, counters, vehicle parts, ships, flooring materials, wall materials, bathtubs (tubs), road traffic signs, and the like.
While maintaining the properties of molding compounds as described above, by providing a better appearance, night visibility, afterglow brightness, and afterglow time, vehicle applications, signage applications, and architectures that require such characteristics. It can be suitably used for internal use and external use of objects. That is, there is a strong demand to further improve the appearance, night visibility, afterglow luminance, and afterglow time while maintaining the above-described characteristics.

In order to overcome such problems, many methods using phosphorescent materials have been proposed. For example, a thermosetting resin composition is blended with a filler, a curing agent, and a phosphorescent material, and artificial marble is manufactured by casting. Is disclosed (for example, see Patent Document 1). However, the reinforcing fiber is not used in the phosphorescent material blend layer, and there are many uses that cannot be adopted due to insufficient strength, and there is room for improvement in the afterglow luminance and the afterglow time.

In addition, a molded body comprising two layers of an outer layer and an inner layer, a phosphorescent phosphor is blended in the outer layer, and titanium oxide is blended in the inner layer is disclosed (for example, see Patent Document 2). . It is said that the light emitted from the phosphorescent phosphor to the inner layer side is reflected by the inner layer surface and increases the amount of light emitted to the outside. Was manufactured. Furthermore, a luminescent flooring material is disclosed in which a luminescent pigment is added to a surface layer of 3 layers of thermoplastic resin in an amount of 5 to 300% by mass with respect to 100 parts by mass of the surface layer resin (see, for example, Patent Document 3). . Although it is said that the persistence of a high afterglow can be exhibited, the molded body was manufactured by calendar molding. And the granular luminous material composition formed by putting a phosphorescent pigment into the resin which does not melt at the molding temperature of the thermoplastic resin to be molded, curing it, and pulverizing it to 10 to 1000 μm is disclosed (for example, see Patent Document 4). ). Although it is supposed that the deterioration of afterglow luminance is suppressed and the cost and the appearance of the molded product are excellent, in the examples, what is molded by casting is described. In these molded objects, there was room for improvement in terms of maintaining physical properties such as strength.

Further, a bathtub is disclosed in which a coating layer containing a phosphorescent material is sandwiched between a transparent resin layer disposed on the front surface side and an FRP backup layer disposed on the back surface side (for example, Patent Documents). 5). It is said that a bathtub that emits light for a certain time in the dark has been obtained, but the surface layer containing the phosphorescent material is not made of reinforcing fibers, but is molded by vacuum molding and hand lay-up molding, and the appearance, cost, There has been a demand for improving physical properties such as strength, afterglow luminance, and afterglow time.

Furthermore, an artificial stone having nocturnal or luminous properties obtained by coating a base material with a phosphorescent pigment, or a building or furniture material made of artificial stone is disclosed (for example, see Patent Documents 6 and 7). It is said that a high-density artificial stone with excellent light characteristics such as nocturnal properties and excellent color tone was obtained. And the light emitting film | membrane coating | coated article which laminated | stacked the 1st layer which made the transparent resin matrix contain the luminous substance etc. in the base-material surface, and the 2nd layer which contained the luster pigment in the transparent resin matrix is disclosed. For example, see Patent Document 8). It is said that the glitter can be improved by combining a glitter pigment in addition to a phosphorescent substance or the like. However, these molded products have room for improvement when applied to other properties such as cost, dimensional accuracy of molded products, physical properties such as the amount of volatile organic substances, and the like.
JP 2000-158457 A (page 1-5) JP 2004-314487 A (1-3, pages 5-7) JP 10-1114030 A (pages 1 and 4-5) JP 2004-182841 A (pages 1, 3 and 6) JP 2006-6603 A (pages 1-2, 5-6) International Publication No. 98/35919 Pamphlet (6th, 12-13, 18-19) JP-A-11-296116 (page 1-3) JP 2004-122772 (pages 1-4 and 14-16)

The present invention has been made in view of the above situation, and a molded product obtained by press-molding a molding material containing a specific phosphorescent material has productivity, surface properties, strength, dimensional stability, It is a molded product with good appearance, nighttime visibility, afterglow brightness, and afterglow time while maintaining excellent physical properties at low VOC, so it can be used for vehicles, signage displays, outdoor use, indoors where nighttime visibility is required. It is an object of the present invention to provide a molding material useful for various fields such as a use, a wall material of a building such as a hospital at the time of disaster, and the like, and a molded product thereof.

The inventors of the present invention have studied various molding materials used for various applications, and the thermosetting resin composition containing a polymerizable oligomer and a polymerizable monomer has productivity, surface properties, strength, lightness, Attention was first focused on excellent performance such as water resistance, corrosion resistance, dimensional stability, and low VOC. And such a molding material contains a specific amount of thermosetting resin, polymerizable unsaturated monomer, filler, glass fiber of a specific fiber length and a phosphorescent material of a specific longest diameter with respect to the total amount of the molding material. If so, it has been found that a molded product having good appearance, night-time visibility, afterglow luminance, and afterglow time can be obtained while maintaining the above performance. As a result, it is possible to obtain molded products that can be used in various fields such as vehicle use, sign display use, outdoor use, indoor use, and wall materials for buildings such as hospitals in the event of a disaster. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a molding material for obtaining a phosphorescent molded product by press molding. When the total amount of the molding material is 100 parts by mass, the thermosetting resin (A) is 5 to 20 parts by mass, polymerizable non-polymerizable. 5-20 parts by mass of saturated monomer (B), 10-70 parts by mass of filler (C), 5-50 parts by mass of glass fiber (D) having a fiber length of 2-50 mm, and the longest diameter of 0.05-10 mm This is a molding material containing 0.1 to 20 parts by mass of the phosphorescent material (E) as an essential component.
The present invention is described in detail below.

The molding material of this invention specified the mass part of each of a thermosetting resin (A), a polymerizable unsaturated monomer (B), a filler (C), a glass fiber (D), and a luminous material (E). Including things.
First, it will be described that specific amounts of these raw materials are included. The technical significance of specifying these numerical ranges is clear from the technical common sense in the technical field of the molding material of the present invention and the results of implementation according to the examples described later.

The said thermosetting resin (A) is contained in 5-20 mass parts in a molding material. If the amount is less than 5 parts by mass, the strength is not sufficiently exhibited, and the wettability of (C), (D), and (E) is lowered. When the amount exceeds 20 parts by mass, the input amounts of (C), (D), and (E) are limited, and the role of each is not sufficiently exhibited. The preferred lower limit is 8% by mass and the upper limit is 18% by mass, the more preferred lower limit is 10% by mass, and the upper limit is 15% by mass.

The polymerizable unsaturated monomer (B) is contained in 5 to 20 parts by mass in the molding material. When the amount is less than 5 parts by mass, the viscosity is high, so that the workability may not be excellent. If it exceeds 20% by mass, the curability may not be improved, and the amount of residual monomer increases, resulting in an increase in the amount of emission from the molded body, the Building Standards Act, etc. There is a risk that it will not be able to fully meet the laws and regulations. The preferred lower limit is 6% by mass and the upper limit is 15% by mass, the more preferred lower limit is 8% by mass, and the upper limit is 12% by mass.

The filler (C) is included in the molding material in an amount of 10 to 70 parts by mass.
If it is less than 10 parts by mass, cracks are likely to occur during molding. When it exceeds 70 mass parts, the viscosity of a resin composition will become high and it will become impossible to work efficiently.
The glass fiber (D) is contained in 5 to 50 parts by mass in the molding material. By setting it within the above range, afterglow luminance can be improved. If it is less than 5 mass parts, the improvement of the afterglow brightness | luminance by the reflection is not enough. When it exceeds 50 mass parts, the wettability of glass will fall, and it will not open to a filament unit, but the reflected light will fall. The glass fiber (D) is preferably contained in an amount of 10 to 30% by weight with respect to 100 parts by mass of the molding material.

The phosphorescent material (E) is included in the molding material in an amount of 0.1 to 20 parts by mass. If it is less than 0.1, the nighttime visibility is not sufficiently exhibited, and if it exceeds 20, the nighttime visibility is not improved any more, and the production as a molding material becomes difficult.

Although it does not specifically limit as said thermosetting resin (A), Unsaturated polyester, vinyl ester, an acrylic resin, etc. are preferable.
The unsaturated polyester is synthesized by an addition reaction or dehydration condensation reaction of an α, β-olefin unsaturated dicarboxylic acid or anhydride thereof and glycol. Further, saturated dicarboxylic acids, aromatic dicarboxylic acids or anhydrides thereof, or dicyclopentadiene that reacts with carboxylic acids can be used in combination. The combined use of dicyclopentadiene is preferred in terms of water resistance, transparency and colorability. Examples of the α, β-olefin unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of these dicarboxylic acids. Among these, maleic acid and fumaric acid are preferable in terms of reactivity. Examples of the dicarboxylic acid used in combination with these α, β-olefinic unsaturated dicarboxylic acids include adipic acid, sebacic acid, succinic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexa Examples include hydrophthalic acid and tetrachlorophthalic acid. Among these, isophthalic acid and / or terephthalic acid are preferable in terms of water resistance and corrosion resistance.

As the glycol, at least one of the following glycols can be used. As the diol, for example, alkanediol, oxaalkanediol, hydrogenated bisphenol A, diol obtained by adding ethylene oxide or propylene oxide to bisphenol A, or a hydrogenated product thereof is used. In addition to this, monool or triol may be used. Examples of the alkanediol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol and cyclohexanediol. Examples of the oxaalkanediol include diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. Examples of monools or triols used in combination with these glycols include octyl alcohol, oleyl alcohol, and trimethylolpropane. Among these, it is preferable to use at least one of hydrogenated bisphenol A or an adduct of bisphenol A and ethylene oxide or propylene oxide from the viewpoint of water resistance, transparency, colorability and the like.

The synthesis of the unsaturated polyester is generally carried out under heating, and the reaction proceeds while removing by-product water. In the present invention, those having a number average molecular weight of 800 to 10,000 and an ester acid value of 5 to 50 mg / KOH are usually used. In the production of the molding material, it is usually used as an unsaturated polyester resin in which an unsaturated polyester is dissolved in a polymerizable unsaturated monomer (B) shown below. Although this invention can be implemented with one type of unsaturated polyester resin, it can also be implemented by blending two or more types of unsaturated polyester resins.

The epoxy (meth) acrylate used for the vinyl ester (epoxy (meth) acrylate) is usually a polymer obtained by a reaction between an epoxy resin and an unsaturated monocarboxylic acid.
As the epoxy resin, a compound having at least two epoxy groups in one molecule can be used. Specifically, polyglycidyl ether of polyhydric phenol or polyhydric alcohol, epoxy novolac, epoxidized diolefin, fatty acid Epoxidized products of the above, epoxidized products of drying oil, etc.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, and derivatives thereof. These exemplary compounds may be used alone or in combination of two or more. If necessary, other monobasic acids and / or polybasic acids may be added for modification.

The acrylic resin can be obtained by mixing a polymerizable monomer with a polymer of (meth) acrylic acid ester such as methyl methacrylate, such as (meth) acrylic acid ester monomer such as methyl methacrylate. A resin (acrylic syrup) dissolved in a polymerizable monomer is preferable. Moreover, in order to raise heat resistance, polyfunctional vinyl monomers, such as ethylene glycol dimethacrylate and a trimethylol propane trimethacrylate, can also be used, and the polymerizable monomer mentioned above can also be used.
In order to introduce an acid or epoxy functional group into the polymer, the acrylic resin is obtained by copolymerizing acrylic acid or glycidyl methacrylic acid, or further reacting with the functional group to give a polymerizable functional group. It is also possible to use a polymer obtained by copolymerizing a monomer such as a polymer or styrene other than acrylic.

As the polymerizable unsaturated monomer (B) used in the molding material of the present invention, at least one monofunctional vinyl monomer is used. Examples of monofunctional vinyl monomers include aromatic monomers such as styrene, p-chlorostyrene, and vinyl toluene, and acrylic monomers such as acrylic acid, acrylic acid methyl ester, methacrylic acid, methacrylic acid methyl ester, and acrylonitrile. Is mentioned. The polymerizable unsaturated monomer is charged into the formulation as a crosslinkable monomer of the thermosetting resin (A), but can also be added as a diluent to the molding material formulation of the present invention.

Moreover, a polyvalent polymerizable unsaturated monomer can also be used in combination as the polymerizable unsaturated monomer (B). Examples of the polyvalent polymerizable unsaturated monomer include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neo Pentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexane Diol diacrylate, trimethylol propane dimethacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, trimethylol prop It can be exemplified dimethacrylate or diacrylate of alkane polyols having 2 to 12 carbon atoms such as diacrylate. One kind of the polymerizable unsaturated monomer (B) may be used, or two or more kinds of polymerizable unsaturated monomers may be blended and used.

Furthermore, as the polyvalent polymerizable unsaturated monomer, C3-C12 such as trimethylolpropane trimethacrylate, glycerin trimethacrylate, dipentaerythritol hexamethacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. Examples thereof include polymethacrylates or polyacrylates of alkane polyols.

The filler (C) in the present invention is usually an inorganic filler, and for example, calcium carbonate, aluminum hydroxide, and glass frit are typically used. The average particle size of the filler (C) is preferably 5 to 50 microns. Furthermore, those surface-treated with a surface modifier such as a silane coupling agent or a titanium coupling agent can be preferably used.
The filler (C) in the molding material of the present invention preferably contains aluminum hydroxide and / or glass frit.
The filler (C) in the molding material of the present invention is preferred because aluminum hydroxide and / or glass frit improves transparency and improves brightness.
The aluminum hydroxide and / or glass frit is a cured product obtained by curing a material containing a thermosetting resin (A), a polymerizable unsaturated monomer (B), a glass fiber (D) and other additives. It is preferable to adjust the addition amount of the filler (C) and the refractive index of the matrix so that the light transmittance is 10% or more.

The glass fiber (D) in the present invention has a fiber length of 2 to 50 mm.
If the fiber length is shorter than 2 mm, the afterglow blurs light due to the influence of irregular reflection and the like, and visibility decreases. When it is longer than 50 mm, dispersion is poor and light becomes uneven.
The fiber length is preferably 6 to 26 mm.
The diameter of the glass fiber (D) is preferably about 8 to 20 μm.
When the diameter of the glass fiber (D) is less than 8 μm, when the molding material is press-molded, the fluidity in the mold is lowered, which may be undesirable. When it exceeds 20 μm, the glass filament is exposed on the surface of the cured product, and smoothness may be impaired.

The phosphorescent material (E) in the molding material of the present invention has a longest diameter of 0.05 to 10 mm.
In the method of directly adding 2 to 100 μm of the luminous pigment, the pigment is uniformly dispersed. An object of the present invention is to localize a pigment on a base material so as to concentrate light and improve nighttime visibility even when a small amount is added. If the thickness is less than 0.05 mm, the amount of the pigment deposited is not stable, and as a result, a large amount of pigment is required as in the case of direct charging. If it exceeds 10 mm, it is difficult to uniformly disperse (E), making it difficult to produce the material.
The phosphorescent material (E) in the molding material of the present invention preferably has a longest diameter of 0.5 to 5 mm.
The phosphorescent material (E) refers to a material containing a phosphorescent pigment (phosphorescent pigment). Luminescent pigments are phosphors having afterglow properties that emit luminescence with a considerably high yield by external stimuli such as light, heat and radiation, and emit light even after the external stimuli are removed. Typical phosphorescent pigments include aluminate-based and sulfide-based pigments, and aluminate-based pigments are more preferable in terms of afterglow luminance and afterglow time. A typical example of an aluminate-based compound is MAl ₂ O _{2 in} which M is any one of Ca, Sr, and Ba and contains a small amount of europium or despronium as an activator. It is.
The luminous material (E) in the molding material of the present invention is preferably obtained by pulverizing a cured resin containing a luminous pigment.
The phosphorescent material (E) in the molding material of the present invention is preferably a plate-like base material and / or a particulate base material coated with a phosphorescent pigment.
By using the phosphorescent material (E) as described above, it is possible to sufficiently exhibit the effects of the present invention.

The longest diameter of the phosphorescent pigment is preferably 15 μm or less, and more preferably 7 μm or less. When the thickness exceeds 15 μm, the amount of adhesion is insufficient when coating on the substrate, and the afterglow luminance may be lowered.
The adhesion amount of the phosphorescent pigment to the substrate is preferably ² to 30 g / m ² . If it is less than 2 g / m ² , the afterglow luminance may not be sufficient, and if it exceeds 30 g / m ² , the pigments may overlap and the afterglow luminance may become saturated.
Moreover, it is preferable that the luminous pigment content rate (attachment rate) with respect to 100 mass parts of luminous materials is 3-70 mass parts.
The method for attaching the phosphorescent pigment to the substrate is as follows.

Method for attaching phosphorescent pigment to substrate;
(1) A base material is coated only with a binder (acrylic resin or urethane resin) and dried.
(2) Next, the binder containing 30% phosphorescent pigment is coated and dried.
(3) Repeat (2) several times.
(4) Finally, only the binder is coated, dried and sized.

Examples of the substrate include mica, glass flakes, and PET films.

Examples of other additives that can be used in the molding material of the present invention include low shrinkage agents such as polystyrene and polyvinyl acetate, curing agents, inhibitors, internal mold release agents, pigments, thickeners, and the like. .

About the said hardening | curing agent, it can select from well-known organic peroxide according to the target shaping | molding cycle. Curing agents blended in the resin composition include t-butyl peroxybenzoate (TBPB), t-butyl peroxyoctoate (TBPO), t-hexylperoxybenzoate (THPB), and t-hexyl peroxyoctoate. Organics such as (THPO), 2,5-dimethyl-2,5-di (benzoylperoxy) cyclohexane (DDBPH), t-amylperoxyoctanoate (TAPO), t-butylisopropylperoxycarbonate (TBIPC) At least one kind can be selected from peroxides according to a desired curing rate, and usually 0.1 to 4 parts by mass is blended with 100 parts by mass of the molding material.

Moreover, a well-known hardening accelerator can also be used together with a hardening | curing agent. Examples of the curing accelerator include cobalt, copper, and manganese organometallic compounds such as octoate, naphthenate, and acetylacetonate. These may be used alone or in combination. Usually, 20 to 200 ppm is used with respect to 100 parts by mass of the molding material.

The said inhibitor can use a well-known thing. For example, PBQ (parabenzoquinone), MTBHQ (mono-t-butylhydroquinone), BHT (di-t-butylhydroxytoluene or 2,5-di-t-butyl-4-methylphenol), HQ (hydroquinone), TBC ( t-butylcatechol) or the like can be used.

A well-known thing can be used as said internal mold release agent. Examples thereof include metal soaps such as zinc stearate (ZnSt) and calcium stearate, fluorine-based organic compounds, and phosphoric acid-based compounds.

Known pigments can be used as the pigment. For example, titanium oxide, carbon black, petal, phthalocyanine blue, and the like can be given.
A well-known thing can be used as said thickener. Examples thereof include oxides or hydroxides such as magnesium and calcium, and isocyanates such as tolylene isocyanate (TDI). Among these, magnesium oxide is preferable.

The molding material of the present invention can be obtained as a sheet-like molding material such as SMC or TMC or a bulk-like molding material such as BMC by kneading and impregnating these components by conventional means. When used, after kneading and impregnation, it is aged at a predetermined temperature for a predetermined time and then used for molding.

The molded article of the present invention is obtained by press molding the above-described molding material.
The press molding is performed, for example, by heating and pressurizing at a predetermined temperature and a predetermined pressure with a molding machine such as a compression molding machine. For example, the molded product of the present invention can be produced by curing at a pressure of 1 to 12 MPa and a temperature of 80 to 160 ° C.

The molding material of the present invention has the above-described configuration, and is excellent in appearance, bending strength, low residual styrene content (low VOC), molding shrinkage ratio, and the like in a press-molded molded article, and excellent in night visibility. Vehicle applications such as airplanes, ship cabin guide lights, outboard motor covers, automobile skins, bicycle frames; road traffic signs, lane markings, guardrails, fishing buoys, mountain roads, etc. Guidance display, gate-to-entrance guidance display paving stone-like molded products, signs display for helmets, etc .; outdoor use of water meter lids, other meter boxes, signs, buildings, etc .; bathtubs, floor pans, waterproofing In various fields such as bread, flooring, wash counters, kitchen counters, electrical appliance switches, breaker boxes, etc .; It can be used to apply.

Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

(Preparation of unsaturated polyester)
(Synthesis Example 1)
A flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser and a stirrer was used as the reactor. This reactor was charged with 30 mol of isophthalic acid, 30 mol of propylene glycol, and 70 mol of neopentyl glycol. Next, while stirring the above contents in a nitrogen gas atmosphere, the reaction was conducted in a temperature range of 200 to 210 ° C., and the acid value of the reaction product was measured as needed by a predetermined method. When the acid value reached 10 mgKOH / g, the contents were cooled to 100 ° C., 70 mol of fumaric acid was added to the above reaction product, heated to 210 ° C., and reacted for 10 hours. The acid value of this unsaturated polyester was 25 mgKOH / g, and the number average molecular weight was 5,500.
Next, after adding a predetermined amount of styrene as a monomer to the unsaturated polyester, hydroquinone was added as a polymerization inhibitor to 100 ppm and mixed uniformly. As a result, an unsaturated polyester resin (UP-A) having a solid content (unsaturated polyester) of 67% and styrene of 33% was obtained.

<Method for measuring acid value>
The measurement was performed according to the method described in JIS K6911-1995 4.3.

(Synthesis Example 2)
In the same apparatus as in Synthesis Example 1, 20 mol of dicyclopentadiene and 100 mol of maleic anhydride were charged, the temperature was raised to 125 ° C., 100 mol of water was added dropwise over 2 hours, and the acid value was 220 mgKOH at a temperature of 120 to 130 ° C. It reacted until it became / g. Next, 100 mol of propylene glycol was charged, the temperature was raised to 205 ° C., and the mixture was reacted for 6 hours. The acid value of this unsaturated polyester was 25 mgKOH / g, and the number average molecular weight was 1600.
Next, after adding a predetermined amount of styrene as a monomer to the unsaturated polyester, hydroquinone was added as a polymerization inhibitor to 100 ppm and mixed uniformly. As a result, an unsaturated polyester resin (UP-B) having a solid content (unsaturated polyester) of 67% and styrene of 33% was obtained.

(Synthesis Example 3)
In the same apparatus as in Synthesis Example 1, 40 mol of isophthalic acid, 30 mol of hydrogenated bisphenol A, 50 mol of neopentyl glycol, and 20 mol of 1,6-hexanediol were charged. Next, while stirring the above contents in a nitrogen gas atmosphere, the reaction was conducted in a temperature range of 200 to 210 ° C., and the acid value of the reaction product was measured as needed by a predetermined method. And when this acid value became 10 mgKOH / g, it cooled, 60 mol of fumaric acids were added to said reaction material, and it was made to react again in the temperature range of 210-220 degreeC. Thereby, unsaturated polyester was obtained. The acid value of this unsaturated polyester was 33 mgKOH / g, and the number average molecular weight was 2500.
Next, after adding a predetermined amount of styrene as a monomer to the unsaturated polyester, hydroquinone was added as a polymerization inhibitor to 100 ppm and mixed uniformly. As a result, an unsaturated polyester resin (UP-C) having a solid content (unsaturated polyester) of 67% and styrene of 33% was obtained.

(Manufacture of phosphorescent materials)
The phosphorescent pigment, the longest pigment diameter of the phosphorescent material, the longest phosphorescent material diameter, the adhesion amount of the pigment, and the phosphorescent pigment content (attachment rate) with respect to 100 parts by mass of the phosphorescent material (E) are as shown in Table 1 below.

“Phosphorescent material A” was obtained by pulverizing a resin composition containing a phosphorescent pigment, and was produced as follows.
In 90 parts of unsaturated polyester resin polyhope N33PT (manufactured by Japan Composite), 10 parts of phosphorescent pigment (N nocturnal luminova: manufactured by Nemoto Special Chemical Co., Ltd.) are dispersed, 1% of MEKPO is added and cured at room temperature, and then at 100 ° C. After curing for 2 hours, it was obtained by pulverizing with a mill until the particle size became 3 mm or less.
“Luminescent material B” and “Luminous material C” are obtained by coating a base material with a luminous pigment. “Luminescent material B (mica)” has a longest diameter of 3 mm and uses mica (“B-112” (trade name) manufactured by Yamaguchi Mica Co., Ltd.) as a base material. “Luminescent material B (film)” has a longest diameter of 3 mm and uses a plastic substrate (PET) as a substrate. “Luminescent material C (GB)” has a longest diameter of 0.3 mm and uses glass beads as a base material.

Example 1
Unsaturated polyester resin UP-A 25.1 parts by mass (unsaturated polyester concentration of 67%), parabenzoquinone as a polymerization inhibitor 0.005 parts by mass, curing agent t-butylperoxyisopropyl carbonate (Kayaku Akzo) Manufactured by Kaya-Carbon BIC-75), 0.3 parts by mass of glass frit (manufactured by Toago Materials Co., Ltd .: M-910S) as filler and 1.3 parts by mass of zinc stearate as an internal mold release agent. Part and phosphorescent material A1.3 parts by mass into a double-arm kneader and kneaded well, and then 10.0 parts by mass of glass fiber cut to 3 mm length as a glass fiber was added to the resin paste and further kneaded. . This BMC (bulk molding compound) is a 30 cm square plate mold, and the mold temperature is 130 ° C. on the product surface, 120 ° C. on the back surface (indicated in the table as molding temperature 130/120), and the surface pressure is 10 MPa. Heat compression molding was performed. Keeping for 6 minutes, a BMC molded flat plate having a thickness of 8 mm was obtained. Using this, various physical properties were measured. The results are shown in Table 2.

(Examples 2 to 7)
The formulations shown in Table 2 (excluding glass fibers) were well kneaded with a disper, and phosphorescent molded products (SMC) were produced with an SMC impregnation machine according to a conventional method. After aging at 40 ° C. for 24 hours, a 30 × 30 × 0.5 cm flat plate was press-molded with a 100-ton press. Molding conditions: temperature (shown in Table 2) pressure 10 MPa, keep time (shown in Table 2). The obtained molded product was measured for night visibility, bending strength, residual styrene content, molding shrinkage, and evaluated for appearance. The results are shown in Table 2.

In Table 2, the following low shrinkage agents (thermoplastic resins) were used as other additives.
SV10B: Polystyrene acetate / polystyrene copolymer styrene solution having a styrene content of 70%.
9965: A styrene solution of polystyrene and a styrene content of 70%.

(Comparative Examples 1-2)
A phosphorescent molded product (SMC) was produced in the same manner as in Example 1 except that each formulation shown in Table 3 was used. At night visibility, bending strength, residual styrene content and molding shrinkage were measured to evaluate the appearance. The results are shown in Table 3.
(Comparative Examples 3 and 4)
A phosphorescent molded article (SMC) was produced in the same manner as in Examples 2 to 7 except that the formulations shown in Table 3 were used.

<Night visibility>
The molded product (30 cm square plate) was stored in a dark room for 15 hours, then stimulated with a light source (200 lux brightness) for 1 hour, and then the afterglow brightness was qualitatively evaluated in the dark room.
◎ The whole surface clearly shines up to the outline ○ It shines enough to recognize the whole area including the outline △ It is dim, but the outline is difficult to see × Cannot be recognized

<Appearance evaluation>
The overall evaluation was made with respect to smoothness, gloss, and color unevenness.
○ Good smoothness, glossy, no color irregularity △ Smoothness, slightly glossy, slightly uneven color × Smoothness, poor gloss, uneven color <Bending strength>
Measurement was performed based on JISK6911.
<Residual styrene content>
The measurement was performed by immersing the molded article in methylene chloride for 16 hours, and styrene eluted in the methylene chloride by gas chromatography (column filler: BX-10, column length: 3 m, carrier gas: nitrogen, Shimadzu GC-2014, C- R8A) was quantified and measured.
<Mold shrinkage>
The shrinkage was measured from the ratio of the room temperature molded article to the mold dimensions.

It was found that a molded product press-molded from the molding material of the present invention has excellent appearance and nighttime visibility while maintaining excellent bending strength, low VOC and molding shrinkage.

From the examples and comparative examples described above, it was found that the following can be said. That is, when the total amount of the molding material of the present invention is 100 parts by mass, the thermosetting resin (A) is 5 to 20 parts by mass, the polymerizable unsaturated monomer (B) is 5 to 20 parts by mass, and the filler. By including 10 to 70 parts by mass of (C), it can be excellent in strength, dimensional accuracy, low VOC, and the like. Among them, by using a phosphorescent material (phosphorescent pigment) of a predetermined size, night visibility becomes excellent from x to ◎, ○ or Δ (Examples 1 to 7, Comparative Examples 1 to 4), When 100 to 50 parts by mass of the molding material, 5 to 50 parts by mass of a glass fiber having a fiber length of 2 to 50 mm, and 0.1 to 20 parts by mass of a phosphorescent material having a longest diameter of 0.05 to 10 mm, While maintaining other excellent physical properties, the nighttime visibility was ◎ or ◯ (Examples 1 to 7). That is, it has been found that by making the molding material to be added as described above, the effect of improving nighttime visibility while maintaining other excellent physical properties becomes remarkable. For example, in the case of manufacturing molded articles to be used as signs in the construction and transportation fields, if night visibility is improved while maintaining various physical properties such as strength, a highly safe molded article can be obtained. It can be manufactured. In addition, it can be safely moved at night as a substitute for a guide light by being used for cabins of airplanes, ships, etc., counters and bathtubs of kitchen bathrooms, and moldings for washing places. The above-described examples and comparative examples clearly demonstrate the advantageous effects of the present invention, and support the technical significance of the present invention.

Claims (9)

A molding material for obtaining a phosphorescent molded product by press molding,
When the total amount of the molding material is 100 parts by mass, the thermosetting resin (A) is 5 to 20 parts by mass, the polymerizable unsaturated monomer (B) is 5 to 20 parts by mass, and the filler (C) is 10 to 70 parts. It contains 5 to 50 parts by mass of glass fiber (D) having a fiber length of 2 to 50 mm and a phosphorescent material (E) having a longest diameter of 0.05 to 10 mm as essential components. Characteristic molding material. The thermosetting resin (A) is an unsaturated polyester and / or vinyl ester.
The molding material according to claim 1. The glass fiber (D) has a fiber length of 6 to 26 mm.
The molding material according to claim 1 or 2, characterized in that. The said luminous material (E) is obtained by grind | pulverizing the resin cured material containing a luminous pigment, The molding material in any one of Claims 1-3 characterized by the above-mentioned. The molding material according to any one of claims 1 to 4, wherein the phosphorescent material (E) is a plate-like substrate and / or a particulate substrate coated with a phosphorescent pigment. The amount of the phosphorescent pigment adhering to the substrate is 2 to 30 g / m. ² Is
The molding material according to claim 5. The phosphorescent pigment has a longest diameter of 15 μm or less.
The molding material according to any one of claims 4 to 6, characterized in that The molding material according to any one of claims 1 to 7 , wherein the filler (C) contains at least one selected from the group consisting of calcium carbonate, aluminum hydroxide, and glass frit . Molded article, characterized in that is obtained by press-molding the molding material according to any one of claims 1-8.