CN1934192B - Low specific gravity unsaturated polyester resin composition for lamp reflector and moldings thereof - Google Patents
Low specific gravity unsaturated polyester resin composition for lamp reflector and moldings thereof Download PDFInfo
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- CN1934192B CN1934192B CN2005800089739A CN200580008973A CN1934192B CN 1934192 B CN1934192 B CN 1934192B CN 2005800089739 A CN2005800089739 A CN 2005800089739A CN 200580008973 A CN200580008973 A CN 200580008973A CN 1934192 B CN1934192 B CN 1934192B
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- 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
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Abstract
A low-specific-gravity unsaturated polyester resin composition for lamp reflector that exhibits low specific gravity of molding, being free from variation and excels in molding properties, such as surface smoothness, thermal stability, mechanical strength, rigidity, dimensional precision and moldability; and a molding thereof. There is provided a low-specific-gravity unsaturated polyester resin composition for lamp reflector, comprising an unsaturated polyester resin and a crosslinking agent and further, per 100 parts by mass thereof, 40 to 210 parts by mass of inorganic filler, such as calcium carbonate, of 0.5 to 15 mum average particle diameter and 30 to 160 parts by mass of hollow filler, such as glass balloon, of 2100x10<4> N/m<2> or greater pressure withstanding strength and 0.3 to 0.7 true specific gravity, the loading mass ratio of inorganic filler : hollow filler being in the range of 2:8 to 8:2.
Description
Technical field
The present invention relates to unsaturated polyester resin composition for lamp reflectors and forming composition thereof, particularly is the unsaturated polyester resin composition for lamp reflectors and the forming composition thereof of representative with the automobile-use headlamp.
Background technology
Now; Unsaturated polyester resin formed material (BMC (Bulk molding composition): BMC); Because its excellent physical strength, rigidity, surface smoothing property, dimensional precision, thermotolerance, formability are widely used in the chassis of office automation instrument, office equipment, the lamp reflector purposes that the automobile-use headlamp is representative etc.
Yet; Though existing unsaturated polyester resin formed material can obtain in forming composition excellent aspect physical strength, rigidity, surface smoothing property, dimensional precision, the thermotolerance through curing molding; Find following problem but then; Owing to the inorganic filling material that is used to keep these excellent characteristics to contain and the amount of fiber reinforcement material, forming composition proportion uprises.In addition, even also uprise, so it utilizes scope to be restricted all the time owing to comparing forming composition proportion with thermoplastic resin.
In order to address these problems; Attempted various methods of seeking low-gravityization,, can enumerate as the gimmick of representational low-gravityization; Reduce packing material, strongthener; And then add the less filler of proportion such as white lake, or to add with hollow glass ball, hollow silica ball be the hollow packing (for example, with reference to patent documentation 1) of representative.
Yet, particularly be defined under the situation that lamp reflector uses, if add the less filler of proportion like this; Then thermotolerance reduces, and when forming composition is carried out application, vapor deposition, can expand, break; In addition sometimes after several years the vapor deposition face expand, electrochromic variable is big.And then find the multiple following low problem of formability, and promptly surface smoothing such as glossiness, planeness property significantly reduces, and the physical strength rerum natura of forming composition declines to a great extent, and produces bubble, smudgy, surface depression etc. during injection moulding.
In addition; The general hollow packing of interpolation that iff is simple; During metering in injection moulding, during injection moulding breaking of hollow packing can be taken place, forming composition takes place has the proportion deviation between deviation, individuality because of position difference proportion, relevant with distortion, the distortion of forming composition.And then, crooked by the luminous intensity distribution that this is distorted, distortion can produce lamp reflector.In addition, also exist because stable on heating reduction causes expanding, breaks, the reduction of surface smoothing property, to fiber reinforcement material surface emersion, formability is hanged down inferior problem, can not be used for the automobile-use headlamp is the lamp reflector purposes of representative.
Patent documentation 1: the spy opens the 2001-261954 communique
Summary of the invention
Therefore; Problem of the present invention is; Provide forming composition proportion little and zero deflection, lamp reflector excellent aspect surface smoothing property, thermotolerance, physical strength, rigidity, dimensional precision, formability is with low specific gravity unsaturated polyester resin composition and forming composition thereof.
Present inventors further investigate in order to solve above-mentioned problem; The result finds; Through in unsaturated polyester resin, specific inorganic filling material and specific hollow packing being added with specific ratio, can solve above-mentioned problem, thereby accomplish the present invention.
Promptly; Lamp reflector of the present invention is with low-gravity unsaturated polyester ester composition; Be characterised in that; With respect to the unsaturated polyester resin and the linking agent that amount to 100 mass parts, with inorganic filling material: the interpolation mass ratio of hollow packing=2: 8～8: 2 scope contain having of 40～210 mass parts be at least 0.5 μ m the averaged particles footpath inorganic filling material and, 30～160 mass parts have at least 2100 * 10
4N/m
2The hollow packing of compressive strength.
In addition, forming composition of the present invention is characterized in that, obtains with low specific gravity unsaturated polyester resin through the above-mentioned lamp reflector of moulding.
At this moment, preferably has-0.15～+ 0.05% molding shrinkage, 1.0～2.5 * 10
-5The forming composition of Pasteur's (Barco1) hardness the when linear expansivity of/K, 5～25 180 ℃ are warm and 1.00～1.60 forming composition proportion.
According to the present invention; Through contain specific inorganic filler and hollow packing with specified quantitative; May be provided in the little and zero deflection of forming composition proportion of type thing; And, the lamp reflector with excellent surface smoothing property, thermotolerance, physical strength, rigidity, dimensional precision, formability with low specific gravity unsaturated polyester resin composition with and forming composition.
Description of drawings
Fig. 1 is the plat of experimental box used among the embodiment.
Fig. 2 is the sectional view of the A-A ' line of Fig. 1.
Embodiment
Unsaturated polyester resin compositions of the present invention; Unsaturated polyester resin and linking agent with respect to 100 mass parts; With inorganic filling material: the interpolation mass ratio of the scope of hollow packing=2: 8～8: 2 contain having of 40～210 mass parts be at least 0.5 μ m the averaged particles footpath inorganic filling material and, 30～160 mass parts have at least 2100 * 10
4N/m
2The compsn of the hollow packing of compressive strength.
There is not special qualification for the kind of employed unsaturated polyester resin among the present invention.So long as polyvalent alcohol and unsaturated polyprotonic acid and/or saturated polybasic acid polycondensation form,, just can suitably use as the normally used polyester of formed material.In addition, as the part of unsaturated polyester resin, can mixed ethylene base ester resin, diallyl phthalate resin.
As the polyvalent alcohol that forms unsaturated polyester resin; For example can enumerate; Terepthaloyl moietie, Ucar 35, NSC 6366, butyleneglycol, glycol ether, dipropylene glycol, triglycol, pentanediol, pinakon, NSC 6366, Hydrogenated Bisphenol A 99; Dihydroxyphenyl propane, glycerine etc., from the viewpoint of thermotolerance, physical strength and formability etc., preferred Ucar 35, NSC 6366, and dihydroxyphenyl propane or Hydrogenated Bisphenol A 99.
As unsaturated polycarboxylic acid; Can enumerate; Maleic anhydride, fumaric acid, citraconic acid, methylene-succinic acid etc.; In addition, also can enumerate Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, hexachloro-endomethylene tetrahydrophthalic acid, succsinic acid, hexanodioic acid, sebacic acid, tetrachlorophthalic tetrachlorophthalic anhydrid, tetrabromophthalic anhydride, interior methylene radical Tetra Hydro Phthalic Anhydride etc. as saturated polybasic acid.Wherein, from the viewpoint of thermotolerance, physical strength and formability etc., preferred unsaturated polyprotonic acid, preferred especially maleic anhydride and fumaric acid.
In addition; From improving viewpoints such as thermotolerance, physical strength and formability; The following unsaturated polyester resin of preferred use, said unsaturated polyester resin are, with respect to 100 moles of at least a unsaturated polyprotonic acids of from the group of maleic anhydride and fumaric acid formation, selecting; With 20～50 moles of Ucar 35 and, 25～65 moles of NSC 6366s and, 15～25 moles dihydroxyphenyl propane or Hydrogenated Bisphenol A 99, add up to according to them that 100 moles ratio polycondensation obtains.
As linking agent,, just can suitably use so long as have the linking agent with the two keys of the polymerisable polymerizability of above-mentioned unsaturated polyester.As such linking agent, for example can enumerate styrene monomer, Phthalic acid, diallyl ester monomer, Phthalic acid, diallyl ester prepolymer, TEB 3K, trimerization triallyl isocyanurate etc.Its usage quantity; Viewpoint from the degree of freedom of the shrinkability of operability, polymerizability, moulding article and amount adjustment; In total 100 mass parts of unsaturated polyester resin and linking agent, linking agent is more than 25 mass parts, is preferably more than 35 mass parts; Below 70 mass parts, be preferably below 65 mass parts.
In addition; From improving the viewpoint of coating; Preferably with respect to total 100 mass parts of unsaturated polyester resin and linking agent, containing above-mentioned linking agent is 35～75 mass parts, is more preferably 45～65 mass parts; And above-mentioned linking agent is preferably according to (A): (B)=5: 95～25: 75, the mass ratio of more preferably 10: 90～20: 80 scope contains the monomer or the linking agent (B) beyond performed polymer (A) and the Phthalic acid, diallyl ester monomer of Phthalic acid, diallyl ester.
Inorganic filling material among the present invention has the averaged particles footpath that is at least more than the 0.5 μ m.If less than 0.5 μ m, then viscosity uprises, and hollow packing perhaps takes place destroy, and the proportion of forming composition uprises, and can not obtain plastic resin.From the viewpoint of formability, the averaged particles of inorganic filling material directly is preferably more than the 0.7 μ m, most preferably is more than the 1.8 μ m.On the other hand, from the surface smoothing property of forming composition, the angle of mechanical characteristics, below the preferred 15 μ m in this averaged particles footpath, further be preferably below the 10 μ m.If surpass 15 μ m, surface smoothing property, the physical strength of forming composition significantly reduce, and perhaps the flowability of material degenerates, and formability degenerates, because of rather than preferably.
In addition, inorganic filler as used herein, the viewpoint from the surface smoothing property of resin combination is preferably lime carbonate.
The use level of inorganic filling material with respect to 100 mass parts unsaturated polyester resin and linking agents, is more than 40 mass parts, more than preferred 50 mass parts, is below 210 mass parts, is preferably below 160 mass parts.If use level is less than 40 mass parts, then the formability variation is understood the emersion of bubbling, fiber reinforcement material etc. in forming composition, can not obtain sufficient surface smoothing property, and physical strength reduces significantly.If use level is more than 210 mass parts, then the proportion of forming composition uprises.
As such inorganic filling material, can use Powdered things such as lime carbonate, white lake, wollastonite, potter's clay, talcum, mica, silicon-dioxide as required.
As the hollow packing among the present invention, as long as have at least 2100 * 10
4N/m
2The then not special restriction of compressive strength, can enumerate hollow glass ball, hollow silica ball, hollow alumina balls etc.If compressive strength less than 2100 * 10
4N/m
2, then thermotolerance and bad mechanical strength are destroyed during manufacturing or during moulding, and the proportion of forming composition can not diminish.Compressive strength is preferably 2800 * 10
4N/m
2More than.
This hollow packing, also preferred true specific gravity are 0.3～0.7 scope.If true specific gravity less than 0.3 then because viscosity rises, has to reduce the addition of inorganic filling material, the formability variation, surface smoothing property, the physical strength of forming composition significantly reduce, thereby are not preferred; If opposite true specific gravity surpasses 0.7, then proportion can be not little, thereby be not preferred.
In addition, from the viewpoint of the surface smoothing property of resin combination, the averaged particles of hollow packing directly is preferably below the 80 μ m.
As the use level of hollow packing, with respect to the unsaturated polyester resin and the linking agent of 100 mass parts, be more than 30 mass parts, be preferably more than 40 mass parts, be below 160 mass parts, be preferably below 150 mass parts.If surpass 160 mass parts, then, have to reduce the addition of inorganic filling material because viscosity rises, the formability variation, surface smoothing property, the physical strength of forming composition significantly reduce.On the contrary, under situation about lacking than 20 mass parts, forming composition proportion uprises.
Inorganic filling material and hollow packing, according to inorganic filling material: the interpolation mass ratio of the scope of hollow packing=2: 8～8: 2 contains in unsaturated polyester resin compositions.If exceed this mass ratio, the empty filler quilt of heavy addition, then physical strength significantly reduces.In addition, the emersion of fiber reinforced material etc. taking place, can not get sufficient surface smoothing property.If the heavy addition inorganic filling material, then forming composition proportion uprises.From the viewpoint of physical strength, above-mentioned interpolation mass ratio is preferably 4: 6～and 7.5: 2.5.
As the unsaturated polyester resin compositions among the present invention, except that above-mentioned each composition, can also use shrinking agent, solidifying agent, remover, tackifier, fiber enhancer, pigment, viscosity depressant etc. as required.Using under the situation of these compositions, can in unsaturated polyester resin compositions of the present invention, cooperate each composition according to used use level usually according to separately purpose.
Can use the common thermoplastic polymer that uses as shrinking agent such as PS more than a kind or 2 kinds, polymethylmethacrylate, Yodo Sol VC 400, saturated polyester, styrene butadiene class rubber as shrinking agent.
Solidifying agent can use the suitable compound in the superoxide.Can enumerate for example Peroxycaprylic acid tertiary butyl ester, Lucidol, 1,1-two-t-butyl peroxy-3,3,5-trimethyl-cyclohexane, BPIC t butyl peroxy isopropyl carbonate, t-butyl-oxybenzoate, dicumyl peroxide, di-t-butyl peroxide etc.
As remover, can use for example hard ester acid, Zinc Stearate, calcium stearate, aluminum foil stearate, magnesium stearate, POLISHING WAX-103 etc. according to suitable ratio.
As tackifier, can enumerate MOX and isocyanate compounds such as Natural manganese dioxide, Marinco H, calcium hydroxide, quicklime.Tackifier can must not use.
As fiber reinforced material, can use the short glass fiber that is cut to about the long 1.5～25mm of fiber.In addition, also can use organic-inorganic fibers such as paper pulp fiber, テ ト mouth Application (login trade mark) fiber, vinylon fiber, thomel, Kevlar, wollastonite.
Unsaturated polyester resin compositions of the present invention by the composition of above that kind constitutes can for example utilize mixing obtaining such as kneader through the method for carrying out usually.
Forming composition among the present invention obtains from unsaturated polyester resin compositions of the present invention.This forming composition; Because have the forming composition rerum natura of aforesaid excellence; Little and the zero deflection of forming composition proportion; And, shown the forming composition rerum natura of excellent physical strength, rigidity, surface smoothing property, dimensional precision, thermotolerance etc., thereby possessed the characteristic of using as lamp reflector with high level.
This forming composition preferably has-0.15～+ 0.05% molding shrinkage, 1.0～2.5 * 10
-5Barcol hardness when the linear expansivity of/K, 5～25 180 ℃ are warm and 1.00～1.60 forming composition proportion.Use such a forming composition, during heating and several years after distortion little.
Here, molding shrinkage is to measure under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time according to JIS K6911.If the molding shrinkage of forming composition is not enough-0.15, then the demoulding from mould becomes difficulty during moulding, on the other hand, if surpass+0.05, then surface smoothing property deterioration, thereby not preferred.In addition, this forming composition, the viewpoint from surface smoothing property and formability preferably has-0.12～0.00 molding shrinkage.
Linear expansivity is to measure under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time according to JIS K6911.If the linear expansivity of forming composition surpasses 2.5 * 10
-5The distortion of moulding article then the time can take place and breaks in heating, thereby be not preferred in/K.In addition, this forming composition from the viewpoint of dimensional stability, preferably has 1.1～2.0 * 10
-5The linear expansivity of/K.
Barcol hardness, be according to JIS K6911 under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time, measure with the Bareol hardness meter GYZJ934-1 of BARBER-COLMAN COMPANY system.If the Barcol hardness of forming composition is lower than 5, then the planeness of moulding article is low when heating, deforms; On the other hand, if surpass 25, then the post-treatment of moulding article becomes difficulty, thereby is not preferred.In addition, this forming composition from stable on heating viewpoint, preferably has 5.5～22, is more preferably 6.0～22 Barcol hardness.
The proportion of forming composition is that the numerical value according to compression molding thing of measuring according to JIS K6911 and injection moulding thing both sides' forming composition proportion obtains.If forming composition proportion is lower than 1.00, then injection moulding property and physical strength are low, on the other hand, if surpass 1.6, then with the proportion indifference of existing BMC, can not realize the lightweight of moulding article, thereby be not preferred.In addition, from the viewpoint of formability, physical strength and proportion, the proportion of preferred forming composition is 1.01～1.45.
The rerum natura of these forming composition can easily be adjusted through changing the cooperation ratio of BMC.
In addition, forming composition of the present invention preferably has 5～20 planeness (smoothness).The forming composition that shows the planeness of this scope, surface smoothing property is excellent.
This planeness is to use BYK Gardner society system wave front aberration somascope (Wavescan) DO1, obtains according to short wavelength's numerical value.If the planeness of forming composition surpasses 20, then surface smoothing property deterioration, thereby be not preferred.In addition, the planeness of this forming composition is preferably 7～15.
Forming composition of the present invention, preferred especially above-mentioned molding shrinkage, linear expansivity, Barcol hardness, forming composition proportion and planeness all satisfy above-mentioned scope.
Forming composition of the present invention can be through utilizing the usual method moulding to come easily to obtain unsaturated polyester resin compositions of the present invention.Such forming method can be enumerated out compression molding, transfer molding, injection moulding etc.
Embodiment
Below, specify the present invention through embodiment and comparative example.Certainly, the present invention is only just passable otherwise surmount its invention main points, does not receive the qualification of following embodiment.
Embodiment 1～29, is to form according to the cooperation shown in table 1～4 to use two bowl type kneaders mixing down at 30 ℃ each gradation composition, obtains unsaturated polyester resin compositions.
In embodiment 1～8, use resin I, the styrene monomer of unsaturated polyester resin that obtains according to 100 moles/80 moles/20 moles ratio polycondensation by fumaric acid/Ucar 35/Hydrogenated Bisphenol A 99 that contains 60 quality % and, 40 quality % as linking agent.
The resin II that in embodiment 9～23 and 26～27, uses, the styrene monomer of unsaturated polyester resin that obtains according to 100 moles/35 moles/45 moles/20 moles ratio polycondensation by fumaric acid/Ucar 35/NSC 6366/Hydrogenated Bisphenol A 99 that contains 70 quality % and, 30 quality % as linking agent.
The resin III that in embodiment 24, uses, the styrene monomer of unsaturated polyester resin that obtains according to 100 moles/25 moles/60 moles/15 moles ratio polycondensation by fumaric acid/Ucar 35/NSC 6366/Hydrogenated Bisphenol A 99 that contains 70 quality % and, 30 quality % as linking agent.
The resin IV that in embodiment 25, uses, the styrene monomer of unsaturated polyester resin that obtains according to 100 moles/50 moles/25 moles/25 moles ratio polycondensation by fumaric acid/Ucar 35/NSC 6366/Hydrogenated Bisphenol A 99 that contains 70 quality % and, 30 quality % as linking agent.
The resin V that in embodiment 28, uses, the styrene monomer of unsaturated polyester resin that obtains according to 100 moles/35 moles/45 moles/20 moles ratio polycondensation by fumaric acid/Ucar 35/NSC 6366/Hydrogenated Bisphenol A 99 that contains 80 quality % and, 20 quality % as linking agent.
The resin VI that in embodiment 29, uses contains the styrene monomer as linking agent by the unsaturated polyester resin of maleic anhydride/Ucar 35/obtain according to 100 moles/100 moles ratio polycondensations and, 30 quality % of 70 quality %.
These compsns are carried out the evaluation of molding shrinkage, linear expansivity, Barcol hardness, proportion, thermotolerance, physical strength, formability, surface smoothing property, manufacturing possibility.The method of test, evaluation is as follows.
(1) molding shrinkage
The shrink disc of .JIS K69115.7 regulation is carried out compression molding under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time, calculate molding shrinkage according to JIS K69115.7.
(2) linear expansivity
Flexural strength and crooked elastic rate test film with JIS K69115.7 regulation; Under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time, carry out compression molding; Downcut the test film of 4 * 4 * 20mm; Use the Thermoplus TMA8310 of リ ガ Network Co., Ltd. system, under the intensification temperature of 2 ℃/min, 40 ℃～80 ℃ mensuration temperature, measure the heat-up rate linear expansivity.
(3) 180 ℃ of Barcol hardnesses when hot
The shrink disc of JIS K6911 regulation is carried out compression molding process test film under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time.In the atmosphere gas of 180 ℃ of Hotaircirculatingovens, above-mentioned test film was placed 30 minutes, taken out the back and measure the Barcol hardness when hot with the Bareol hardness meter GYZJ934-1 of BARBER-COLMAN COMPANY system at once.
(4) proportion
1) proportion of compression molding thing
Under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time,, cut out test film, measure proportion according to JIS K6911 through the shrink disc moulding of compression molding with JIS K6911 regulation.
2) proportion of injection moulding thing
At such as shown in Figures 1 and 2 chamber (360 * 120 * 25mm; Wall thickness: long side 4mm, short brink 5mm, bottom surface 3mm) in; Under 160 ℃ of forming temperatures, injection pressure 30MPa, 2 minutes condition of molding time, use the made injection moulding machine NNT250PSCH 7000 of Nigata ironworker to carry out injection mo(u)lding.Cut out the gate portions (watering oral-lateral) of the proofing box forming composition that obtains and the test film of final filling part (cast gate opposition side), measure proportion according to JIS K6911.
(5) thermotolerance (outward appearance after the heating)
Outward appearance after the JIS K6911 predetermined heating is measured with disk under 3 minutes conditions of 150 ℃ of mold temperatures, forming pressure 10MPa, molding time; Carry out compression molding, test the cosmetic variation evaluation of carrying out under 180 ℃ according to the outward appearance after the JIS K6911 heating.Evaluation method is carried out as follows, as the mark in the table, and zero: no change, △: expand, *: break.
(6) physical strength
Flexural strength and crooked elastic rate test film with JIS K6911 regulation carry out compression molding under 150 ℃ of mold temperatures, forming pressure 10MPa, 3 minutes condition of molding time, measure flexural strength and crooked elastic rate according to JISK6911.
(7) formability
With such as shown in Figures 1 and 2 chamber (360 * 120 * 25mm; Wall thickness: long side 4mm, short brink 5mm, bottom surface 3mm); Under 160 ℃ of forming temperatures, injection pressure 30MPa, 2 minutes condition of molding time; Use the made injection moulding machine NNT250PSCH7000 of Nigata ironworker to carry out injection mo(u)lding, the visual valuation fillibility.Evaluation method is carried out as follows, as the mark in the table, and ◎: very good, zero: good, △: poor slightly, *: bad.
(8) surface smoothing property
1) appearance
With such as shown in Figures 1 and 2 chamber (360 * 120 * 25mm; Wall thickness: long side 4mm, short brink 5mm, bottom surface 3mm); Under 160 ℃ of forming temperatures, injection pressure 30MPa, 2 minutes condition of molding time; Use the made injection moulding machine NNT250PSCH 7000 of Nigata ironworker to carry out injection mo(u)lding, the visual valuation appearance.Evaluation method is carried out as follows, as the mark in the table, and ◎: very good, zero: good, △: poor slightly, *: bad.
2) planeness
With such as shown in Figures 1 and 2 chamber (360 * 120 * 25mm; Wall thickness: long side 4mm, short brink 5mm, bottom surface 3mm); Under 160 ℃ of forming temperatures, injection pressure 30MPa, 2 minutes condition of molding time; Use the made injection moulding machine NNT250PSCH 7000 of Nigata ironworker to carry out injection mo(u)lding, use the wave front aberration somascope DOI of BYK Gardner society system to carry out long wavelength (Long Wave) and short wavelength's (Short Wave) mensuration then, thereby estimate flatness.With the long wavelength is below 10, and the short wavelength is evaluated as good planeness below 20.
3) glossiness
With such as shown in Figures 1 and 2 chamber (360 * 120 * 25mm; Wall thickness: long side 4mm, short brink 5mm, bottom surface 3mm); Under 160 ℃ of forming temperatures, injection pressure 30MPa, 2 minutes condition of molding time; Use the made injection moulding machine NNT250PSCH 7000 of Nigata ironworker to carry out injection mo(u)lding, use the HANDY GLOSSMETER PG-1M of Japanese electric look Industrial Co., Ltd system then, measure glossiness according to JISZ8741 mirror surface luster assay method 3.
(9) coating
Use the checker test that the proofing box moulding article that use in above-mentioned (4) carry out stipulating in the cohesiveness of JIS K54008.5 item (cut at interval: 1mm), count with the evaluation of stipulating in the cohesiveness (table 18) of JIS K54008.5 item and to estimate.
The result of these evaluation of measuring is shown in table 1～4.
Table 4
1) the symbol implication is following: zero: no change △: expand *: break
2) the symbol implication is following: ◎: very good zero: good △: poor slightly *: bad
3) the symbol implication is following: ◎: zero: 8～7 △ more than 9: 6～5 *: below 4
That kind shown in these tables 1～4, during fabrication, the destruction of hollow packing is few during moulding stable and have the forming composition proportion below 1.6 in any embodiment, and almost do not have the heterogeneity on the position of forming composition.And, obtain having excellent thermotolerance, surface smoothing property, and have the forming composition of excellent size precision, mechanical characteristics, formability.Further, in the embodiment of the monomer that uses Phthalic acid, diallyl ester as linking agent or performed polymer (A) and, Phthalic acid, diallyl ester free-radical polymerised unsaturated monomer (B) in addition, can obtain having the forming composition of excellent coating.
Moreover, directly be that physical strength, formability, appearance have significantly improved under the situation of the inorganic filling material below the 15.0 μ m using averaged particles.In addition, at any one all under the situation in the scope 1.00～1.60 of compression molding thing proportion and injection moulding thing proportion, excellently special on physical strength.
On the other hand, the same with embodiment 1～29 to comparative example 1～18, it is mixing to use two bowl type kneaders to carry out each gradation composition according to the composition of the cooperation shown in table 5～6, obtains unsaturated polyester resin compositions.
To these compsns, the same with embodiment, carry out the evaluation of molding shrinkage, linear expansivity, Barcol hardness, proportion, thermotolerance, physical strength, formability, surface smoothing property, manufacturing possibility.The result of these evaluation of measuring has been shown in table 5～6.
As table 5～6 show; The interpolation mass ratio of the use level of inorganic filling material, the use level of hollow packing, inorganic filling material and hollow packing departs from above-mentioned specified range; Volume has been added the unsaturated polyester resin compositions of hollow packing; Thermotolerance, surface smoothing property, physical strength, formability, forming composition outward appearance significantly reduce, and maybe can not make.On the contrary, under insufficient situation, can not obtain the goods that meet the demands aspect the forming composition proportion.In addition; Be to depart from above-mentioned specified range equally, volume has been added the unsaturated polyester resin compositions of inorganic filling material, can not get the goods that meet the demands aspect the forming composition proportion; Under insufficient situation, physical strength, formability, forming composition outward appearance significantly reduce on the contrary.
In addition, the compressive strength of hollow packing does not satisfy the unsaturated polyester resin compositions of above-mentioned particular value, and hollow packing is destroyed during fabrication or during moulding, and forming composition proportion increases, and thermotolerance reduces.And the unsaturated polyester resin compositions that the use level of hollow packing is increased can not obtain the goods that meet the demands aspect thermotolerance, surface smoothing property, physical strength, the formability.
On the other hand, the averaged particles of inorganic filling material is the unsaturated polyester resin compositions of discontented above-mentioned particular value directly, and viscosity of material uprises and can not make.
Further, compression molding thing proportion, Barcol hardness depart from specialized range, it is apparent that poor heat resistance.
Therefore; Of the present invention from being the forming composition that the unsaturated polyester resin compositions of characteristic obtains to contain inorganic filling material and hollow packing; Different with in the past it is apparent that to have harmonious good and low proportion and forming composition rerum naturas such as excellent thermotolerance, surface smoothing property, mechanical characteristics, formability.In addition; Forming composition from the unsaturated polyester resin compositions of the monomer that used Phthalic acid, diallyl ester as linking agent or performed polymer and, free-radical polymerised unsaturated monomer beyond the Phthalic acid, diallyl ester monomer obtains it is apparent that further have excellent coating.
Hence one can see that, and the forming composition of the present invention that obtains from this unsaturated polyester resin compositions requires in the lamp reflector field of high heat resistance, surface smoothing property and mechanical characteristics at automobile-use headlamp etc. and is very useful, can in wide scope, using.
Claims (7)
1. a lamp reflector is used low specific gravity unsaturated polyester resin composition; It is characterized in that; Unsaturated polyester resin and linking agent with respect to 100 mass parts; According to inorganic filling material: the interpolation mass ratio of the scope of hollow packing=2: 8～8: 2 contains the averaged particles footpath with 0.5 μ m～15 μ m of 40～210 mass parts; And be selected from lime carbonate, white lake, wollastonite, potter's clay, talcum, mica and silicon-dioxide inorganic filling material and, 30～160 mass parts have at least 2100 * 10
4N/m
2Averaged particles footpath below compressive strength, the 80 μ m and 0.3～0.7 true specific gravity; Be selected from the hollow packing of hollow glass ball, hollow silica ball and hollow alumina balls; With respect to above-mentioned unsaturated polyester resin of 100 mass parts and above-mentioned linking agent; Containing above-mentioned linking agent is 35～75 mass parts, and above-mentioned linking agent is according to (A): (B)=mass ratio of 5: 95～25: 75 scope contain Phthalic acid, diallyl ester monomer or performed polymer (A) and, the linking agent (B) beyond the Phthalic acid, diallyl ester monomer.
2. lamp reflector as claimed in claim 1 is used low specific gravity unsaturated polyester resin composition; It is characterized in that; Above-mentioned unsaturated polyester resin is; With respect to 100 moles of at least a unsaturated polyprotonic acids of from the group that fumaric acid and maleic anhydride constitute, selecting, with 20～50 moles of Ucar 35 and, 25～65 moles of NSC 6366s and, 15～25 moles dihydroxyphenyl propane or Hydrogenated Bisphenol A 99, the ratio that adds up to 100 moles according to them comes polycondensation to obtain.
3. lamp reflector as claimed in claim 1 is used low specific gravity unsaturated polyester resin composition, it is characterized in that, the forming composition of above-mentioned resin combination has-0.15～+ 0.05% molding shrinkage, 1.0～2.5 * 10
-5Barcol hardness when the linear expansivity of/K, 5～25 180 ℃ are warm and 1.00～1.60 forming composition proportion.
4. lamp reflector as claimed in claim 2 is used low specific gravity unsaturated polyester resin composition, it is characterized in that, the forming composition of above-mentioned resin combination has-0.15～+ 0.05% molding shrinkage, 1.0～2.5 * 10
-5Barcol hardness when the linear expansivity of/K, 5～25 180 ℃ are warm and 1.00～1.60 forming composition proportion.
5. use low specific gravity unsaturated polyester resin composition like each described lamp reflector of claim 1～4, it is characterized in that the forming composition of above-mentioned resin combination has 5～20 planeness.
6. forming composition is that each the described lamp reflector through moulding claim 1～5 obtains with low specific gravity unsaturated polyester resin composition.
7. forming composition as claimed in claim 6 is characterized in that, said forming composition has-0.15～+ 0.05% molding shrinkage, 1.0～2.5 * 10
-5Barcol hardness when the linear expansivity of/K, 5～25 180 ℃ are warm and 1.00～1.60 forming composition proportion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2004/004586 WO2005103152A1 (en) | 2004-03-31 | 2004-03-31 | Low specific gravity unsaturated polyester resin composition for lamp reflector and moldings thereof |
| JPPCT/JP2004/004586 | 2004-03-31 | ||
| PCT/JP2005/004107 WO2005097895A1 (en) | 2004-03-31 | 2005-03-09 | Low-specific-gravity unsaturated polyester resin composition for lamp reflector and molding thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1934192A CN1934192A (en) | 2007-03-21 |
| CN1934192B true CN1934192B (en) | 2012-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800089739A Expired - Fee Related CN1934192B (en) | 2004-03-31 | 2005-03-09 | Low specific gravity unsaturated polyester resin composition for lamp reflector and moldings thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JPWO2005103152A1 (en) |
| CN (1) | CN1934192B (en) |
| HK (1) | HK1101698A1 (en) |
| TW (1) | TWI361818B (en) |
| WO (2) | WO2005103152A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5225793B2 (en) * | 2008-09-11 | 2013-07-03 | 京セラケミカル株式会社 | Thermosetting molding material and low specific gravity molding |
| JP5262846B2 (en) * | 2009-03-05 | 2013-08-14 | ダイソー株式会社 | Diallyl phthalate cross-linked low shrinkable unsaturated polyester resin molding composition and molded article thereof |
| CN102061053B (en) * | 2009-10-22 | 2013-05-08 | 上海琥达投资发展有限公司 | Resin matrix composite material sanitary appliance and preparation method thereof |
| KR101655475B1 (en) * | 2010-10-22 | 2016-09-07 | 현대모비스 주식회사 | Bulk molding compound used for lamp reflector |
| WO2013137327A1 (en) * | 2012-03-14 | 2013-09-19 | 昭和電工株式会社 | Unsaturated polyester resin composition for lamp reflector and molded product thereof, and lamp reflector |
| WO2013151151A1 (en) * | 2012-04-05 | 2013-10-10 | ジャパンコンポジット株式会社 | Molding material for lamp reflectors and molded article |
| DE112013002687T5 (en) * | 2012-05-28 | 2015-03-19 | Showa Denko K.K. | Unsaturated polyester resin composition, molded article thereof and lamp reflector |
| DE102012109803A1 (en) * | 2012-06-21 | 2013-12-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | High-tensile materials based on unsaturated polyesters |
| JP5946592B2 (en) * | 2014-07-17 | 2016-07-06 | フドー株式会社 | Light reflector material, light reflector, and lighting apparatus |
| CN106795252B (en) * | 2014-09-04 | 2019-01-08 | 昭和电工株式会社 | Unsaturated polyester resin compositions, lamp reflector and its manufacturing method |
| KR20180048637A (en) * | 2015-08-26 | 2018-05-10 | 나가세케무텍쿠스가부시키가이샤 | PRINTING MATERIAL, PATTERNING METHOD, AND PATTERNING DEVICE |
| CN110903622B (en) * | 2019-11-05 | 2022-03-08 | 珠海格力绿色再生资源有限公司 | BMC composite material for air conditioner electrical appliance box and preparation method thereof |
| CN111777846B (en) * | 2020-07-03 | 2023-02-03 | 无锡朴业橡塑有限公司 | SMC (sheet molding compound) molding compound for low-temperature low-pressure weather-resistant agricultural machinery and preparation method thereof |
| WO2023112439A1 (en) * | 2021-12-16 | 2023-06-22 | 株式会社レゾナック | Molding material, acoustic matching member, and ultrasonic sensor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110216A (en) * | 1993-11-25 | 1995-10-18 | 龙烜华 | Special unsaturated polyester film plastics and making method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2531892B2 (en) * | 1992-03-04 | 1996-09-04 | 昭和高分子株式会社 | Unsaturated polyester resin composition |
| JP3174271B2 (en) * | 1995-07-27 | 2001-06-11 | 株式会社小糸製作所 | Molding composition for lamp reflector, method for producing lamp reflector using the same, and lamp reflector |
| JP3662058B2 (en) * | 1995-12-27 | 2005-06-22 | 三井化学株式会社 | Molding material |
| JPH09272795A (en) * | 1996-04-03 | 1997-10-21 | Showa Highpolymer Co Ltd | Low-specific-gravity molding compound for low-pressure molding |
| JP2001064500A (en) * | 1999-08-26 | 2001-03-13 | Matsushita Electric Works Ltd | Unsaturated polyester resin composition and its molded product |
| JP2001261954A (en) * | 2000-03-14 | 2001-09-26 | Showa Highpolymer Co Ltd | Flame-retardant low-specific gravity unsaturated polyester resin composition |
-
2004
- 2004-03-31 WO PCT/JP2004/004586 patent/WO2005103152A1/en active Application Filing
- 2004-03-31 JP JP2006516824A patent/JPWO2005103152A1/en active Pending
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2005
- 2005-03-09 CN CN2005800089739A patent/CN1934192B/en not_active Expired - Fee Related
- 2005-03-09 JP JP2006511927A patent/JP4673298B2/en not_active Expired - Fee Related
- 2005-03-09 WO PCT/JP2005/004107 patent/WO2005097895A1/en active Application Filing
- 2005-03-30 TW TW094110087A patent/TWI361818B/en active
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- 2007-06-12 HK HK07106255.0A patent/HK1101698A1/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110216A (en) * | 1993-11-25 | 1995-10-18 | 龙烜华 | Special unsaturated polyester film plastics and making method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JP平2-38086A 1990.08.29 |
| JP特开2001-261954A 2001.09.26 |
| JP特开平5-247333A 1993.09.24 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005103152A1 (en) | 2005-11-03 |
| JPWO2005103152A1 (en) | 2007-08-16 |
| HK1101698A1 (en) | 2007-10-26 |
| JPWO2005097895A1 (en) | 2008-02-28 |
| JP4673298B2 (en) | 2011-04-20 |
| TWI361818B (en) | 2012-04-11 |
| TW200604289A (en) | 2006-02-01 |
| CN1934192A (en) | 2007-03-21 |
| WO2005097895A1 (en) | 2005-10-20 |
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