CN105246941B - Polyester resin and the surface mounting LED reflecting plate polyester and resin composition using polyester resin - Google Patents
Polyester resin and the surface mounting LED reflecting plate polyester and resin composition using polyester resin Download PDFInfo
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- CN105246941B CN105246941B CN201480028826.7A CN201480028826A CN105246941B CN 105246941 B CN105246941 B CN 105246941B CN 201480028826 A CN201480028826 A CN 201480028826A CN 105246941 B CN105246941 B CN 105246941B
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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
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- 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
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- 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 with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
Abstract
The invention discloses the polyester resin of a kind of diol component and melting point comprising the dicarboxylic acid component containing 50 moles of more than % of aromatic dicarboxylic acid and containing 15 moles of more than % of 4,4' biphenyl dimethanol more than 280 DEG C.In addition, also disclose a kind of polyester and resin composition, the polyester and resin composition contains the polyester resin (A), titanium oxide (B), the at least one reinforcing material (C) selected from the group being made up of fibrous reinforcements and needle-like reinforcing material, and Non-fibrous or non-needle-like packing material (D), and relative to the mass parts of polyester resin (A) 100, titanium oxide (B), reinforcing material (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.The polyester and resin composition is suitable for use in surface mounting LED reflecting plate.
Description
Technical field
The present invention relates to a kind of its mouldability, mobility, dimensional stability, low water absorbable, scolding tin heat resistance, surface reflection
Rate etc. preferably, and its gold/soldering tin heat resistance, light resistance, low water absorbable also preferably polyester resin, and used this to gather
The polyester and resin composition for being highly suitable for being used on surface mounting LED reflecting plate of ester resin.
Background technology
In recent years, the feature such as the low power consumption of LED (light emitting diode) flexible utilizations, long-life, high brightness, Miniaturizable and answer
For ligthing paraphernalia, optical element, mobile phone, liquid crystal display backlight, automobile control panel, semaphore, display board etc..This
Outward, paying attention in appearance design, the purposes of portability, surface mounting technique has been used to realize compact.
Surface mounting LED, generally by light LED chip, wire, and for housing reflecting plate and sealing resin
Constitute, but in order to all parts being arranged on electric substrate are engaged by pb-free solder, each part must be by energy
The material of enough 260 DEG C of tolerance Reflow Soldering temperature is formed.The melting point (peak melting temperature) of material must be more than 280 DEG C.Especially
It is, on reflecting plate, in addition to these heat resistances, also to require light extraction efficiency surface reflectivity higher and to heat and purple
The durability of outside line.Consider from view of the above, inquired into ceramics and semiaromatic polyamide composition, liquid crystal polymer, thermosetting silicone
Etc. various heat resistant plastics materials, wherein, the contour refraction of titanium oxide is dispersed with semiaromatic polyamide composition and polyester and is filled out
The balance of the resin of material, its mass productivity, heat resistance, surface reflectivity etc. preferably, uses the most universal.Recently,
Along with the generalization of LED, it is necessary to further improve the machinability and reliability of reflecting plate, and requirement improves heat-resisting for a long time
Coloring, light resistance.
As LED reflection plate polyester and resin composition, for example, it is proposed that patent document 1~5.
In patent document 1,2, a kind of polyester resin being made up of dicarboxylic acid component (a) and diol component (b) is disclosed,
Wherein, dicarboxylic acid component (a) includes：I) 70~100 moles of % of terephthalic acid residue；Ii) carbon number is less than 20 aromatic series
0~30 mole of % of dicarboxylic acid residue；And iii) carbon number be less than 16 0~10 mole of % of aliphatic dicarboxylic acid residue；Glycol
Component (b) is included：I) 1~99 mole of % of 2,2,4,4- tetramethyls -1,3- cyclobutanediols；And ii) 1,4- hexamethylenes two
(herein, the total moles percentage of dicarboxylic acid component is 100 moles of % to 1~99 mole of % of methyl alcohol residue, and diol component always rubs
100%) your percentage be, although has the trend that mechanical performance is better, but in terms of there is mouldability, light resistance.
Additionally, in patent document 3, disclosing a kind of lighting device reflecting plate with semiconductor light-emitting elements as light source and using
Flame-retardant polyester resin composition, it is characterised in that being mixed with anionicsite relative to the mass parts of polyester resin (A) 100 is
The calcium salt of phosphinic acids or the mass parts of phosphinates (B) 2~50 of aluminium salt, the mass parts of titanium dioxide (C) 0.5~30 and tool
The mass parts of vistanex (D) 0.01~3 of polarized group, however, in the presence of gold/soldering tin heat resistance, heat resistance, light resistance
The problem of aspect.
Additionally, in patent document 4, disclosing a kind of resin combination, it is by the matter of all aromatic thermotropic liquor polyester 100
Amount part, by by the mass % of titanium oxide obtained in the manufacture method including roasting technique 97~85 with aluminum oxide (include hydrate)
The mass of Titanium particles 8~42 that 3~15 mass % (it is 100 mass % that both are combined) are surface-treated and are formed
Part, the mass parts of glass fibre 25~50 and other mass parts of inorganic filling material 0~8 are constituted, and by including following work
The melting mixing technique of skill and obtain, i.e. twin screw compounder is used, under the cylinder body total length more than 30% of twin screw compounder
Trip side position supplies at least a portion of the glass fibre.However, in terms of there is heat resistance, weatherability in the resin combination
Problem.
Additionally, in patent document 5, disclosing a kind of LED reflection plate unsaturated polyester resin compositions, its feature exists
In including at least unsaturated polyester resin, polymerization initiator, inorganic filler, Chinese white, releasing agent and reinforcement material
Dry type unsaturated polyester resin compositions, the unsaturated polyester resin is relative to the composition entire amount in 14~40 matter
Within the scope of amount %, the combined amount of the inorganic filler and the Chinese white is amounted to relative to the composition entire amount
Within the scope of 44~74 mass %, the Chinese white is total in the combined amount of the inorganic filler and the Chinese white
Shared ratio is more than 30 mass % in meter, and the unsaturated polyester resin is by unsaturated alkyd resin and crosslinking agent mixing
Into, but in terms of there is mouldability, light resistance.
Additionally, so far, as surface mounting LED reflecting plate, various polyamide have been used always, but exist resistance to
Problem in terms of hot tinting, light resistance, water imbibition.
As described above, heat-resisting coloring, light resistance, shaping sex chromosome mosaicism be not resolved in the case of, be continuing with
It is truth toward the polyester and polyamide for proposing.
Additionally, in recent years, also actively extending the purposes in illumination.In the case where the extension to lighting use is considered,
Further requirement reduces cost and high power, raising life-span, raising long-term reliability.Accordingly, as the side for improving reliability
Case, in the engagement of lead frame and LED chip, not using conventional epoxy resin/silver paste, and be currently in use deterioration less and
Thermal conductivity gold higher/tin eutectic solder.However, because the processing of gold/tin eutectic solder needs 280 DEG C less than 290
DEG C temperature, so requiring the melting point of used resin more than 290 DEG C in order to tolerate technique.Additionally, processing gold/
During tin eutectic solder, in order to prevent the expansion (sand holes) on the shaped article surface caused by the moisture in resin, resin is also required
With low water absorbable.
As described above, fully meeting the polyester resin composition that the characteristic in surface mounting LED reflecting plate can be used
Thing, does not report also up to now.
【Patent document】
Patent document 1：Japanese documentation spy No. 2008-544030 bulletin of table
Patent document 2：Japanese documentation spy No. 2008-544031 bulletin of table
Patent document 3：No. 2010-270177 bulletin of Japanese Patent Laid-Open
Patent document 4：No. 2008-231368 bulletin of Japanese Patent Laid-Open
Patent document 5：Japanese documentation speciallys permit No. 4844699 bulletins
The technical problems to be solved by the invention
The present invention be in view of above-mentioned problem of the prior art and complete, its object is to provide a kind of polyester resin and
Using the surface mounting LED reflecting plate polyester and resin composition of the polyester resin, the polyester resin is in injection moulding
When mouldability, mobility, dimensional stability, low water absorbable, scolding tin heat resistance, surface reflectivity and light resistance it is good, and
And, to ensure long-term reliability, realizing can apply the melting point high of gold/tin eutectic solder technique, be intended in reduction welding procedure
Moisture caused by the low water absorbable of expansion of products formed, outdoor use and light resistance during long-term use.
The content of the invention
In order to achieve the above object, the present inventor attentively have studied that not only meet can also as the characteristic of LED reflecting plates
It is enough to be easily molded and solder reflow process, also, its gold/tin eutectic solder heat resistance, low water absorbable, light resistance are preferable
Polyester composition, be finally completed the present invention.
That is, composition of the present invention with following (1)~(11).
(1) polyester resin, it is characterised in that include：Contain 50 moles of dicarboxylic acid components of more than % of aromatic dicarboxylic acid
With contain 4,4'- biphenyl dimethanol, 15 moles of diol components of more than %, and melting point is more than 280 DEG C.
(2) polyester resin described in (1), it is characterised in that aromatic dicarboxylic acid is included from by 4,4'- xenyl dicarboxyls
At least one dicarboxylic acids selected in the group of acid, terephthalic acid (TPA) and 2,6 naphthalene dicarboxylic acid composition.
(3) polyester resin described in (1) or (2), it is characterised in that constitute polyester resin 4,4'- biphenyl dimethanol with
Outer diol component, comprising from by ethylene glycol, 1,4-CHDM, 1,3-PD, neopentyl glycol and Isosorbide-5-Nitrae-fourth two
At least one glycol selected in the group of alcohol composition.
(4) polyester resin described in any one of (1)~(3), it is characterised in that the melting point (Tm) and drop of polyester resin
The difference of crystallized temperature (Tc2) is less than 42 DEG C when warm.
(5) polyester resin described in any one of (1)~(4), it is characterised in that the acid value of polyester resin be 1~
40eq/t
(6) polyester and resin composition used in surface mounting LED reflecting plate, it is characterised in that the polyester
Resin combination contains polyester resin (A) described in any one of (1)~(5), titanium oxide (B), from by fibrous strengthening material
At least one reinforcing material (C) and Non-fibrous that are selected in the group of material and needle-like reinforcing material composition or non-needle-like are filled out
Material (D) is filled, also, relative to the mass parts of polyester resin (A) 100, titanium oxide (B), reinforcing material (C) and Non-fibrous
Or non-needle-like packing material (D) is deposited with the ratio of 0.5~100 mass parts, 0~100 mass parts and 0~50 mass parts respectively
.
(7) polyester and resin composition described in (6), it is characterised in that Non-fibrous or non-needle-like packing material (D) are cunning
Stone flour, and relative to the mass parts of polyester resin (A) 100, its content ratio is 0.1~5 mass parts.
(8) polyester and resin composition described in (6) or (7), it is characterised 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), it is characterised in that Reflow Soldering heat resisting temperature exists
More than 280 DEG C.
(10) polyester and resin composition described in any one of (6)~(9), it is characterised in that polyester and resin composition
Peak melting temperature (Tm) more than 280 DEG C, peak melting temperature (Tm) and cooling when crystallized temperature (Tc2) difference 42
Below DEG C.
(11) surface mounting LED reflecting plate, it is characterised in that use poly- described in any one of (6)~(10)
Ester resin composition is molded and is obtained.
Invention effect
Polyester resin of the invention, not only with heat resistance and relatively low water imbibition higher, during injection moulding into
The machinability such as type and scolding tin heat resistance is also preferable.Therefore, polyester and resin composition of the invention is due to using the polyester
Resin, the surface mounting LED reflecting plate that height meets all essential features is produced to industrialization therefore, it is possible to convenient.
Additionally, polyester and resin composition of the invention, the melting point high due to main component polyester resin with more than 280 DEG C
And heat resistance is also preferable, so gold/tin eutectic solder technique can also be applied to, also, because aromatic rings concentration is higher, so
Not only there is good heat resistance, toughness, light resistance, additionally it is possible to show also more good etc. with the stickiness of encapsulating material
Feature.
Specific embodiment
Polyester resin of the invention, uses as on the formed bodies such as film, thin slice, injection-molded article, special-shaped formed body
Material, especially as the material used in surface mounting LED reflecting plate, with good characteristic.Additionally, this hair
Bright polyester and resin composition, uses in surface mounting LED reflecting plate.Surface mounting LED, can include and use
The chip LED type of printed wiring board, the gull aerofoil profile using lead frame, PLCC types etc., and polyester and resin composition of the invention
The above-mentioned all reflecting plates enumerated can be produced by injection moulding.
Polyester and resin composition of the invention contain polyester resin (A), titanium oxide (B), from by fibrous reinforcements with
And at least one reinforcing material (C) and Non-fibrous or non-needle-like filling material selected in the group of needle-like reinforcing material composition
Material (D).
Polyester resin (A), in order to assign reliability higher, in addition to realizing melting point high, low water absorbable, alsos for reality
Now preferably uv-resistance and allocate and form, it is characterised in that include：Contain 50 moles of dicarboxylic acids of more than % of aromatic dicarboxylic acid
Component and contain 4,4'- biphenyl dimethanol, 15 moles of diol components of more than %, and melting point is more than 280 DEG C.Polyester resin
(A) melting point, preferably more than 290 DEG C, more preferably more preferably more than 300 DEG C, more than 310 DEG C.Polyester resin (A) melts
The upper limit of point is simultaneously not particularly limited, but from the restriction of the raw material components that can be used, below 340 DEG C.Melting point is by real
The method described in the project of example is applied to measure.
The aromatic dicarboxylic acid used as the dicarboxylic acid component of polyester resin (A), can include 4,4'- xenyls
Dicarboxylic acids, terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid, M-phthalic acid, diphenoxyethanedicarboxylic acid, 4,4'- diphenyl ether diformazans
Acid, 4,4'- benzophenone dicarboxylic acids etc..In above-mentioned aromatic dicarboxylic acid, consider from polymerism, cost and heat resistance, it is excellent
Elect 4,4'- diphenyldicarboxylic acids, terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid or these mixture as.Aromatic dicarboxylic acid,
From from the viewpoint of heat resistance, in 50 moles of more than % of dicarboxylic acid component, preferably 60 moles more than %, more preferably 70 rub
You are more than %, more preferably 80 moles more than %, particularly preferably 90 moles more than %, and can also be 100 moles of %.
Additionally, as the dicarboxylic acids beyond aromatic dicarboxylic acid, adipic acid, decanedioic acid, succinic acid, glutaric acid, dimerization can be included
The aliphatic dicarboxylic acids such as acid, hexahydroterephthalic acid, hexahydro M-phthalic acid, 1,2- cyclohexyl dicarboxylic acids, 1,3- hexamethylenes two
Alicyclic dicarboxylic acids such as formic acid, 1,4- cyclohexyl dicarboxylic acids etc..Further, it is also possible to use p- hydroxybenzoic acids, epoxide caproic acid simultaneously
Deng multivalence such as oxyacid, trimellitic acid, Pyromellitic Acid, benzophenone tetracarboxylic, diphenyl sulfone tetrabasic carboxylic acid, biphenyltetracarboxyacid acids
Carboxylic acid and its anhydride.
Additionally, needing to contain whole glycol groups as 4, the 4'- biphenyl dimethanol that the diol component of polyester resin (A) is used
Point 15 moles of more than %, preferably 4,4'- biphenyl dimethanol in 50 moles of more than %, more preferably 60 moles more than %, more
Plus preferably 65 moles more than %, most preferably 70 moles more than %.4,4'- biphenyl dimethanols are to improve mouldability, weldering
Tin heat resistance, light resistance and add, its ratio be less than above-mentioned numerical value when, these characteristics have a declining tendency.Join as 4,4'
Diol component beyond benzene dimethanol, for example, can include ethylene glycol, diethylene glycol, propane diols, 1,3-PD, Isosorbide-5-Nitrae-
Butanediol, 1,2- butanediols, 1,3 butylene glycol, 2,3- butanediols, 1,5- pentanediols, 1,6-HD, 1,2- cyclohexanediols, 1,
3- cyclohexanediols, 1,4- cyclohexanediols, 1,2- cyclohexanedimethanols, 1,3- cyclohexanedimethanols, 1,4 cyclohexane dimethanol, 1,
4- hexamethylenes diethanol, 3- methyl isophthalic acids, 5- pentanediols, 2- methyl isophthalic acids, 5- pentanediols, 2- methyl-1,3-propanediols, 2- ethyls-
1,3- propane diols, neopentyl glycol, 2- Ethyl-2-Methyl -1,3- propane diols, 2,2- diethyl -1,3- propane diols, 2- methyl -2-
Double-n- butyl -1,3- the propane diols of n- butyl -1,3- propane diols, 2-n- butyl -2- ethyl -1,3- propane diols, 2,2-, 2- ethyls -
Double-n- hexyl -1,3- the propane diols of 2-n- hexyl -1,3- propane diols, 2,2-, 1,9- nonanediols, 1,10- decanediols, 1,12- 12
The aliphatic dihydroxy alcohols such as alkane glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypropylene glycol, benzenediol, 4,
Double (beta-hydroxy ethoxyl phenenyl) sulfones of double (beta-hydroxy ethyoxyl) benzene of 4'- dihydroxy bis-phenols aldehyde, 1,4-, 1,4-, double (p- is to oxybenzene
Base) ether, double (p- p-hydroxyphenyls) sulfones, double (p- p-hydroxyphenyls) methane, 1,2- double (p- p-hydroxyphenyls) ethane, bisphenol-A, bisphenol-As
The aromatic diol such as alkylene oxide adduct etc..In above-mentioned glycol, in terms of heat resistance, polymerism, mouldability, cost etc.
Consider, selected preferably from ethylene glycol, 1,4-CHDM, 1,3-PD, neopentyl glycol, BDO
Plant or two or more mixtures.More preferably, one or more mixed for being selected from ethylene glycol, BDO
Compound.In addition, if having used ethylene glycol in diol component, then when polyester resin (A) is manufactured, secondary diethyl two can be born
Alcohol, sometimes as copolymerization component.In this case, secondary diethylene glycol depends on manufacturing condition, but relative to embedding
The ethylene glycol entered in polyester resin is about 1~5 mole of %.Further, it is also possible to use trimethylolethane, trihydroxy methyl simultaneously
The polyalcohols such as propane, glycerine, pentaerythrite.
Polyester resin, when whole components are 200 moles of %, the total of above-mentioned dicarboxylic acid component and diol component, preferably
It is 160 moles of more than %, more preferably 180 moles more than %, more preferably 190 moles more than %, and can also 200 rub
You are %.But, either any situation, dicarboxylic acid component and diol component are not over 100 moles of %.
Additionally, in 20 moles of scopes of below % of whole acid constituents or whole diol component, it is also possible to using containing
There are the metals such as 5- sulfonic groups M-phthalic acid, 4- sulfonaphthol -2,7- dicarboxylic acids, 5- [4- sulfophenoxies] M-phthalic acid
The Sulfonic acid metal alkali such as the slaine such as salt or 2- sulfo group -1,4- butanediols, 2,5- dimethyl -3- sulfo groups -2,5-HD
Dicarboxylic acids or glycol.
As the catalyst that uses when polyester resin (A) is manufactured, although be not particularly limited, but preferably with from
At least one compound selected in the compound of Ge, Ti, Sb, Al, Mn or Mg.These compounds as powder, the aqueous solution,
Ethylene glycol solution, slurry of ethylene glycol etc. and be added in reaction system.
Additionally, as resin stabilizer, it is preferable to use from by the phosphoric acid esters such as phosphoric acid, polyphosphoric acid and trimethyl phosphate,
Phosphonic acids compounds, phosphinic acids class compound, phosphine oxide-type compound, phosphonous acid-type compound, phosphinous acid class compound, phosphine
Class compound group into group in select at least one phosphorus compound.
As the acid value of polyester resin (A), preferably 1~40eq/ton.If acid value is more than 40eq/ton, light resistance
Have a declining tendency.Additionally, when acid value is less than 1eq/ton, polycondensation reaction declines, productivity tends to reducing.
Polyester resin (A) of the invention, the melting point (Tm) during dsc measurement more than 280 DEG C, preferably more than 290 DEG C, more
Plus preferably more than 300 DEG C, particularly preferably more than 310 DEG C, most preferably more than 320 DEG C.On the other hand, polyester of the invention
The upper limit of the melting point (Tm) of resin, preferably less than 340 DEG C.If melting point (Tm) is more than 340 DEG C, to having used the present invention
The processing temperature required when carrying out injection moulding of the composition of polyester resin (A) can become high, so polyester during processing
Resin can be decomposed, and desired physical property and outward appearance are cannot get sometimes.If conversely, melting point (Tm) is less than above-mentioned lower limit, crystallized
Change slows, and is molded sometimes and can become difficulty, and, it is also possible to scolding tin heat resistance can be reduced.If melting point (Tm) is 310
More than DEG C, then 280 DEG C of reflow tin soldering heat resistance is met, and can also apply to gold/tin eutectic solder technique, therefore more
It is preferable.
Additionally, polyester resin (A) of the invention, crystallized temperature (Tc2) during melting point (Tm) and cooling in dsc measurement
Difference, preferably less than 42 DEG C, more preferably less than 40 DEG C, most preferably more preferably less than 35 DEG C, less than 30 DEG C.It is so-called
Crystallized temperature (Tc2) during cooling, refers in dsc measurement, when being lowered the temperature from more than 10 DEG C high than melting point of temperature, to start
The temperature of crystallization.Crystallized temperature (Tc2) when melting point (Tm) and cooling, the method described in the project by embodiment is carried out
Measurement.When the difference of crystallized temperature (Tc2) is below said temperature when melting point (Tm) and cooling, crystallization becomes easy, can
Give full play to dimensional stability and physical property etc..On the other hand, if melting point (Tm) and cooling when crystallized temperature (Tc2) difference surpass
Said temperature is crossed, then LED reflecting plates are molded in the shorter cycle of injection moulding, therefore crystallization can become not fill sometimes
Point, the difficult forming such as cause the demoulding insufficient, or crystallization complete it is insufficient, so occurring in the heating of subsequent technique
Deformation or crystallization are shunk, and the problem peeled off from encapsulating material or lead frame occurs, and lack reliability.
The limiting viscosity (IV) of polyester resin (A), more preferably preferably 0.10~0.70dl/g, 0.20~0.65dl/
G, more preferably 0.25~0.60dl/g.
Polyester resin (A), in polyester and resin composition of the invention, preferably with the ratio of 25~90 mass %, more
Preferably exist with the ratio of 40~75 mass %.If the ratio of polyester resin (A) is less than above-mentioned lower limit, mechanical strength drop
It is low, and if it exceeds the above-mentioned upper limit, then the combined amount meeting deficiency of titanium oxide (B) and reinforcing material (C), hardly results in desired
Effect.
Titanium oxide (B) is mixed to improve the surface reflectivity of reflecting plate, can be included, such as by sulfuric acid
Rutile-type and the titanium dioxide (TiO of anatase titanium dioxide that method or chloridising are made2), titanium monoxide (TiO), titanium oxide
(Ti2O3) etc., especially preferably use the titanium dioxide (TiO of rutile-type2).The average grain diameter of titanium oxide (B) is generally 0.05
~2.0 μm, preferably 0.15~0.5 μm of scope, it is also possible to using a kind of, the oxygen with different-grain diameter can also be applied in combination
Change titanium.As titanium oxide concentration of component, in more than 90 mass %, more preferably preferably more than 95 mass %, 97 mass %
More than.Additionally, titanium oxide (B) can be using using the metal oxides such as silica, aluminum oxide, zinc oxide, zirconium oxide, coupling
Agent, organic acid, organic polyhydric alcohol, siloxanes etc. implement the material of surface treatment.
The ratio of titanium oxide (B), is 0.5~100 mass parts, preferably 10 relative to the mass parts of polyester resin (A) 100
~80 mass parts.If the ratio of titanium oxide (B) is less than above-mentioned lower limit, surface reflectivity can be reduced, if it exceeds on above-mentioned
Limit, then physical property is greatly lowered or mobility reduction etc. is possible to make the molding processibility reduce.
Reinforcing material (C) is mixed to improve the mouldability of polyester and resin composition and the intensity of products formed, is used
At least one selected from fibrous reinforcements and needle-like reinforcing material.As fibrous reinforcements, can enumerate
Go out, for example glass fibre, carbon fiber, boron fibre, ceramic fibre, metallic fiber etc., as needle-like reinforcing material, can enumerate
Go out, for example potassium titanate crystal whisker, aluminium borate whisker, ZnOw, calcium carbonate crystal whisker, magnesium sulfate crystal whisker, wollastonite etc..As glass
Glass fiber, it is possible to use chopped strand or continuous filament fibers with 0.1mm~100mm length.As cutting for glass fibre
Face shape, it is possible to use the glass fibre of circular cross-section and noncircular cross section.The diameter of circular cross-section glass fibre, preferably
Less than 20 μm, more preferably more preferably less than 15 μm, less than 10 μm.Additionally, consider from physical property and mobility, preferably
It is the glass fibre of noncircular cross section.As the glass fibre of noncircular cross section, cut in vertical with the length direction that fiber is long
In face, also including general oval, general oval, substantially cocoon shape section, and compression is preferably 1.5~8.Herein, institute
Meaning compression, refer to assuming that the rectangle of the external minimum area in the section vertical with the length direction of glass fibre, and should
The length on rectangular side long as major axis, using the length of short side as the ratio of major axis/minor axis during short axle.Glass fibre it is thick
It is thin and be not particularly limited, but short axle is 1~20 μm or so, and major axis is 2~100 μm or so.Additionally, glass fibre is fiber
Beam, can preferably use the fibre bundle of the chopped strand shape for being cut into fiber 1~20mm long or so.Additionally, in order to improve
The surface reflectivity of polyester and resin composition, it is larger with the refringence of polyester resin to be preferred, so using by changing glass
The polyester resin for constituting or being surface-treated and improve refractive index is preferred.
The ratio of reinforcing material (C), is 0~100 mass parts relative to the mass parts of polyester resin (A) 100, preferably 5~
100 mass parts, more preferably 10~60 mass parts.Although reinforcing material (C) is not neccessary composition, if its ratio
More than 5 mass parts, then the mechanical strength of products formed can be improved, so ideal.If the ratio of reinforcing material (C) exceedes
The above-mentioned upper limit, then may make surface reflectivity, molding processibility reduction.
As Non-fibrous or non-needle-like packing material (D), according to the difference of purpose, can include enhancing filler and
Conductive filler, magnetic fillers, fire-retardant filler, heat filling, hot xanthochromia suppression filler etc., can specifically include glass micro-
Pearl, glass flake, bead, silica, talcum powder, kaolin, mica, aluminum oxide, Hydrotalcite, montmorillonite, graphite, carbon
Nanotube, fullerene, indium oxide, tin oxide, iron oxide, magnesia, aluminium hydroxide, magnesium hydroxide, calcium hydroxide, red phosphorus, carbon
The wollastonite of sour calcium, magnesium acetate, lead zirconate titanate, barium titanate, aluminium nitride, boron nitride, lead borate, barium sulfate and non-needle-like,
Potassium titanate, aluminium borate, magnesium sulfate, zinc oxide, calcium carbonate etc..These packing materials not only can be used alone one kind, can be with
Multiple combination is used.In the middle of these, talcum powder has the effect for accelerating crystallization, improves mouldability, therefore ideal.
The addition of packing material can select optimised quantity, and relative to the mass parts of polyester resin (A) 100, maximum can add 50 matter
Amount part, but from from the viewpoint of the mechanical strength of resin combination, preferably 0.1~20 mass parts, more preferably 1~10 matter
Amount part.In the case of using talcum powder, relative to the mass parts of polyester resin (A) 100, preferably 0.1~5 mass parts are more excellent
Elect 0.5~3 mass parts as.Additionally, fibrous reinforcements, packing material can improve the affinity with polyester resin, therefore
Preferably with the material through organic process or coupling agent treatment, or used simultaneously with coupling agent in melting compound；Make
It is coupling agent, it is possible to use any one in silane coupling agent, titanate coupling agents, aluminium class coupling agent, but wherein, especially
It is preferably amino silicane coupling agent, epoxy silane coupling agent.
In polyester and resin composition of the invention, it is possible to use LED reflection plate polyester and resin composition was each in the past
Class additive.As additive, can include stabilizer, modified impact agent, fire retardant, releasing agent, sliding improved materials,
Thermoplastic resin beyond colouring agent, fluorescent whitening agent, plasticizer, Nucleating Agent, polyester etc..
As the stabilizer of resin combination, Hinered phenols antioxidant, sulphur kind antioxidant, Phosphorus antioxygen can be included
The light stabilizer such as organic kind antioxidant such as agent or heat stabilizer, hindered amines, Benzophenone class, imidazoles or ultra-violet absorber,
Matal deactivator, copper compound etc..As copper compound, it is possible to use stannous chloride, cuprous bromide, cuprous iodide, copper chloride,
Cuprates of organic carboxyl acid such as copper bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, copper sulfide, copper nitrate, jealous woman acid copper etc..Additionally,
As the component beyond copper compound, preferably containing halogenation alkali metal compound, as halogenation alkali metal compound, Ke Yilie
Enumerate lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, KBr, fluorine
Change potassium etc..These additives not only can be used alone one kind, it is also possible to use multiple combination.The addition of stabilizer can be with
From optimised quantity, and relative to the mass parts of polyester resin (A) 100, maximum can add 5 mass parts.
In polyester and resin composition of the invention, the thermoplastic resins different from polyester resin (A) can be added.Example
Such as：Polyamide (PA), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE) (PTFE), fluorine-containing tree can be included
Fat, aramid fiber resin, polyether-ether-ketone (PEEK), polyether-ketone (PEK), PEI (PEI), TPI, polyamide
It is acid imide (PAI), PEKK (PEKK), polyphenylene oxide (PPE), polyether sulfone (PES), polysulfones (PSU), polyarylate (PAR), poly- right
It is PET, polybutylene terephthalate, PEN, PBN, poly-
Carbonic ester (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene
(PS), polymethyl methacrylate, acrylonitritrile-styrene resin (AS), acrylonitrile-butadiene-styrene copolymer
(ABS).These thermoplastic resins can be mixed in the molten state by melting mixing, can also be made thermoplastic resin
Threadiness, graininess, and be distributed in polyester and resin composition of the invention.The addition of thermoplastic resin can be from optimal
Amount, and relative to the mass parts of polyester resin (A) 100, maximum can add 50 mass parts.
As modified impact agent, ethylene-propylene rubber (EPM), ethylene/propylene/diene rubber can be included
(EPDM), ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, ethylene-methacrylic acid copolymer, ethene-methyl
The polyolefin resins such as acrylate copolymer, EVAc, s-B-S block are total to
Polymers (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-phenylethene block
The ethene polymers resinoids such as copolymer (SIS), acrylate copolymer, by polybutylene terephthalate or poly- naphthalenedicarboxylic acid
Butanediol ester as hard section, using polytetramethylene glycol or polycaprolactone or PCDL as soft section polyester block copolymer,
Nylon elastomer, urethane elastomer, acrylic elastomer, silicon rubber, fluorine class rubber, with what is be made up of two kinds of different polymer
Polymer particle of core shell structure etc..The addition of impact modifying agent can select optimised quantity, and relative to polyester resin (A)
100 mass parts, maximum can add 30 mass parts.
For polyester and resin composition of the invention, thermoplastic resin and resistance to punching beyond addition polyester resin (A)
When hitting modifying agent, preferably combined polymerization have can with the reactive group of pet reaction, and reactive group be can be with polyester
The end group of resin is the group of hydroxyl and/or carboxyl reaction.Specifically, anhydride group, epoxide group, oxazole can be included
Quinoline group, amino, isocyanate groups etc., but at these when epoxide epoxy group group, the reactivity of isocyanate groups are optimal.This
Sample, the thermoplastic resin subdivision that also reporting weighing-appliance has the reactive group reacted with polyester resin is scattered in polyester, just because of
Finely divided, interparticle distance is shortened, and impact resistance is greatly improved.
As fire retardant, the preferably combination of halogen based flame retardant and flame retardant；As halogen based flame retardant, preferably
Brominated Polystyrene, brominated polyphenylether, brominated bisphenol type epoxide polymer, brominated styrene maleic anhydride polymer,
Brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, brominated polycarbonate, perchloro- cyclopentadecane and
Bromination crosslinked aromatic polymer etc.；As flame retardant, antimony oxide, antimony pentaoxide, sodium antimonate, stannic acid can be included
The phyllosilicates such as zinc, Firebrake ZB, montmorillonite, fluorine-based polymer, silicone etc..Wherein, from from the aspect of heat endurance, as halogen
Plain based flame retardant is preferably dibromo polystyrene, is preferably as flame retardant and appointed with antimony oxide, sodium antimonate, zinc stannate
The combination of meaning one.Additionally, as non-halogen based flame retardant, MCA, red phosphorus, phosphinic acids gold can be included
Category salt, nitrogenous phosphate compound.In particular it is preferred that be the combination of metal phosphinate and nitrogenous phosphate compound, as
Nitrogenous phosphate compound include melamine or the condensation product of melamine as melam, melem, mellon and
The reaction product of polyphosphoric acid or their mixture.As other fire retardants, flame retardant, these fire retardants are being used
When, in order to prevent the metal erosion of mould etc., preferably add Hydrotalcite class compound or alkali cpd.The addition of fire retardant
Amount can select optimised quantity, and relative to the mass parts of polyester resin (A) 100, maximum can add 50 mass parts.
As releasing agent, LCFA or its ester and slaine, amide-type compound, polyethylene can be included
Wax, silicone, PEO etc..Used as LCFA, particularly preferably carbon number more than 12 can for example include tristearin
Acid, 12- hydroxy stearic acids, docosoic acid, montanic acid etc., some or all carboxylic acids can be by Monoethylene Glycol (MEG) or PVOH
It is esterified, or slaine can also be formed.As amides compound, can include the double terephthalamides of vinyl,
Methylene distearyl acid amides etc..These releasing agents can be used alone or as mixtures thereof.The addition of releasing agent can be selected
With optimised quantity, and relative to the mass parts of polyester resin (A) 100, maximum can add 5 mass parts.
Polyester and resin composition of the invention, because comprising polyester resin as described above (A), therefore in dsc measurement
Peak melting temperature (Tm) is preferably more than 280 DEG C, more preferably more than 290 DEG C, more preferably more than 300 DEG C, especially excellent
Elect more than 310 DEG C, most preferably more than 320 DEG C as.On the other hand, the upper limit of the Tm of polyester and resin composition of the invention is preferred
It is less than 340 DEG C.
Additionally, polyester and resin composition of the invention, because comprising polyester resin as described above (A), therefore surveyed in DSC
In amount peak melting temperature (Tm) and cooling when crystallized temperature (Tc2) difference, preferably less than 42 DEG C, more preferably 40 DEG C
Hereinafter, more preferably less than 35 DEG C, more preferably less than 30 DEG C.
Polyester resin (A), in addition to melting point and mouldability higher, the balance of low water absorbable and mobility is good
It is good, and light resistance is good.Therefore, the polyester and resin composition of the invention for being obtained by the polyester resin (A), in surface peace
In the shaping of dress type LED reflection plate, not only with more than 280 DEG C of melting point high and low water absorbable, but also thin-walled can be realized
With short-period shaping.
Polyester and resin composition of the invention, can mix above-mentioned each component and manufacture by well-known method in the past
Out.For example, can include：In the polycondensation reaction of polyester resin (A), each composition is added, or by polyester resin (A)
Dry-mixed, or the method that each component is carried out melting mixing with twin screw type extruders is carried out with other compositions.
Embodiment
Hereinafter, the present invention is further specifically described by embodiment, but the present invention is not limited to these embodiments.And
And, the measured value described in embodiment is measured by the following method.
(1) limiting viscosity (IV) of polyester resin
In 1,1,2,2- tetrachloroethanes/phenol (2：3 weight ratios) mixed solvent in, according to the solution viscosity at 30 DEG C
Try to achieve.
(2) acid value
After by polyester resin 0.1g heating for dissolving in 10ml phenmethylols, the methyl alcohol/benzene first of the NaOH of 0.1N is used
The solution of alcohol (1/9 volumetric ratio) is titrated and tried to achieve.
(3) crystallization temperature when the peak melting temperature (Tm) of the melting point (Tm) of polyester resin and resin combination, cooling
Degree (Tc2)
Measured using the differential scanning calorimeter (DSC) of Seiko Instruments Inc's manufacture, RDC-220.With
20 DEG C/minute of programming rate is heated up, and 3 minutes are kept at 330 DEG C afterwards, is cooled to from 330 DEG C with 10 DEG C/minute of speed
130℃.In addition, when not melted at 330 DEG C, 3 minutes are kept at 340 DEG C afterwards, with 10 DEG C/minute of speed from 340 DEG C of drops
Temperature is to 130 DEG C.The summit temperature of the peak melting that will be observed when heating up will be observed as melting point (Tm) in cooling
Crystallization peak summit temperature as cooling when crystallized temperature (Tc2).
(4) mouldability and dimensional stability
The injection moulding machine EC-100 manufactured using toshiba machine, is set as+20 DEG C of resin melting point, by mould by temperature cylinder
Tool temperature is set as 125 DEG C, and uses 100mm long, width 100mm, the flat panel production mould of thickness 1mm with film gate
Tool, implements injection moulding.Carried out under injection moulding speed 50mm/ seconds, pressurize 30Mpa, 10 seconds injection times, 10 seconds cool times
Type, the evaluation of mouldability is carried out according to following standard.
○：Obtain products formed with having no problem.
Δ：Sometimes slag can be remained in a mold.
×：Release property is not enough, and products formed is pasted onto on mould or deforms.
Additionally, the dimensional stability in order to evaluate gained products formed, at 180 DEG C, heated 1 small to above-mentioned products formed
When.Size before and after measurement heating on the direction vertical with flow direction, tries to achieve size changing amount as follows.
Size (mm) before size changing amount (%)={ size (mm) after size (mm)-heating before heating }/heating
×100
The evaluation of dimensional stability is carried out according to following standard.
○：Size changing amount is less than 0.2%
×：Size changing amount is more than 0.2%
(5) scolding tin heat resistance
The injection moulding machine EC-100 manufactured using toshiba machine, is set as+20 DEG C of resin melting point, by mould by temperature cylinder
Tool temperature is set as 140 DEG C, and injection moulding goes out 127mm long, width 12.6mm, the UL combustion test test specimens of thickness 0.8mmt, makes
Test specimen.Test specimen is placed 72 hours in 85 DEG C, the atmosphere of 85%RH (relative temperature).(Eightech is manufactured in reflow ovens
AIS-20-82C), made test specimen from room temperature to 150 DEG C using 60 seconds, and preheated, then until 190 DEG C of utilizations 0.5
DEG C/minute programming rate implement preheating.Then, the design temperature of regulation is warming up to 100 DEG C/minute of speed, in the temperature of regulation
Degree is lower to be kept for 10 seconds, is cooled down.Design temperature, every 5 DEG C of increases, will not occur superficial expansion or change since 240 DEG C
The highest setting temperature of shape is set to the heat resisting temperature that flows back, and have rated scolding tin heat resistance with following standard.
◎：Backflow heat resisting temperature is more than 280 DEG C
○：Backflow heat resisting temperature is at 260 DEG C less than 280 DEG C
×：Backflow heat resisting temperature is less than 260 DEG C
(6) scattered reflection rate
The injection moulding machine EC-100 manufactured using toshiba machine, is set as+20 DEG C of resin melting point, by mould by temperature cylinder
Tool temperature is set as 140 DEG C, and injection moulding goes out 100mm long, width 100mm, the flat board of thickness 2mm, and system is evaluated uses test specimen.Make
The test specimen is used, the integrating sphere of the said firm's manufacture is set on the uatomatic recording spectrophotometer " U3500 " of Hitachi's manufacture,
Measure the reflectivity of 350nm to 800nm wavelength.As the comparing of reflectivity, the scattered reflection in 460nm wavelength is tried to achieve
Rate.Barium sulfate is consulted and used.
(7) saturated water absorption
The injection moulding machine EC-100 manufactured using toshiba machine, is set as+20 DEG C of resin melting point, by mould by temperature cylinder
Tool temperature is set as 140 DEG C, and injection moulding goes out 100mm long, width 100mm, the flat board of thickness 1mm, and system is evaluated uses test specimen.Will
The test specimen impregnates 50 hours in 80 DEG C of hot water, when being absorbed water according to saturation and the weight and below equation of the when of drying is tried to achieve
Saturated water absorption.
Saturated water absorption (%)={ weight when (weight during weight-dry when saturation absorbs water)/dry } × 100
(8) mobility
The injection moulding machine IS-100 manufactured using toshiba machine, 330 DEG C are set as by temperature cylinder, and mold temperature is set
Be set to 120 DEG C, and injection pressure setting value be 40%, injection moulding speed setting value be 40%, metering 35mm, 6 seconds injection times,
Under conditions of 10 seconds cool times, the injection moulding in 1mm wide, the length of flow measurement mould of thickness 0.5mm, system is evaluated
Use test specimen.The length of flow (mm) for measuring the test specimen is used as the evaluation of mobility.
(9) silicone stickiness
The injection moulding machine EC-100 manufactured using toshiba machine, is set as+20 DEG C of resin melting point, by mould by temperature cylinder
Tool temperature is set as 140 DEG C, and injection moulding goes out 100mm long, width 100mm, the flat board of thickness 2mm, and system is evaluated uses test specimen.
In the one side of the test specimen, silicone-coating encapsulating material (silicone commercial firm of SHIN-ETSU HANTOTAI manufactures, ASP-1110, encapsulating material hardness D60) makes
Its coating thickness is about 100 μm, and 1 hour is preheated at 100 DEG C afterwards, cure process 4 hours at 150 DEG C, so that encapsulation
Material film is formed in the one side of test specimen.
Next, for the encapsulation material film on test specimen, according to JIS K5400 carry out cross cut test (1mm it is wide 100
Individual grid), have rated stickiness according to following standard.
○：Stripping grid eye number is below 10
×：Before disbonded test grid eye number form into when, have stripping
(10) light resistance
The injection moulding machine EC-100 manufactured using toshiba machine, is set as+20 DEG C of resin melting point, by mould by temperature cylinder
Tool temperature is set as 140 DEG C, and injection moulding goes out 100mm long, width 100mm, the flat board of thickness 2mm, and system is evaluated uses test specimen.It is right
In the test specimen, using super promotion weathering tester " Eye super UV testing machines-SUV-F11 ", in 63 DEG C, the ring of 50%RH
Under border, with 50mW/cm2Illumination implement UV irradiation.Pre-irradiation and irradiation 60 hours afterwards, measure the wavelength of test specimen
The light reflectivity of 460nm.The conservation rate of light reflectivity of the light reflectivity relative to pre-irradiation test specimen according to test specimen after irradiation, presses
Light resistance is have rated according to following standard.
◎：Conservation rate is more than 95%
○：Conservation rate is less than 95%, and more than 90%
Δ：Conservation rate is less than 90%, and more than 85%
×：Conservation rate is less than 85%
(11) it is heat-resisting yellowing
The injection moulding machine EC-100 manufactured using toshiba machine, is set as+20 DEG C of resin melting point, by mould by temperature cylinder
Tool temperature is set as 140 DEG C, and injection moulding goes out 100mm long, width 100mm, the flat board of thickness 2mm, and system is evaluated uses test specimen.Make
The test specimen is used, is processed 2 hours using air drier at 150 DEG C, it is yellowing by estimating confirmation, carried out according to following standard
Evaluate.
○：It is unchanged
Δ：A little yellowing
×：Yellowing
(embodiment 1)
In 20 liters of stainless steel autoclaves equipped with mixer, load high purity dimethyl terephthalic acid (TPA) 3880g, 4,
4'- biphenyl dimethanols 2782g, ethylene glycol 1922g, manganese acetate 2g, germanium dioxide 0.86g, after ester exchange is carried out, using 60 points
Clock time is warming up to 300 DEG C, and the pressure of reaction system is dropped to 13.3Pa (0.1Torr), so 310 DEG C,
Implement polycondensation reaction under 13.3Pa.After pressure release, it is silk thread shape that the resin under micro- pressurization is discharged in water, after cooling,
Obtain being about the tubular bead of 3mm, diameter about 2mm with cutting knife cut-out.The limiting viscosity of gained polyester resin is 0.60dl/g,
Foundation1H-NMR is measured, and in resin composition, terephthalic acid (TPA) is 100 moles of %, and 4,4'- biphenyl dimethanols are 65 moles of %, second
Glycol is 34.5 moles of %, and diethylene glycol is 0.5 mole of %.The composition and characteristic value of gained polyester resin are as shown in table 1.
(embodiment 2~4)
In addition to amount and species that change uses raw material, the polymerization with the polyester resin of embodiment 1 is identical, obtains each
Polyester resin.The composition and characteristic value of each polyester resin of gained are as shown in table 1.In addition, diethylene glycol is ethylene glycol contracting
Close and it is secondary.
(embodiment 5)
In 20 liters of stainless steel autoclaves equipped with mixer, load high purity dimethyl terephthalic acid (TPA) 3880g, 4,
4'- biphenyl dimethanols 2782g, ethylene glycol 1922g, manganese acetate 2g, germanium dioxide 0.86g, after carrying out ester exchange, add high-purity
Terephthalic acid (TPA) 8g, 300 DEG C are warming up to using 60 minutes, the pressure of reaction system is dropped to 13.3Pa
(0.1Torr), and implement polycondensation reaction under 310 DEG C, 13.3Pa.After pressure release, by the resin under micro- pressurization in water
It is silk thread shape to discharge, and after cooling, obtains being about the tubular bead of 3mm, diameter about 2mm using cutting knife cut-out.Gained polyester tree
The limiting viscosity of fat is 0.60dl/g, foundation1H-NMR measure, resin composition in, terephthalic acid (TPA) be 100 moles of %, 4,
4'- biphenyl dimethanol is 65 moles of %, and ethylene glycol is 34.5 moles of %, and diethylene glycol is 0.5 mole of %.Gained polyester resin
Composition and characteristic value are as shown in table 1.
(comparative example 1)
In 20 liters of stainless steel autoclaves equipped with mixer, load the terephthalic acid (TPA) and its twice mole of high-purity
The ethylene glycol of amount, relative to 0.3 mole of % of triethylamine of sour composition, pressurize 0.25MPa, by water from system at 250 DEG C for addition
In carry out esterification while be distilled off, obtain esterification yield be about 95% double (2- ethoxys) terephthalates with it is oligomeric
The mixture (hereinafter referred to as BHET mixtures) of thing.In the BHET mixtures, germanium dioxide is added as polymerization catalyst
(Ge is 100ppm), then, under nitrogen atmosphere and normal pressure, stirs 10 minutes at 250 DEG C.Then, using 60 minutes
280 DEG C are warming up to, and the pressure of reaction system is dropped to 13.3Pa (0.1Torr), implemented under 280 DEG C, 13.3Pa
Polycondensation reaction.After pressure release, it is silk thread shape that the resin under micro- pressurization is discharged in water, after cooling, with cutting knife cut-out
Obtain being about the tubular bead of 3mm, diameter about 2mm.The limiting viscosity of gained polyester is 0.61dl/g, foundation1H-NMR is measured,
In resin composition, terephthalic acid (TPA) is 100 moles of %, and ethylene glycol is 98.0 moles of %, and diethylene glycol is 2.0 moles of %.Institute
The composition and characteristic value for obtaining polyester resin are as shown in table 2.
(comparative example 2~4)
In addition to the species that change uses raw material, the polymerization with the polyester resin of comparative example 1 is identical, has obtained each poly-
Ester resin.The composition and characteristic value of each polyester resin of gained are as shown in table 2.
(comparative example 5：Polyamide)
By terephthalic acid (TPA) 3272.9g (19.70 moles), 1,9- diamino nonanes 2849.2g (18.0 moles), 2- first
Base -1,8- octamethylenediamines 316.58g (2.0 moles), benzoic acid 73.27g (0.60 mole), ortho phosphorous acid sodium-hydrate 6.5g
(being 0.1% relative to the percentage by weight of raw material) and 6 liters of distilled water are put into the autoclave that internal volume is 20 liters, carry out nitrogen
Gas is replaced.Stirred 30 minutes at 100 DEG C, internal temperature is warming up to 210 DEG C using 2 hours.Now, reactor is boosted to
22kg/cm2.Continue to react 1 hour afterwards, be warming up to 230 DEG C, then kept for 2 hours at 230 DEG C, slowly remove water vapour,
Pressure is kept in 22kg/cm2While, reacted it.Secondly, pressure to 10kg/cm was reduced using 30 minutes2, further
Make its reaction 1 hour, obtain the prepolymer that limiting viscosity [η] is 0.25dl/g.It is dried 12 hours under 100 DEG C, decompression,
It is ground into the size of below 2mm.By it under 230 DEG C, 0.1mmHg, solid phase 10 hours obtains melting point for 310 DEG C, the limit
Viscosity [η] is 1.33dl/g, the white polyamide that end seal rate is 90%.The composition of gained polyamide and spy
Property value is as shown in table 2.
Table 1
Table 2
(embodiment 6~13, comparative example 6~10)
With composition and mass ratio described in table 3,4, the twin-screw manufactured by using Coperion Co., Ltd. is squeezed
Go out machine STS-35, melting mixing carried out at+15 DEG C of the melting point of polyester resin (A) or polyamide, obtain embodiment 6~
13rd, the resin combination of comparative example 6~10.In table 3,4, the details of the use material beyond polyester resin (A) is as follows
It is described.
Titanium oxide (B)：The Tipaque CR-60 of Ishihara Sangyo Kaisha, Ltd.'s manufacture, rutile TiO2, average grain diameter
0.2μ
Reinforcing material (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 of Hayashi Kasei Co., Ltd.'s manufacture)
Releasing agent：Magnesium stearate
Stabilizer：Four [3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid] pentaerythritol esters, (Ciba Co., Ltd
The antioxidant 1010 of (Ciba Specialty Chemicals Inc.) manufacture)
The resin combination obtained in embodiment 6~13, comparative example 6~10 is applied in the evaluation of various characteristics.Its
Evaluation result is also as shown in Table 3, 4.
Table 3
Table 4
By table 1 and table 3 as can be seen that using the polyester resin (embodiment 1~5) for meeting necessary condition of the present invention
In resin combination (embodiment 6~13), when polyester and resin composition is based on the peak melting temperature of DSC more than 280 DEG C, can
Solder reflow process is applied to, and when peak melting temperature is more than 310 DEG C, because backflow heat resisting temperature is more than 280 DEG C,
The scolding tin heat resistance that can also be applied to gold/tin eutectic solder technique is shown, while in the key property of LED purposes, can
Confirm, and mouldability, mobility, dimensional stability, low water suction good with the stickiness of encapsulating material, surface reflectivity
Property, light resistance, it is heat-resisting it is yellowing on also good remarkable result.On the other hand, by table 2 and table 4 as can be seen that using
In the resin combination (comparative example 6~9) of the polyester resin (comparative example 1~4) for not meeting necessary condition of the present invention, fail to meet
These all characteristics.Although the water imbibition that the polyamide of comparative example 5 is brought with melting point high but due to amide structure, uses
The resin combination (comparative example 10) of polyamide in comparative example 5, backflow heat resisting temperature fails to meet more than 280 DEG C, and resistance to
It is photosensitiveness, heat-resisting yellowing also poor.
Industrial utilizability
Polyester and resin composition of the invention, has used not only heat resistance, mouldability, mobility, low water absorbable preferable, and
And in LED purposes with the stickiness of encapsulating material also preferably, the better specific polyester resin of light resistance, so highly
While meeting required characteristic, can be with it is preferable that being used for surface mounting LED reflecting plate.
Claims (11)
1. a kind of polyester resin, it is characterised in that include：Containing 50 moles of dicarboxylic acid components of more than % of aromatic dicarboxylic acid,
And contain 4,4'- biphenyl dimethanol, 15 moles of diol components of more than %, and melting point is more than 280 DEG C.
2. polyester resin as claimed in claim 1, it is characterised in that aromatic dicarboxylic acid is included from by 4,4'- xenyls two
At least one dicarboxylic acids selected in the group of carboxylic acid, terephthalic acid (TPA) and 2,6 naphthalene dicarboxylic acid composition.
3. polyester resin as claimed in claim 2, it is characterised in that constitute beyond 4, the 4'- biphenyl dimethanols of polyester resin
Diol component, including from by ethylene glycol, 1,4-CHDM, 1,3-PD, neopentyl glycol and BDO
At least one glycol selected in the group of composition.
4. the polyester resin as described in any one of claims 1 to 3, it is characterised in that the melting point Tm and drop of polyester resin
The difference of crystallized temperature Tc2 is below 42 DEG C when warm.
5. the polyester resin as described in any one of claims 1 to 3, it is characterised in that the acid value of polyester resin is 1~
40eq/t。
6. a kind of polyester and resin composition used in surface mounting LED reflecting plate, it is characterised in that the polyester resin
Composition contains：Polyester resin (A), titanium oxide (B), at least one described in any one of Claims 1 to 5 is from by fiber
The reinforcing material (C) and Non-fibrous that are selected in the group of shape reinforcing material and needle-like reinforcing material composition or non-needle-like are filled out
Fill material (D), and relative to the mass parts of polyester resin (A) 100, titanium oxide (B), reinforcing material (C) and Non-fibrous or
Non- needle-like packing material (D) exists with the ratio of 0.5~100 mass parts, 0~100 mass parts and 0~50 mass parts respectively.
7. polyester and resin composition as claimed in claim 6, it is characterised in that Non-fibrous or non-needle-like packing material (D)
It is talcum powder, and relative to the mass parts of polyester resin (A) 100, content ratio is 0.1~5 mass parts.
8. polyester and resin composition as claimed in claims 6 or 7, it is characterised in that Reflow Soldering heat resisting temperature 260 DEG C with
On.
9. polyester and resin composition as claimed in claims 6 or 7, it is characterised in that Reflow Soldering heat resisting temperature 280 DEG C with
On.
10. polyester and resin composition as claimed in claims 6 or 7, it is characterised in that the peak melting of polyester and resin composition
More than 280 DEG C, the difference of crystallized temperature Tc2 is below 42 DEG C when peak melting temperature Tm and cooling for temperature Tm.
11. a kind of surface mounting LED reflecting plates, it is characterised in that described in any one of usage right requirement 6~10
Polyester and resin composition is molded and obtains.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013116764 | 2013-06-03 | ||
| JP2013-116764 | 2013-06-03 | ||
| JP2013-119893 | 2013-06-06 | ||
| JP2013119893 | 2013-06-06 | ||
| PCT/JP2014/063679 WO2014196378A1 (en) | 2013-06-03 | 2014-05-23 | Polyester resin, and polyester resin composition for surface-mount-type led reflective plate which comprises same |
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| Publication Number | Publication Date |
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| CN105246941A CN105246941A (en) | 2016-01-13 |
| CN105246941B true CN105246941B (en) | 2017-06-16 |
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| CN201480028826.7A Active CN105246941B (en) | 2013-06-03 | 2014-05-23 | Polyester resin and the surface mounting LED reflecting plate polyester and resin composition using polyester resin |
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| Country | Link |
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| JP (1) | JP5915948B2 (en) |
| KR (1) | KR102158764B1 (en) |
| CN (1) | CN105246941B (en) |
| TW (1) | TWI599594B (en) |
| WO (1) | WO2014196378A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7065382B2 (en) * | 2016-07-19 | 2022-05-12 | パナソニックＩｐマネジメント株式会社 | Molding material for light reflector and its manufacturing method, light reflector, base body and its manufacturing method, and light emitting device |
| GB2567456B (en) * | 2017-10-12 | 2021-08-11 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
| US11220599B2 (en) * | 2018-11-26 | 2022-01-11 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article comprising the same |
| CN113785017B (en) * | 2019-04-18 | 2024-03-05 | 科思创知识产权两合公司 | Thermally conductive polycarbonate with flame retardancy improved by barium sulfate |
| JP6687793B1 (en) * | 2019-08-09 | 2020-04-28 | 住友化学株式会社 | Resin composition and molded article |
| CN110804284A (en) * | 2019-11-29 | 2020-02-18 | 江苏胜帆电子科技有限公司 | High-strength LCP substrate packaging material and preparation method thereof |
| CN114685766B (en) * | 2020-12-31 | 2024-02-02 | 中国石油化工股份有限公司 | Modified biodegradable polyester and preparation method thereof |
| CN113292708A (en) * | 2021-05-25 | 2021-08-24 | 吉林建筑大学 | Bio-based copolyester and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011075628A (en) * | 2009-09-29 | 2011-04-14 | Sumitomo Chemical Co Ltd | Base material for light reflecting component |
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| JPS55106222A (en) * | 1979-02-08 | 1980-08-14 | Toray Ind Inc | Preparation of modified polyester |
| JPH06116373A (en) * | 1992-10-02 | 1994-04-26 | Polyplastics Co | Copolymer polyester and polyester resin composition |
| JPH06239982A (en) * | 1993-02-16 | 1994-08-30 | Polyplastics Co | Copolyester and polyester resin composition |
| JPH10316741A (en) * | 1997-05-20 | 1998-12-02 | Teijin Ltd | Material for electronic part adaptable to surface mounting |
| JP4159160B2 (en) * | 1999-01-20 | 2008-10-01 | ダイセル化学工業株式会社 | Method for purifying acetic acid |
| JP3679641B2 (en) * | 1999-02-05 | 2005-08-03 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| JP4082836B2 (en) * | 1999-11-08 | 2008-04-30 | 日本化薬株式会社 | Resin composition and cured products thereof |
| JP2001131397A (en) * | 1999-11-08 | 2001-05-15 | Nippon Kayaku Co Ltd | Resin compositions and their cured products |
| US7906610B2 (en) | 2005-06-17 | 2011-03-15 | Eastman Chemical Company | Food service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
| JP2008231368A (en) | 2007-03-23 | 2008-10-02 | Nippon Oil Corp | Liquid crystal polyester resin composition excellent in light reflectance and hardness |
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| JP6048833B2 (en) * | 2012-02-24 | 2016-12-21 | 東洋紡株式会社 | Polyester resin composition used for reflector for surface mount LED |
| JP5903732B2 (en) * | 2012-02-28 | 2016-04-13 | 住友化学株式会社 | Liquid crystal polyester composition and molded body |
| JP5924525B2 (en) * | 2012-03-26 | 2016-05-25 | 住友化学株式会社 | Liquid crystal polyester resin composition and molded body |
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|---|---|---|---|---|
| JP2011075628A (en) * | 2009-09-29 | 2011-04-14 | Sumitomo Chemical Co Ltd | Base material for light reflecting component |
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| Publication number | Publication date |
|---|---|
| TW201504274A (en) | 2015-02-01 |
| JPWO2014196378A1 (en) | 2017-02-23 |
| KR102158764B1 (en) | 2020-09-22 |
| WO2014196378A1 (en) | 2014-12-11 |
| KR20160016858A (en) | 2016-02-15 |
| JP5915948B2 (en) | 2016-05-11 |
| TWI599594B (en) | 2017-09-21 |
| CN105246941A (en) | 2016-01-13 |
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