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CN105246941A - Polyester resin, and polyester resin composition for surface-mount-type led reflective plate which comprises same - Google Patents

Polyester resin, and polyester resin composition for surface-mount-type led reflective plate which comprises same Download PDF

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Publication number
CN105246941A
CN105246941A CN201480028826.7A CN201480028826A CN105246941A CN 105246941 A CN105246941 A CN 105246941A CN 201480028826 A CN201480028826 A CN 201480028826A CN 105246941 A CN105246941 A CN 105246941A
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vibrin
resin composition
polyester
acid
mass parts
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CN105246941B (en
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户川惠一朗
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Toyobo Co Ltd
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Toyobo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Led Device Packages (AREA)

Abstract

Disclosed is a polyester resin which comprises a dicarboxylic acid component containing 50 mol% or more of an aromatic dicarboxylic acid and a glycol component containing 15 mol% or more of 4,4'-biphenyldimethanol, and which has a melting point of 280oC or higher. Also disclosed is a polyester resin composition comprising the polyester resin (A), titanium oxide (B), at least one reinforcing material (C) selected from the group consisting of a fibrous reinforcing material and a needle-like reinforcing material, and a non-fibrous or non-needle-like filler (D), wherein titanium oxide (B), the reinforcing material (C) and the non-fibrous or non-needle-like filler (D) are contained in amounts of 0.5 to 100 parts by mass, 0 to 100 parts by mass and 0 to 50 parts by mass, respectively, relative to 100 parts by mass of the polyester resin (A). The polyester resin composition can be used suitably for a reflective plate for a surface-mount-type LED.

Description

The surface mounting LED reflector polyester and resin composition of vibrin and use vibrin
Technical field
The present invention relates to a kind of its formability, mobility, dimensional stability, low water absorbable, scolding tin thermotolerance, surface albedo etc. better, and its gold/soldering tin thermotolerance, photostabilization, low water absorbable also preferably vibrin, and employ this vibrin be highly suitable for the polyester and resin composition that surface mounting LED reflector uses.
Background technology
In recent years, features such as LED (photodiode) flexible utilization low power consumption, long lifetime, high brightness, Miniaturizable and be applied to lighting fixtures, optical element, mobile phone, liquid-crystal display backlight, automobile control panel, teleseme, display panel etc.In addition, in the purposes paying attention to appearance design, portability, surface mounting technique is employed for realizing compact.
Surface mounting LED, usually by the LED chip of luminescence, wire, hold concurrently as the reflector of housing and sealing resin are formed, but in order to be engaged by pb-free solder by all parts be arranged on electric substrate, each part must be formed by the material that can tolerate Reflow Soldering temperature 260 DEG C.The melting point (peak melting temperature) of material must more than 280 DEG C.Especially, about reflector, except these thermotolerances, also require the surface albedo that light extraction efficiency is higher and to heat and ultraviolet weather resistance.Consider from above viewpoint, the various heat resistant plastics material such as pottery and semiaromatic polyamide composition, liquid crystalline polymers, thermosetting silicone are inquired into, wherein, the resin of the contour refraction filler of titanium oxide is dispersed with in semiaromatic polyamide composition and polyester, the balance of its mass productivity, thermotolerance, surface albedo etc. is better, uses the most general.Recently, along with the generalization of LED, need the workability and the reliability that improve reflector further, and require to improve heat-resisting tint permanence, photostabilization for a long time.
As LED reflection plate polyester and resin composition, such as, patent documentation 1 ~ 5 is proposed.
In patent documentation 1,2, disclose a kind of vibrin be made up of dicarboxylic acid component (a) and diol component (b), wherein, dicarboxylic acid component (a) comprises: i) terephthalic acid residue 70 ~ 100 % by mole; Ii) carbon number is the aromatic dicarboxylic acid residue 0 ~ 30 % by mole of less than 20; And iii) carbon number be less than 16 aliphatic dicarboxylic acid residue 0 ~ 10 % by mole; Diol component (b) comprises: i) TMCBD residue 1 ~ 99 % by mole; And ii) 1,4-cyclohexanedimethanol residues 1 ~ 99 % by mole (here, total molecular fraction of dicarboxylic acid component is 100 % by mole, total molecular fraction of diol component is 100%), although there is the trend that mechanical property is better, there is the problem of formability, photostabilization aspect.
In addition, in patent documentation 3, disclosing a kind of take semiconductor light-emitting elements as the means of illumination reflector flame-retardant polyester resin composition of light source, it is characterized in that, be mixed with phosphinates (B) 2 ~ 50 mass parts of calcium salt that anionicsite is phospho acid or aluminium salt, titanium dioxide (C) 0.5 ~ 30 mass parts relative to vibrin (A) 100 mass parts and there is polyolefin resin (D) 0.01 ~ 3 mass parts of polar group, but, there is the problem of gold/soldering tin thermotolerance, thermotolerance, photostabilization aspect.
In addition, in patent documentation 4, disclose a kind of resin combination, it is by all aromatic thermotropic liquor polyester 100 mass parts, titanium oxide 97 ~ 85 quality % aluminum oxide (comprising hydrate) 3 ~ 15 quality % (both are combined is 100 quality %) that manufacture method by comprising sinter process is obtained is carried out Titanium particles 8 ~ 42 mass parts that surface treatment is formed, glass fibre 25 ~ 50 mass parts, and other inorganic filling material 0 ~ 8 mass parts are formed, and process comprises the melting mixing technique of following technique and obtains, namely, use twin screw compounder, described glass fibre is supplied at least partially from the downstream side position of the cylinder body total length more than 30% of twin screw compounder.But there is the problem of thermotolerance, weathering resistance aspect in this resin combination.
In addition, in patent documentation 5, disclose a kind of LED reflection plate unsaturated polyester resin compositions, it is characterized in that, at least comprise unsaturated polyester resin, polymerization starter, inorganic filler, white pigment, releasing agent, and the dry type unsaturated polyester resin compositions of reinforcement material, described unsaturated polyester resin relative to described composition in its entirety amount within the scope of 14 ~ 40 quality %, the combined amount of described inorganic filler and described white pigment amounts to relative to described composition in its entirety amount within the scope of 44 ~ 74 quality %, described white pigment shared ratio in the combined amount of described inorganic filler and described white pigment amounts to is more than 30 quality %, described unsaturated polyester resin is mixed by unsaturated alkyd resin and linking agent, but there is formability, the problem of photostabilization aspect.
In addition, up to now, as surface mounting LED reflector, employ various polymeric amide always, but there is the problem of heat-resisting tint permanence, photostabilization, water-absorbent aspect.
As mentioned above, when heat-resisting tint permanence, photostabilization, formability problem are not resolved, the polyester that continuation use proposed in the past and polymeric amide are truths.
In addition, in recent years, also the purposes in illumination is actively expanded.When considering the expansion to lighting use, requiring further to reduce costs with superpower, improve the life-span, improving long-term reliability.Therefore, as improving the scheme of reliability, on the joint of lead frame and LED chip, do not use epoxy resin/silver paste in the past, and use deterioration less and the higher gold/tin eutectic solder of thermal conductivity.But the processing due to gold/tin eutectic solder needs more than 280 DEG C and lower than the temperature of 290 DEG C, so require that the melting point of used resin is more than 290 DEG C to tolerate technique.In addition, when processing gold/tin eutectic solder, in order to prevent the expansion (sand holes) on the moulding product surface of causing because of the moisture in resin, also require that resin has low water absorbable.
As mentioned above, fully meet the polyester and resin composition of the characteristic that can be used in surface mounting LED reflector, also do not report up to now.
[patent documentation]
Patent documentation 1: Japanese documentation spy table No. 2008-544030 bulletin
Patent documentation 2: Japanese documentation spy table No. 2008-544031 bulletin
Patent documentation 3: No. 2010-270177, Japanese Patent Laid-Open bulletin
Patent documentation 4: No. 2008-231368, Japanese Patent Laid-Open bulletin
Patent documentation 5: Japanese documentation speciallys permit No. 4844699 bulletins
Invent technical problem to be solved
The present invention completes in view of the problem of above-mentioned prior art, its object is to the surface mounting LED reflector polyester and resin composition a kind of vibrin being provided and using this vibrin, the formability of described vibrin when injection moulding, mobility, dimensional stability, low water absorbable, scolding tin thermotolerance, surface albedo and photostabilization good, and, for guaranteeing long-term reliability, achieve the high melting point can applying gold/tin eutectic solder technique, be intended to the low water absorbable of the expansion reducing the products formed that the moisture in weldprocedure causes, photostabilization when outdoor use and life-time service.
Summary of the invention
In order to achieve the above object, the present inventor attentively have studied not only to meet and can also carry out injection moulding and solder reflow process easily as the characteristic of LED reflector, further, the composition of its gold/tin eutectic solder thermotolerance, low water absorbable, photostabilization preferably polyester, finally completes the present invention.
That is, the present invention has the formation of following (1) ~ (11).
(1) vibrin, is characterized in that, be made up of, and melting point is more than 280 DEG C the dicarboxylic acid component containing aromatic dicarboxylic acid more than 50 % by mole and the diol component containing 4,4'-biphenyl dimethanol more than 15 % by mole.
(2) vibrin described in (1), is characterized in that, aromatic dicarboxylic acid comprises at least one dicarboxylic acid selected from the group be made up of 4,4'-diphenyldicarboxylic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acids.
(3) (1) or the vibrin described in (2), it is characterized in that, form 4 of vibrin, diol component beyond 4'-biphenyl dimethanol, comprise from by ethylene glycol, 1, the at least one glycol selected in the group of 4-cyclohexanedimethanol, 1,3-PD, neopentyl glycol and BDO composition.
(4) vibrin described in any one of (1) ~ (3), is characterized in that, when the melting point (Tm) of vibrin and cooling, the difference of crystallized temperature (Tc2) is less than 42 DEG C.
(5) vibrin described in any one of (1) ~ (4), is characterized in that, the acid value of vibrin is 1 ~ 40eq/t
(6) polyester and resin composition used on surface mounting LED reflector, it is characterized in that, described polyester and resin composition contains the vibrin (A) described in any one of (1) ~ (5), titanium oxide (B), the at least one strongthener (C) selected from the group be made up of fibrous reinforcements and needle-like strongthener, and Non-fibrous or non-needle-like packing material (D), and, relative to vibrin (A) 100 mass parts, titanium oxide (B), strongthener (C), and Non-fibrous or non-needle-like packing material (D) are respectively with 0.5 ~ 100 mass parts, 0 ~ 100 mass parts, and 0 ~ 50 mass parts ratio exist.
(7) polyester and resin composition described in (6), it is characterized in that, Non-fibrous or non-needle-like packing material (D) are talcum powder, and relative to vibrin (A) 100 mass parts, it contains proportional is 0.1 ~ 5 mass parts.
(8) (6) or the polyester and resin composition described in (7), is characterized in that, Reflow Soldering heat resisting temperature is more than 260 DEG C
(9) polyester and resin composition described in any one of (6) ~ (8), is characterized in that, Reflow Soldering heat resisting temperature is more than 280 DEG C.
(10) polyester and resin composition described in any one of (6) ~ (9), it is characterized in that, the peak melting temperature (Tm) of polyester and resin composition is more than 280 DEG C, and when peak melting temperature (Tm) and cooling, the difference of crystallized temperature (Tc2) is below 42 DEG C.
(11) surface mounting LED reflector, is characterized in that, uses the polyester and resin composition described in any one of (6) ~ (10) carry out shaping and obtain.
Invention effect
Vibrin of the present invention, not only have higher thermotolerance and lower water-absorbent, the workabilitys such as formability during injection moulding and scolding tin thermotolerance are also better.Therefore, polyester and resin composition of the present invention owing to using described vibrin, therefore, it is possible to convenient and industrialization produce the surface mounting LED reflector highly meeting all essential feature.
In addition, polyester and resin composition of the present invention, because main component vibrin has the high melting point of more than 280 DEG C and thermotolerance is also better, so gold/tin eutectic solder technique can also be applied to, and, because aromatic nucleus concentration is higher, so not only have good thermotolerance, tenacity, photostabilization, can also demonstrate and the stickiness of the packaged material also feature such as comparatively good.
Embodiment
Vibrin of the present invention, as the material used on the moldinies such as film, thin slice, injection-molded article, special-shaped formed body, particularly as the material used on surface mounting LED reflector, has good characteristic.In addition, polyester and resin composition of the present invention, surface mounting LED reflector uses.Surface mounting LED, can list the chip LED type using printed wiring board, the gull aerofoil profile, PLCC type etc. that use lead frame, and polyester and resin composition of the present invention can produce the above-mentioned all reflectors enumerated by injection moulding.
Polyester and resin composition of the present invention contains vibrin (A), titanium oxide (B), at least one strongthener (C) selected from the group be made up of fibrous reinforcements and needle-like strongthener and Non-fibrous or non-needle-like packing material (D).
Vibrin (A), in order to give higher reliability, except realizing high melting point, low water absorbable, also form to realize preferably uv-resistance and allocating, it is characterized in that, be made up of the dicarboxylic acid component containing aromatic dicarboxylic acid more than 50 % by mole and the diol component containing 4,4'-biphenyl dimethanol more than 15 % by mole, and melting point is more than 280 DEG C.The melting point of vibrin (A), is preferably more than 290 DEG C, is more preferably more than 300 DEG C, is more preferably more than 310 DEG C.The upper limit of vibrin (A) melting point is also not particularly limited, but from the restriction of operable feed composition, below 340 DEG C.Melting point is measured by the method described in the project of embodiment.
As the dicarboxylic acid component of vibrin (A) and the aromatic dicarboxylic acid used, can 4 be listed, 4'-diphenyldicarboxylic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acids, m-phthalic acid, diphenoxyethanedicarboxylic acid, 4,4'-oxydibenzoic acid, 4,4'-benzophenone dicarboxylic acid etc.In above-mentioned aromatic dicarboxylic acid, consider from polymerizability, cost and thermotolerance, be preferably 4,4'-diphenyldicarboxylic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acids or these mixture.Aromatic dicarboxylic acid, from the viewpoint of thermotolerance, at more than 50 % by mole of dicarboxylic acid component, be preferably more than 60 % by mole, be more preferably more than 70 % by mole, be more preferably more than 80 % by mole, be particularly preferably more than 90 % by mole, and also can be 100 % by mole.In addition, as the dicarboxylic acid beyond aromatic dicarboxylic acid, aliphatic dicarboxylic acid, hexahydroterephthalic acid, the hexahydro-m-phthalic acids, 1 such as hexanodioic acid, sebacic acid, succinic acid, pentanedioic acid, dimeracid can be listed, 2-cyclohexyl dicarboxylic acid, 1, the alicyclic dicarboxylic acids etc. such as 3-cyclohexyl dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid.In addition, polyvalent carboxylic acid and the anhydrides thereof such as the oxygen acid such as p-hydroxy-benzoic acid, oxygen base caproic acid, trimellitic acid, Pyromellitic Acid, benzophenone tetracarboxylic, sulfobenzide tetracarboxylic acid, biphenyltetracarboxyacid acid can also be used simultaneously.
In addition, diol component as vibrin (A) use 4,4'-biphenyl dimethanol needs more than 15 % by mole containing whole diol component, be preferably 4,4'-biphenyl dimethanol is more than 50 % by mole, be more preferably more than 60 % by mole, be more preferably more than 65 % by mole, most preferably be more than 70 % by mole.4,4'-biphenyl dimethanol is in order to improve formability, scolding tin thermotolerance, photostabilization and adding, and when its ratio is lower than above-mentioned numerical value, these characteristics have a declining tendency.As the diol component beyond 4,4' biphenyl dimethanol, such as, ethylene glycol can be listed, Diethylene Glycol, propylene glycol, 1,3-PD, BDO, 1,2-butyleneglycol, 1,3 butylene glycol, 2,3-butanediol, 1,5-PD, 1,6-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1,2-CHDM, 1,3-CHDM, 1,4 cyclohexane dimethanol, Isosorbide-5-Nitrae-hexanaphthene di-alcohol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, ammediol, 2-ethyl-1,3-PD, neopentyl glycol, 2-Ethyl-2-Methyl-1,3-PD, 2,2-diethyl-1,3-PD, 2-methyl-2-n-butyl-1,3-PD, 2-n-butyl-2-ethyl-1,3-PD, two-n-butyl-the 1,3-PD of 2,2-, 2-ethyl-2-n-hexyl-1,3-PD, two-n-hexyl-the 1,3-PD of 2,2-, 1,9-nonanediol, decamethylene-glycol, 1,12-dodecanediol, triethylene glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, the aliphatic dihydroxy alcohols such as polypropylene glycol, dihydroxy-benzene, 4,4'-dihydroxyl bis-phenol aldehyde, Isosorbide-5-Nitrae-bis-(beta-hydroxy oxyethyl group) benzene, Isosorbide-5-Nitrae-bis-(beta-hydroxy ethoxyl phenenyl) sulfone, two (p-is to hydroxyphenyl) ether, two (p-is to hydroxyphenyl) sulfone, two (p-is to hydroxyphenyl) methane, two (p-is to the hydroxyphenyl) ethane of 1,2-, dihydroxyphenyl propane, the aromatic diols etc. such as the alkylene oxide adduct of dihydroxyphenyl propane.In above-mentioned glycol, from the viewpoint of thermotolerance, polymerizability, formability, cost etc., one or more the mixture preferably selected from ethylene glycol, 1,4 cyclohexane dimethanol, 1,3-PD, neopentyl glycol, BDO.Be more preferably, one or more the mixture selected from ethylene glycol, BDO.In addition, if employ ethylene glycol in diol component, then when manufacturing vibrin (A), secondary can bear Diethylene Glycol, becoming copolymerization component sometimes.In this case, secondary Diethylene Glycol depends on manufacturing condition, but is about 1 ~ 5 % by mole relative to the ethylene glycol be embedded in vibrin.In addition, the polyvalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), glycerine, tetramethylolmethane can also be used simultaneously.
Vibrin, when whole component is 200 % by mole, the total of above-mentioned dicarboxylic acid component and diol component, is preferably more than 160 % by mole, is more preferably more than 180 % by mole, is more preferably more than 190 % by mole, and also can be 200 % by mole.But no matter be any situation, dicarboxylic acid component and diol component all can not more than 100 % by mole.
In addition, in the scope of less than 20 % by mole of all acid component or whole diol components, also can use containing 5-sulfonic group m-phthalic acid, 4-sulfonaphthol-2, metal-salt or the 2-sulfo groups-1 such as 7-dicarboxylic acid, 5-[4-sulfophenoxy] m-phthalic acid, 4-butyleneglycol, 2, the dicarboxylic acid of the Sulfonic acid metal alkali such as metal-salt such as 5-dimethyl-3-sulfo group-2,5-hexylene glycol or glycol.
As the catalyzer used when manufacturing vibrin (A), although be not particularly limited, preferably use at least one compound selected from the compound of Ge, Ti, Sb, Al, Mn or Mg.These compounds as powder, the aqueous solution, ethylene glycol solution, ethylene glycol slurry etc. and be added in reactive system.
In addition, as resin stabilizer, preferably use at least one phosphorus compound selected from the group be made up of phosphoric acid ester, phosphonic acids compounds, phospho acid compounds, phosphine oxide-type compound, phosphonous acid-type compound, phosphinous acid compounds, phosphiness such as phosphoric acid, Tripyrophosphoric acid and trimethyl phosphite 99s.
As the acid value of vibrin (A), be preferably 1 ~ 40eq/ton.If acid value is more than 40eq/ton, then photostabilization has a declining tendency.In addition, when acid value is lower than 1eq/ton, polycondensation declines, and productivity is tending towards reducing.
Vibrin of the present invention (A), the melting point (Tm) during dsc measurement, more than 280 DEG C, is preferably more than 290 DEG C, is more preferably more than 300 DEG C, is particularly preferably more than 310 DEG C, most preferably be more than 320 DEG C.On the other hand, the upper limit of the melting point (Tm) of vibrin of the present invention, is preferably less than 340 DEG C.If melting point (Tm) is more than 340 DEG C, then when carrying out injection moulding to the composition employing vibrin of the present invention (A), required processing temperature can become high, can decompose so add man-hour vibrin, can not get desired physical property and outward appearance sometimes.On the contrary, if melting point (Tm) is lower than above-mentioned lower limit, then crystallization rate is slack-off, sometimes shaping all can become difficulty, and, also may reduce scolding tin thermotolerance.If melting point (Tm) is more than 310 DEG C, then meets the reflow tin soldering thermotolerance of 280 DEG C, and also can be applied to gold/tin eutectic solder technique, therefore ideal.
In addition, vibrin of the present invention (A), the difference of crystallized temperature (Tc2) when the melting point (Tm) when dsc measurement and cooling, be preferably less than 42 DEG C, be more preferably less than 40 DEG C, be more preferably less than 35 DEG C, most preferably be less than 30 DEG C.During so-called cooling, crystallized temperature (Tc2), refers in dsc measurement, when lowering the temperature from the temperature of higher than melting point more than 10 DEG C, starts the temperature of crystallization.When melting point (Tm) and cooling, crystallized temperature (Tc2), is measured by the method described in the project of embodiment.When melting point (Tm) and cooling, the difference of crystallized temperature (Tc2) is below said temperature, crystallization becomes easy, can give full play to dimensional stability and physical property etc.On the other hand, if the difference of crystallized temperature (Tc2) exceedes said temperature when melting point (Tm) and cooling, then LED reflector injection moulding compared with short period in shaping, therefore crystallization can become insufficient sometimes, the difficult forming such as cause the demoulding insufficient, or crystallization complete insufficient, so to deform when the heating of subsequent technique or crystallization is shunk, and there is the problem peeled off from packaged material or lead frame, lack reliability.
The limiting viscosity (IV) of vibrin (A), is preferably 0.10 ~ 0.70dl/g, is more preferably 0.20 ~ 0.65dl/g, is more preferably 0.25 ~ 0.60dl/g.
Vibrin (A), in polyester and resin composition of the present invention, is preferably with the ratio of 25 ~ 90 quality %, is more preferably and exists with the ratio of 40 ~ 75 quality %.If the ratio of vibrin (A) is lower than above-mentioned lower limit, then physical strength reduce, and if exceed the above-mentioned upper limit, then titanium oxide (B) and strongthener (C) combined amount can deficiency, be difficult to obtain desired effect.
Titanium oxide (B) mixes in order to the surface albedo improving reflector, can exemplify out, the rutile-type such as made by sulfuric acid process or chlorination process and the titanium dioxide (TiO of anatase titanium dioxide 2), titanium monoxide (TiO), titanium trioxide (Ti 2o 3) etc., be especially preferably the titanium dioxide (TiO using rutile-type 2).The median size of titanium oxide (B) is generally 0.05 ~ 2.0 μm, is preferably the scope of 0.15 ~ 0.5 μm, also can use one, can also combinationally use the titanium oxide with different-grain diameter.As titanium oxide concentration of component, at more than 90 quality %, be preferably more than 95 quality %, be more preferably more than 97 quality %.In addition, titanium oxide (B) can use metal oxides such as utilizing silicon-dioxide, aluminum oxide, zinc oxide, zirconium white, coupling agent, organic acid, organic polyhydric alcohol, siloxanes etc. to implement surface-treated material.
The ratio of titanium oxide (B), relative to vibrin (A) 100 mass parts, is 0.5 ~ 100 mass parts, is preferably 10 ~ 80 mass parts.If the ratio of titanium oxide (B) is lower than above-mentioned lower limit, then surface albedo can reduce, if exceed the above-mentioned upper limit, then physical property significantly reduces or mobility reduction etc. likely can make molding processibility reduce.
Strongthener (C) mixes for improving the formability of polyester and resin composition and the intensity of products formed, uses at least one selected from fibrous reinforcements and needle-like strongthener.As fibrous reinforcements, can list, such as glass fibre, carbon fiber, boron fibre, ceramic fiber, steel fiber etc., as needle-like strongthener, can list, such as potassium titanate crystal whisker, aluminium borate whisker, ZnOw, calcium carbonate crystal whisker, magnesium sulfate crystal whisker, wollastonite etc.As glass fibre, the chopped strand or continuous filament fibers with 0.1mm ~ 100mm length can be used.As the cross-sectional shape of glass fibre, the glass fibre of rounded section and noncircular cross section can be used.The diameter of rounded section glass fibre, is preferably less than 20 μm, is more preferably less than 15 μm, is more preferably less than 10 μm.In addition, consider from physicals and mobility, be preferably the glass fibre of noncircular cross section.As the glass fibre of noncircular cross section, in the cross section that the length direction long with fiber is vertical, also comprise the cross section of general oval, general oval, substantially cocoon shape, and compression is preferably 1.5 ~ 8.Here, so-called compression, refers to the rectangle at the external minimum area in the cross section that hypothesis is vertical with the length direction of glass fibre, and using the length on this rectangular long limit as major axis, the ratio of major axis/minor axis during using the length of minor face as minor axis.The thickness of glass fibre is also not particularly limited, but minor axis is about 1 ~ 20 μm, and major axis is about 2 ~ 100 μm.In addition, glass fibre is fibrous bundle, preferably can use the fibrous bundle of the chopped strand shape being cut into long about the 1 ~ 20mm of fiber.In addition, in order to improve the surface albedo of polyester and resin composition, better with the refringence of vibrin, so use the vibrin being improved specific refractory power by change glass formation or surface treatment to be good.
The ratio of strongthener (C), relative to vibrin (A) 100 mass parts, is 0 ~ 100 mass parts, is preferably 5 ~ 100 mass parts, is more preferably 10 ~ 60 mass parts.Although strongthener (C) is not neccessary composition, if its ratio is more than 5 mass parts, then the physical strength of products formed can improve, so ideal.If the ratio of strongthener (C) exceedes the above-mentioned upper limit, then surface albedo, molding processibility may be made to reduce.
As Non-fibrous or non-needle-like packing material (D), according to the difference of object, enhancing filler and conductive filler material can be listed, magnetic fillers, fire-retardant filler, heat conductive filler, hot xanthochromia suppression filler etc., glass microballon can be listed particularly, glass flake, granulated glass sphere, silicon-dioxide, talcum powder, kaolin, mica, aluminum oxide, hydrotalcite, polynite, graphite, carbon nanotube, soccerballene, Indium sesquioxide, stannic oxide, ferric oxide, magnesium oxide, aluminium hydroxide, magnesium hydroxide, calcium hydroxide, red phosphorus, calcium carbonate, magnesium acetate, lead zirconate titanate, barium titanate, aluminium nitride, boron nitride, lead borate, barium sulfate, and the wollastonite of non-needle-like, potassium titanate, aluminum borate, magnesium sulfate, zinc oxide, calcium carbonate etc.These packing materials not only can be used alone one, multiple combination can also be used.In the middle of these, talcum powder has the effect accelerating crystallization, improves formability, therefore ideal.The addition of packing material can select optimum quantity, and relative to vibrin (A) 100 mass parts, maximum 50 mass parts of can adding, but from the viewpoint of the physical strength of resin combination, be preferably 0.1 ~ 20 mass parts, be more preferably 1 ~ 10 mass parts.In the talcous situation of use, relative to vibrin (A) 100 mass parts, be preferably 0.1 ~ 5 mass parts, be more preferably 0.5 ~ 3 mass parts.In addition, fibrous reinforcements, packing material can improve the affinity with vibrin, are therefore preferably the material used through organic process or coupling agent treatment, or when melting compound and coupling agent use simultaneously; As coupling agent, can use in silane coupling agent, titanate coupling agents, aluminium class coupling agent any one, but wherein, be especially preferably amino silicane coupling agent, epoxy silane coupling agent.
In polyester and resin composition of the present invention, the various additives of LED reflection plate polyester and resin composition in the past can be used.As additive, the thermoplastic resin etc. beyond stablizer, modified impact material, fire retardant, releasing agent, sliding improved materials, tinting material, white dyes, softening agent, Nucleating Agent, polyester can be listed.
As the stablizer of resin combination, photostabilizer or UV light absorber, metal passivator, the copper compound etc. such as the organic oxidation inhibitor such as Hinered phenols antioxidant, sulphur kind antioxidant, Phosphorus oxidation inhibitor or thermo-stabilizer, hindered amines, benzophenone class, imidazoles can be listed.As copper compound, the cuprate etc. of the organic carboxyl acids such as cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, cupric sulfide, cupric nitrate, jealous woman acid copper can be used.In addition, as the component beyond copper compound, be preferably containing alkali halide metallic compound, as alkali halide metallic compound, lithium chloride, lithiumbromide, lithium iodide, Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide, Potassium monofluoride, Repone K, Potassium Bromide, Potassium monofluoride etc. can be listed.These additives not only can be used alone one, also multiple combination can be used.The addition of stablizer can select optimum quantity, and relative to vibrin (A) 100 mass parts, maximumly can add 5 mass parts.
In polyester and resin composition of the present invention, the thermoplastic resin different from vibrin (A) can be added.Such as: polymeric amide (PA) can be listed, polyphenylene sulfide (PPS), liquid crystalline polymers (LCP), tetrafluoroethylene (PTFE), fluorine resin, aramid fiber resin, polyether-ether-ketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, polyamidoimide (PAI), PEKK (PEKK), polyphenylene oxide (PPE), polyethersulfone (PES), polysulfones (PSU), polyarylester (PAR), polyethylene terephthalate, polybutylene terephthalate, PEN, PBN, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene (PS), polymethylmethacrylate, acrylonitritrile-styrene resin (AS), acrylonitrile-butadiene-styrene copolymer (ABS).These thermoplastic resins, by melting mixing, can mix in the molten state, thermoplastic resin can also be made threadiness, particulate state, and be distributed in polyester and resin composition of the present invention.The addition of thermoplastic resin can select optimum quantity, and relative to vibrin (A) 100 mass parts, maximumly can add 50 mass parts.
As impact modifying agent, ethylene-propylene rubber (EPM) can be listed, ethylene/propylene/diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate multipolymer, the polyolefin resins such as ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene isoprene styrene block copolymer (SIS) (SIS), the ethene polymers resinoids such as acrylate copolymer, using polybutylene terephthalate or PBN as hard section, using polytetramethylene glycol or polycaprolactone or the polycarbonate diol polyester block copolymer as soft section, nylon elastomer, urethane elastomer, acrylic elastomer, silicon rubber, fluorine class rubber, there is the polymer particle etc. of the nucleocapsid structure be made up of two kinds of different polymkeric substance.The addition of impact modifying agent can select optimum quantity, and relative to vibrin (A) 100 mass parts, maximumly can add 30 mass parts.
For polyester and resin composition of the present invention, when the thermoplastic resin added beyond vibrin (A) and shock-resistant improved materials, be preferably copolymerization have can with the reactive group of pet reaction, and reactive group be can with the group of the end group of vibrin and hydroxyl and/or carboxyl reaction.Specifically, anhydride group, epoxide group, oxazoline group, amino, isocyanate groups etc. can be listed, but the reactivity of epoxide group, isocyanate groups is best in the middle of these.Like this, also have report weighing-appliance to have the thermoplastic resin of the reactive group reacted with vibrin finely divided in polyester, just because of finely divided, interparticle distance shortens, and shock-resistance obtains significantly to be improved.
As fire retardant, be preferably the combination of halogen fire retardant and flame retardant; As halogen fire retardant, be preferably brominated Polystyrene, brominated polyphenylether, brominated bisphenol type epoxide polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perchloro-cyclopentadecane and bromination crosslinked aromatic polymkeric substance etc.; As flame retardant, the layered silicates such as antimonous oxide, antimony pentaoxide, sodium antimonate, zinc, zinc borate, polynite, fluorine type polymer, silicone etc. can be listed.Wherein, from the viewpoint of thermostability, be preferably dibromo polystyrene as halogen fire retardant, be preferably and any one combination in antimonous oxide, sodium antimonate, zinc as flame retardant.In addition, as non-halogen based flame retardant, melamine cyanurate, red phosphorus, metal phosphinate, Nitrogen-and Phosphorus-containing acid compounds can be listed.Particularly, be preferably the combination of metal phosphinate and Nitrogen-and Phosphorus-containing acid compounds, comprise the such condensation product of trimeric cyanamide of trimeric cyanamide or melam, melem, mellon and the resultant of reaction of Tripyrophosphoric acid or their mixture as Nitrogen-and Phosphorus-containing acid compounds.As other fire retardant, flame retardant, when using these fire retardants, in order to prevent the metallic corrosion of mould etc., being preferably and adding hydrotalcite compounds or alkali cpd.The addition of fire retardant can select optimum quantity, and relative to vibrin (A) 100 mass parts, maximumly can add 50 mass parts.
As releasing agent, longer chain fatty acid or its ester and metal-salt, amides compound, polyethylene wax, silicone, polyethylene oxide etc. can be listed.As longer chain fatty acid, be particularly preferably carbon number more than 12, such as can list stearic acid, 12-oxystearic acid, docosanoic acid, montanic acid etc., part or all carboxylic acid can be esterified by Monoethylene Glycol (MEG) or PVOH, or also can form metal-salt.As amides, vinyl biconjugate benzenedicarboxamide, methylene radical distearyl acid amides etc. can be listed.These releasing agents can use separately or as mixture.The addition of releasing agent can select optimum quantity, and relative to vibrin (A) 100 mass parts, maximumly can add 5 mass parts.
Polyester and resin composition of the present invention, because comprise vibrin as above (A), therefore in dsc measurement, peak melting temperature (Tm) is preferably more than 280 DEG C, be more preferably more than 290 DEG C, be more preferably more than 300 DEG C, be particularly preferably more than 310 DEG C, most preferably be more than 320 DEG C.On the other hand, the upper limit of the Tm of polyester and resin composition of the present invention is preferably less than 340 DEG C.
In addition, polyester and resin composition of the present invention, because comprise vibrin as above (A), therefore in dsc measurement peak melting temperature (Tm) and cooling time crystallized temperature (Tc2) difference, be preferably less than 42 DEG C, be more preferably less than 40 DEG C, be more preferably less than 35 DEG C, be more preferably less than 30 DEG C.
Vibrin (A), except having higher melting point and formability, the balance of low water absorbable and mobility is good, and photostabilization is good.Therefore, the polyester and resin composition of the present invention obtained by described vibrin (A), surface mounting LED reflector shaping in, not only there is high melting point and the low water absorbable of more than 280 DEG C, but also thin-walled and short-period shaping can be realized.
Polyester and resin composition of the present invention, can pass through well-known method in the past and mix above-mentioned each component and create.Such as, can list: when the polycondensation of vibrin (A), add each composition, or vibrin (A) and other compositions are dry mixed, or each component be carried out the method for melting mixing with twin screw type extruders.
Embodiment
Below, specifically describe the present invention further by embodiment, but the present invention is not limited to these embodiments.Further, the observed value described in embodiment is measured by the following method.
(1) limiting viscosity (IV) of vibrin
In the mixed solvent of sym.-tetrachloroethane/phenol (2:3 weight ratio), try to achieve according to the soltion viscosity at 30 DEG C.
(2) acid value
By after vibrin 0.1g heating for dissolving is in 10ml phenylcarbinol, the solution of the methyl alcohol/phenylcarbinol (1/9 volumetric ratio) of the NaOH of 0.1N is used to carry out titration and try to achieve.
(3) melting point (Tm) of vibrin and resin combination peak melting temperature (Tm), cooling time crystallized temperature (Tc2)
The differential scanning calorimeter (DSC) using Seiko Instruments Inc to manufacture, RDC-220 measure.Heat up with heat-up rate 20 DEG C/minute, after keeping 3 minutes at 330 DEG C, be cooled to 130 DEG C with the speed of 10 DEG C/minute from 330 DEG C.In addition, at 330 DEG C during not melting, after keeping 3 minutes at 340 DEG C, be cooled to 130 DEG C with the speed of 10 DEG C/minute from 340 DEG C.Using the summit temperature of peak melting observed when heating up as melting point (Tm), and using the summit temperature of crystallization peak observed when lowering the temperature as crystallized temperature (Tc2) during cooling.
(4) formability and dimensional stability
Use the injection moulding machine EC-100 that toshiba machine manufactures, temperature cylinder is set as resin melting point+20 DEG C, be 125 DEG C by mold temperature set, and use the flat panel production mould with the long 100mm of film gate, wide 100mm, thick 1mmt, implement injection moulding.Carry out shaping under injection moulding speed 50mm/ second, pressurize 30Mpa, 10 seconds injection times, 10 seconds cooling times, the evaluation of formability is carried out according to following standard.
Zero: obtain products formed no problemly.
Δ: slag can remain in a mold sometimes.
×: release property is not enough, and products formed is pasted onto on mould or distortion.
In addition, in order to evaluate the dimensional stability of gained products formed, at 180 DEG C, 1 hour be heated to above-mentioned products formed.Measure the size on direction vertical with flow direction before and after heating, try to achieve size changing amount as follows.
Size (mm) × 100 before size changing amount (%)={ size (mm) after the size (mm) before heating-heating }/heating
The evaluation of dimensional stability is carried out according to following standard.
Zero: size changing amount is lower than 0.2%
×: size changing amount is more than 0.2%
(5) scolding tin thermotolerance
Use the injection moulding machine EC-100 that toshiba machine manufactures, temperature cylinder being set as resin melting point+20 DEG C, is 140 DEG C by mold temperature set, and injection moulding goes out the UL combustion test test specimen of long 127mm, wide 12.6mm, thick 0.8mmt, has made test specimen.Test specimen 85 DEG C, place 72 hours in the atmosphere of 85%RH (relative temperature).In reflow ovens (AIS-20-82C that Eightech manufactures), utilize within 60 seconds, make test specimen from room temperature to 150 DEG C, and carry out preheating, then until 190 DEG C utilize the heat-up rate of 0.5 DEG C/minute to implement preheating.Then, be warming up to the design temperature of regulation with the speed of 100 DEG C/minute, kept for 10 seconds at an established temperature, cool.The highest design temperature that superficial expansion or distortion do not occur, from 240 DEG C, every 5 DEG C of increases, is set to backflow heat resisting temperature, and have rated scolding tin thermotolerance in order to lower standard by design temperature.
◎: backflow heat resisting temperature is more than 280 DEG C
Zero: backflow heat resisting temperature is more than 260 DEG C and lower than 280 DEG C
×: backflow heat resisting temperature is lower than 260 DEG C
(6) diffuse reflectance
Use the injection moulding machine EC-100 that toshiba machine manufactures, temperature cylinder being set as resin melting point+20 DEG C, be 140 DEG C, and injection moulding goes out the flat board of long 100mm, wide 100mm, thick 2mm by mold temperature set, and system is evaluated uses test specimen.Use this test specimen, the automatic recording spectrophotometer " U3500 " that Hitachi manufactures arranges the integrating sphere that the said firm manufactures, measures the reflectivity of 350nm to 800nm wavelength.As the comparison of reflectivity, try to achieve the diffuse reflectance in 460nm wavelength.Consult and use barium sulfate.
(7) saturated water absorption
Use the injection moulding machine EC-100 that toshiba machine manufactures, temperature cylinder being set as resin melting point+20 DEG C, be 140 DEG C, and injection moulding goes out the flat board of long 100mm, wide 100mm, thick 1mm by mold temperature set, and system is evaluated uses test specimen.This test specimen is flooded 50 hours in the hot water of 80 DEG C, has tried to achieve saturated water absorption according to weight during saturated water suction and time dry and following formula.
Saturated water absorption (%)=(saturated water suction time weight-drying time weight)/drying time weight × 100
(8) mobility
Use the injection moulding machine IS-100 that toshiba machine manufactures, temperature cylinder is set as 330 DEG C, it is 120 DEG C by mold temperature set, and injection pressure set(ting)value be 40%, injection moulding speed set(ting)value is 40%, metering 35mm, 6 seconds injection times, 10 seconds cooling times condition under, injection moulding in the length of flow measurement mould of wide 1mm, thick 0.5mm, system is evaluated uses test specimen.The length of flow (mm) measuring this test specimen is used as the evaluation of mobility.
(9) silicone stickiness
Use the injection moulding machine EC-100 that toshiba machine manufactures, temperature cylinder being set as resin melting point+20 DEG C, be 140 DEG C, and injection moulding goes out the flat board of long 100mm, wide 100mm, thick 2mm by mold temperature set, and system is evaluated uses test specimen.In the one side of this test specimen, (silicone commercial firm of SHIN-ETSU HANTOTAI manufactures silicone-coating packaged material, ASP-1110, packaged material hardness D60), its coating thickness is made to be about 100 μm, at 100 DEG C after preheating 1 hour, hardening treatment 4 hours at 150 DEG C, thus encapsulation material film is formed in the one side of test specimen.
Next, for the encapsulation material film on test specimen, carry out cross cut test (100 grid that 1mm is wide) according to JISK5400, the stickiness according to following standard evaluation.
Zero: peel off grid eye number below 10
×: when the grid eye number form before stripping test becomes, there is stripping
(10) photostabilization
Use the injection moulding machine EC-100 that toshiba machine manufactures, temperature cylinder being set as resin melting point+20 DEG C, be 140 DEG C, and injection moulding goes out the flat board of long 100mm, wide 100mm, thick 2mm by mold temperature set, and system is evaluated uses test specimen.For this test specimen, use and super promote weathering tester " EyesuperUV trier-SUV-F11 ", 63 DEG C, under the environment of 50%RH, with 50mW/cm 2illumination implement UV irradiate.After pre-irradiation with irradiation 60 hours, measure the luminous reflectance factor of the wavelength 460nm of test specimen.According to the luminous reflectance factor of test specimen after irradiating relative to the conservation rate of the luminous reflectance factor of pre-irradiation test specimen, the photostabilization according to following standard evaluation.
◎: conservation rate is more than 95%
Zero: conservation rate lower than 95%, and more than 90%
Δ: conservation rate lower than 90%, and more than 85%
×: conservation rate is lower than 85%
(11) heat-resisting yellowing
Use the injection moulding machine EC-100 that toshiba machine manufactures, temperature cylinder being set as resin melting point+20 DEG C, be 140 DEG C, and injection moulding goes out the flat board of long 100mm, wide 100mm, thick 2mm by mold temperature set, and system is evaluated uses test specimen.Use this test specimen, use hot air dryer process 2 hours at 150 DEG C, confirm yellowing by range estimation, evaluate according to following standard.
Zero: unchanged
Δ: a little yellowing
×: yellowing
(embodiment 1)
In the 20 liters of stainless steel autoclaves being furnished with stirrer, load high purity dimethyl terephthalic acid 3880g, 4,4'-biphenyl dimethanol 2782g, ethylene glycol 1922g, manganese acetate 2g, germanium dioxide 0.86g, after carrying out transesterify, 60 minutes are utilized to be warming up to 300 DEG C, and slowly make the pressure drop of reactive system to 13.3Pa (0.1Torr), and then 310 DEG C, implement polycondensation under 13.3Pa.After pressure release, micro-resin adding pressure is discharged in water for silk thread shape, after cooling, cut off with cutting knife and obtain being about 3mm, tubular bead that diameter is about 2mm.The limiting viscosity of gained vibrin is 0.60dl/g, foundation 1h-NMR measures, and in resin composition, terephthalic acid is 100 % by mole, and 4,4'-biphenyl dimethanol is 65 % by mole, and ethylene glycol is 34.5 % by mole, and Diethylene Glycol is 0.5 % by mole.Composition and the characteristic value of gained vibrin are as shown in table 1.
(embodiment 2 ~ 4)
Except change use raw material amount and kind except, identical with the polymerization of the vibrin of embodiment 1, obtain each vibrin.Composition and the characteristic value of each vibrin of gained are as shown in table 1.In addition, Diethylene Glycol is ethylene glycol generation condensation and secondary.
(embodiment 5)
In the 20 liters of stainless steel autoclaves being furnished with stirrer, load high purity dimethyl terephthalic acid 3880g, 4,4'-biphenyl dimethanol 2782g, ethylene glycol 1922g, manganese acetate 2g, germanium dioxide 0.86g, after carrying out transesterify, add high purity terephthalic acid 8g, utilize 60 minutes to be warming up to 300 DEG C, slowly make the pressure drop of reactive system to 13.3Pa (0.1Torr), and 310 DEG C, implement polycondensation under 13.3Pa.After pressure release, micro-resin adding pressure is discharged in water for silk thread shape, after cooling, utilize cutting knife to cut off and obtain being about 3mm, tubular bead that diameter is about 2mm.The limiting viscosity of gained vibrin is 0.60dl/g, foundation 1h-NMR measures, and in resin composition, terephthalic acid is 100 % by mole, and 4,4'-biphenyl dimethanol is 65 % by mole, and ethylene glycol is 34.5 % by mole, and Diethylene Glycol is 0.5 % by mole.Composition and the characteristic value of gained vibrin are as shown in table 1.
(comparative example 1)
In the 20 liters of stainless steel autoclaves being furnished with stirrer, load the ethylene glycol of highly purified terephthalic acid and its twice molar weight, add the triethylamine 0.3 % by mole relative to sour composition, pressurization 0.25MPa, esterification is carried out while being distilled away from system by water at 250 DEG C, obtain esterification yield and be about two (2-hydroxyethyl) terephthalate of 95% and the mixture (hereinafter referred to as BHET mixture) of oligopolymer.In this BHET mixture, add germanium dioxide (Ge is 100ppm) as polymerizing catalyst, then, under nitrogen atmosphere and normal pressure, stir 10 minutes at 250 DEG C.Then, utilize 60 minutes to be warming up to 280 DEG C, and slowly make the pressure drop of reactive system to 13.3Pa (0.1Torr), 280 DEG C, implement polycondensation under 13.3Pa.After pressure release, micro-resin adding pressure is discharged in water for silk thread shape, after cooling, cut off with cutting knife and obtain being about 3mm, tubular bead that diameter is about 2mm.The IV of gained polyester is 0.61dl/g, foundation 1h-NMR measures, and in resin composition, terephthalic acid is 100 % by mole, and ethylene glycol is 98.0 % by mole, and Diethylene Glycol is 2.0 % by mole.Composition and the characteristic value of gained vibrin are as shown in table 2.
(comparative example 2 ~ 4)
Except change use raw material kind except, identical with the polymerization of the vibrin of comparative example 1, obtain each vibrin.Composition and the characteristic value of each vibrin of gained are as shown in table 2.
(comparative example 5: polyamide resin)
By terephthalic acid 3272.9g (19.70 moles), 1,9-diamino nonane 2849.2g (18.0 moles), 2-methyl isophthalic acid, it is in the autoclave of 20 liters that 8-octamethylenediamine 316.58g (2.0 moles), phenylformic acid 73.27g (0.60 mole), ortho phosphorous acid sodium-hydrate 6.5g (be 0.1% relative to the weight percent of raw material) and distilled water 6 lifting enter internal volume, carries out nitrogen replacement.Stir 30 minutes at 100 DEG C, utilize 2 hours by internal temperature and be warming up to 210 DEG C.Now, reactor boosts to 22kg/cm 2.After continuation reaction 1 hour, be warming up to 230 DEG C, then keep 2 hours at 230 DEG C, slowly remove water vapor, keep pressure at 22kg/cm 2while, make it react.Secondly, utilize 30 minutes and reduce pressure to 10kg/cm 2, make it react 1 hour further, obtain the prepolymer that limiting viscosity [η] is 0.25dl/g.By it at 100 DEG C, under decompression dry 12 hours, be ground into the size of below 2mm.By its 230 DEG C, under 0.1mmHg, solid state polymerization 10 hours, obtains the white polyamide resin that melting point is 310 DEG C, limiting viscosity [η] is 1.33dl/g, end seal rate is 90%.Composition and the characteristic value of gained polyamide resin are as shown in table 2.
Table 1
Table 2
(embodiment 6 ~ 13, comparative example 6 ~ 10)
With the composition described in table 3,4 and mass ratio, by the twin screw extruder STS-35 using Coperion Co., Ltd. to manufacture, at the melting point+15 DEG C of vibrin (A) or polyamide resin, carry out melting mixing, obtain the resin combination of embodiment 6 ~ 13, comparative example 6 ~ 10.In table 3,4, the details of the use material beyond vibrin (A) is as described below.
Titanium oxide (B): the TipaqueCR-60 that Ishihara Sangyo Kaisha, Ltd. manufactures, rutile TiO 2, median size 0.2 μ
Strongthener (C): glass fibre (Nitto Boseki Co. Ltd manufactures, CS-3J-324), acicular wollastonite (NYCO Co., Ltd. manufactures, NYGLOS8)
Packing material (D): talcum powder (micro-wollastonite 5000A that Hayashi Kasei Co., Ltd. manufactures)
Releasing agent: Magnesium Stearate
Stablizer: four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, (antioxidant 1010 that Ciba company limited (CibaSpecialtyChemicalsInc.) manufactures)
The resin combination obtained at embodiment 6 ~ 13, comparative example 6 ~ 10 is applied in the evaluation of various characteristic.Its evaluation result also as shown in Table 3, 4.
Table 3
Table 4
Can be found out by table 1 and table 3, meet in the resin combination (embodiment 6 ~ 13) of the vibrin (embodiment 1 ~ 5) of prerequisite of the present invention in use, polyester and resin composition is based on when the peak melting temperature of DSC is more than 280 DEG C, can be applicable to solder reflow process, and when peak melting temperature is more than 310 DEG C, because backflow heat resisting temperature is more than 280 DEG C, show the scolding tin thermotolerance that also can be applicable to gold/tin eutectic solder technique, simultaneously in the key property of LED purposes, the stickiness with packaged material can be confirmed, surface albedo is good, and formability, mobility, dimensional stability, low water absorbable, photostabilization, heat-resisting yellowing on also good unusual effect.On the other hand, can be found out by table 2 and table 4, in the resin combination (comparative example 6 ~ 9) employing the vibrin (comparative example 1 ~ 4) not meeting prerequisite of the present invention, fail to meet these all characteristics.Although the polyamide of comparative example 5 has high melting point but the water-absorbent brought due to amide structure, use the resin combination (comparative example 10) of polyamide in comparative example 5, backflow heat resisting temperature fails satisfied more than 280 DEG C, and photostabilization, heat-resisting yellowing also poor.
Industrial utilizability
Polyester and resin composition of the present invention, employ not only thermotolerance, formability, mobility, low water absorbable better, and it is also better with the stickiness of packaged material in LED purposes, the specific vibrin that photostabilization is better, so while meeting desired characteristic to heavens, can preferably be used on surface mounting LED reflector.

Claims (11)

1. a vibrin, is characterized in that, be made up of, and melting point is more than 280 DEG C the dicarboxylic acid component containing aromatic dicarboxylic acid more than 50 % by mole and the diol component containing 4,4'-biphenyl dimethanol more than 15 % by mole.
2. vibrin as claimed in claim 1, is characterized in that, aromatic dicarboxylic acid comprises at least one dicarboxylic acid selected from the group be made up of 4,4'-diphenyldicarboxylic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acids.
3. vibrin as claimed in claim 1 or 2, it is characterized in that, form 4 of vibrin, diol component beyond 4'-biphenyl dimethanol, comprise from by ethylene glycol, 1, the at least one glycol selected in the group of 4-cyclohexanedimethanol, 1,3-PD, neopentyl glycol and BDO composition.
4. the vibrin as described in any one of claims 1 to 3, is characterized in that, when the melting point Tm of vibrin and cooling, the difference of crystallized temperature Tc2 is below 42 DEG C.
5. the vibrin as described in any one of Claims 1 to 4, is characterized in that, the acid value of vibrin is 1 ~ 40eq/t.
6. the polyester and resin composition used on surface mounting LED reflector, it is characterized in that, this polyester and resin composition contains: the vibrin (A) described in any one of Claims 1 to 5, titanium oxide (B), the strongthener (C) that at least one is selected from the group be made up of fibrous reinforcements and needle-like strongthener, and Non-fibrous or non-needle-like packing material (D), and relative to vibrin (A) 100 mass parts, titanium oxide (B), strongthener (C), and Non-fibrous or non-needle-like packing material (D) are respectively with 0.5 ~ 100 mass parts, 0 ~ 100 mass parts, and 0 ~ 50 mass parts ratio exist.
7. polyester and resin composition as claimed in claim 6, it is characterized in that, Non-fibrous or non-needle-like packing material (D) they are talcum powder, and relative to vibrin (A) 100 mass parts, containing proportional be 0.1 ~ 5 mass parts.
8. polyester and resin composition as claimed in claims 6 or 7, it is characterized in that, Reflow Soldering heat resisting temperature is more than 260 DEG C.
9. the polyester and resin composition as described in any one of claim 6 ~ 8, is characterized in that, Reflow Soldering heat resisting temperature is more than 280 DEG C.
10. the polyester and resin composition as described in any one of claim 6 ~ 9, is characterized in that, the peak melting temperature Tm of polyester and resin composition is more than 280 DEG C, and when peak melting temperature Tm and cooling, the difference of crystallized temperature Tc2 is below 42 DEG C.
11. 1 kinds of surface mounting LED reflectors, is characterized in that, use the polyester and resin composition described in any one of claim 6 ~ 10 shaping and obtain.
CN201480028826.7A 2013-06-03 2014-05-23 Polyester resin and the surface mounting LED reflecting plate polyester and resin composition using polyester resin Active CN105246941B (en)

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