JPH03152152A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent appearance, heat- resistance, optical properties, etc., and suitable for reflection plate of light- emitting diode display element, etc., by compounding specific amounts of titanium oxide, a specific modified polyolefin, etc., to a polyester resin and a polyamide resin. CONSTITUTION:The objective composition is produced by compounding (A) a resin composition composed of (A1) 10-90 pts.wt. of a polyester resin and (A2) 90-10 pts.wt. of a polyamide resin with (B) 10-50wt.% of titanium oxide, (C) 0.3-30wt.% of one or more kinds of materials selected from modified polyolefin produced by grafting or copolymerizing an alpha,beta-unsaturated dicarboxylic acid anhydride to a poly alpha-olefin (copolymer), etc., (D) 0.3-30wt.% of a silicon compound and, as necessary, (E) 3-25ppm of carbon black.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a resin composition that has excellent optical properties such as reflectance and light-shielding properties, and heat resistance, and in particular, a resin composition that has extremely excellent appearance and light-shielding properties. It is something.

More specifically, it relates to a resin composition suitable for a light-emitting diode display element (hereinafter referred to as LED) reflecting plate, which has excellent moldability and light-shielding properties in internal molding, as well as excellent printability and epoxy adhesion. It is.

(Prior Art) Synthetic resins containing inorganic fillers, especially titanium oxide, are widely used as materials for reflective plates.

However, in some cases, such as LED reflectors, a manufacturing process is required in which diodes are inserted into a box-shaped reflective frame made of synthetic resin and hardened with thermosetting epoxy resin, and in other cases, such as reflectors for lighting, which require constant high temperature. When exposed to sunlight, heat resistance is required in addition to optical properties such as reflectance and light-shielding properties, and for this purpose, compositions containing titanium oxide and modified polyphenylene oxide (hereinafter referred to as modified PPO) are currently used. has been done.

(Problem to be solved by the invention) However, when conventional modified PPO is used, it itself has a yellowish tinge, so even if inorganic fillers such as titanium oxide are added, sufficient reflectance cannot be obtained. As a result, L
Inferior brightness as an ED, heat resistant temperature is approximately 120°C
There was a problem that the curing time of the epoxy resin was low and the curing time of the epoxy resin was long.

Further, when displaying characters, the LED displays a predetermined symbol by combining nine lit cells, and sharp symbols can be displayed by thinning the partition walls between the cells. However, in order to prevent light from lit cells from leaking to unlit cells by thinning the partition walls inside the cells, LE
There is a need to improve the light-shielding properties of D reflectors. but,
Conventional reflective materials using modified PPO have limited light-shielding properties, resulting in unclear display overall.

In addition, when only titanium oxide is blended into a synthetic resin, especially when it is highly loaded, white spots may appear on the surface of the molded product due to poor dispersion of titanium oxide, which may damage the screen printing plate during printing or cause poor appearance. There was a problem in that the product value was significantly reduced.

The present inventors have solved these problems of the conventional technology, and have developed a product that has an excellent appearance, excellent heat resistance, 9 reflectance, and light shielding properties even when thin, and has excellent productivity, moldability, printability, and epoxy adhesion. The purpose of this invention is to provide a resin composition that is extremely useful as a material for an LED reflector with excellent properties.

(Means for Solving the Problems) In order to solve the problems of the conventional technology, the present inventors have conducted intensive research and research and found that titanium oxide and α,β-unsaturated dicarbonate are added to polyester resin and polyamide resin. By compounding at least one modified polyolefin grafted or copolymerized with an acid anhydride or a modified polyolefin containing a glycidyl group, 15
It has heat resistance that does not deform even in an atmosphere of 0℃, and has a reflectance of 9.

We have discovered a resin composition useful as a material for an LED reflector that has excellent light-shielding properties, productivity, moldability, printability, and epoxy adhesion, and has also improved its appearance by adding a silicon compound to the composition. It was discovered that not only the printing processability was improved, but also the light-shielding property was significantly improved.Furthermore, by adding a small amount of silicon compound and carbon black to the above composition, not only the appearance and printing processability were improved, but also the light-shielding property was improved. We have found that this can be significantly improved and have arrived at the present invention.

That is, 1 the present invention is (A) polyester resin 10-90
parts by weight and 90 to 10 parts by weight of polyamide resin, (B) 10 to 50 parts by weight of titanium oxide, (C) α-olefin or olefin copolymer, and α, β-unsaturated dicarboxylic acid. Modified polyolefin made by kraft or copolymerization of anhydride.

or α-olefin or olefin copolymer;
A resin composition comprising 0.3 to 30% by weight of at least one modified polyolefin comprising glycidyl ester of an α,β-unsaturated acid and 0.3 to 30% by weight of (D) a silicon compound and the above composition. (E) Carbon black 3~
It relates to a resin composition consisting of 25 ppm.

The polyester resin used as component (A) of the present invention is polyethylene terephthalate or at least 80%
A polyester having ethylene terephthalate repeating units of mol % or more, or polybutylene terephthalate or a polyester having at least 80 mol % or more of butylene terephthalate repeating units, and containing phthalic acid, hexahydrophthalate in an amount of 10 mol % or less of the total acid component. It is possible to use dicarboxylic acids such as naphthalene dicarboxylic acid, adipic acid, and sebacic acid, polyhydric carboxylic acids such as trimellitic acid and biromellitic acid, or oxyacids such as p-oxybenzoic acid as the acid component. ,
In addition, 1.2-
Propanediol, 1.3-propanediol, 1.4
-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol.

Dihydric alcohols such as cyclohexane dimetatool,
Polyhydric alcohols such as trimethylolpropane, triethylolpropane, and pentaerythritol can be used as the alcohol component. Such a polyester resin is obtained by a conventional melt polycondensation reaction, and preferably has an intrinsic viscosity of 0.5 or more, preferably 0.55 or more, as measured at 20° C. in a mixed solvent of equal weights of phenol/tetrachloroethane.

The polyamide resin used as component (A) of the present invention is polycapramide or polylaurin lactam.

Polytetramethylene adipamide, polyhexamethylene adipamide, polyhexamethylene sebacamide.

Examples include polydecamethylene adipamide, poly-11-aminoundecanoic acid, poly-12-aminododecanoic acid, polyhexamethylene dimamide, and the like. These may be used alone, as a copolymer, or as a mixture. The preferred polyamide resin has a relative solution viscosity of 25° in 96% sulfuric acid.
The value measured by C is 2.0 or more.

The titanium oxide used as component (B) of the present invention is preferably of rutile type.

Examples of the α-olefin used as a starting material for producing the modified polyolefin used as component (C) of the present invention include ethylene, propylene, butene-1, butadiene, isoprene, and chlorobrene.

Examples of the α,β-unsaturated dicarboxylic acids include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride, citraconic anhydride, butynylsuccinic anhydride, and tetrahydrophthalic anhydride.

In addition, as glycidyl esters of α,β-unsaturated acids,
Examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate.

Further, copolymerizable unsaturated monomers include vinyl ethers, vinyl esters such as vinyl acetate and vinyl propylate, and esters of acrylic acid and methacrylic acid such as methyl, ethyl, and propyl.

Acrylonitrile, styrene, etc. may be copolymerized.

The silicon compound used as component (D) of the present invention is 9
Examples include silicon dioxide, silicates, silicate esters, etc., but preferred silicon compounds are silicates and silicon dioxide, commonly called silica.

Carbon black used as component (II) of the present invention includes tunnel black, thermal black,
Examples include oil furnace black, granulated carbon black, and acetylene black.

In the resin composition according to the present invention, the blend ratio of the polyester resin and the polyamide resin in the component (^) is in the range of 10:90 to 90:10 in terms of weight ratio.

Preferably it is in the range of 20:80 to 80:20.

In the blended resin composition, if the weight ratio of one of the resins is less than 10, sufficient light-shielding properties cannot be obtained, which is not preferable.

In the present invention, the amount of titanium oxide used as component (B) is 10 to 50% by weight.

Preferably it is 20 to 40% by weight.

If it is less than 10% by weight, sufficient reflectance and light shielding properties cannot be obtained,
Further, sufficient heat resistance cannot be obtained, which is not preferable.

On the other hand, even if the amount exceeds 50% by weight, the optical properties remain unchanged.

It is not preferable because it does not improve heat resistance, but instead becomes brittle, and titanium oxide becomes difficult to disperse, resulting in poor appearance.

In the present invention, the blending amount of the modified polyoffine used as component (C) is 0.3 to 30% by weight, preferably 1 to 20% by weight. If it is less than 0.3% by weight, productivity will be poor and it may not be possible to take it off depending on the composition, and even if it is taken up, sufficient light-shielding properties will not be expressed.
On the other hand, if it exceeds 30% by weight, heat resistance and moldability will deteriorate, which is not preferable.

In the present invention, the amount of the silicon compound used as component (D) is 0.3 to 30% by weight, preferably 1 to 20% by weight. If it is less than 0.3% by weight, the dispersibility of titanium oxide cannot be sufficiently improved,
In particular, if titanium oxide is highly loaded, poor dispersion will occur and the appearance will be impaired; conversely, if it is more than 30% by weight, printability and epoxy adhesion will deteriorate, which is not preferable.

In the present invention, the amount of carbon black used as component (E) is 3 to 25 ppm, preferably 5 to 15 ppm. If it is less than 5 ppm, a sufficient effect of improving the light shielding property will not be exhibited, and if it is more than 2 sppn+, the reflectance will decrease, which is not preferable.

As a method for producing the resin composition of the present invention, a melt extrusion method using a conventionally used extruder is preferred. The extruder is characterized by a single-axis and multi-axis type.

In that case, (B) is added to the blended resin composition (A) obtained by melt extruding polyester resin and polyamide resin.
, (C), (D) components, and further (E) component may be added and melt-extruded in the same manner, or polyester resin, polyamide resin, (B), (C), (
Component D) and component (E) may be melt-extruded at the same time. Especially in the latter case, extruding each component simultaneously using a melt extruder with good kneading ability will shorten the residence time in the heated molten state. It is possible to economically obtain a resin composition that is short, suppresses coloration due to thermal deterioration of the resin, and has an excellent reflectance. Furthermore, since carbon black is present in a small amount, sufficient consideration must be given to its dispersion.

Furthermore, the resin composition according to the present invention includes calcium carbonate,
Kaolin, mica, talc, quartz powder, antimony oxide,
Barium sulfate, calcium sulfate.

One or more crystallization promoters can be used, such as alumina, among which mica, kaolin, and talc are useful in the present invention.

Furthermore, the resin composition according to the present invention contains flame retardants such as halogenated hydrocarbons and antimony oxide to improve flame retardancy, optical brighteners to increase the apparent whiteness, and easy release properties during molding. In order to do this, mold release agents such as silicone resin and wax, and antioxidants such as polyhydric phenols and copper compounds may be added and mixed. Among these additives, the amount of flame retardants and antioxidants added is regulated as appropriate depending on the degree required for the product, but the amount of optical brighteners, carbon black, and mold release agents added is based on the resin composition. The amount may be as small as 0.1% by weight or less.

Next, the present invention will be specifically explained by showing examples and comparative examples.

(Example) Example 1,1°, Comparative Example 1,1°~2,2゛Polyethylene terephthalate (intrinsic viscosity measured at 20°C in a mixed solvent of equal weight of phenol/tetrachloroethane is 0.68)
30 parts by weight of polycapramide (1°C in 96% l sulfuric acid)
g/d l and a relative viscosity measured at a temperature of 25°C of 3.
10) To 70 parts by weight, 25% by weight of rutile titanium oxide (DuPont ■R-101), maleic anhydride grafted ethylene-propylene copolymer (Mitsui Petrochemical ■N-
Mix and stir 5% by weight of Tafmar MA8510) and 5% by weight of finely powdered silica (Mizukashiru by Suizuka Kagaku) in a blender, or if carbon black is added, use carbon black (MCF-88B by Mitsubishi Kasei). 5
ppm mixed with a Henschel mixer and stirred to 110″
After drying under vacuum for 6 hours at C, it was melt-extruded using an extruder to create a string, which was then cooled with water and cut to obtain chips.

After drying the obtained chip under vacuum at 110°C for 6 hours, it was molded using an injection molding machine into a disc with a thickness of 2m+i or 1mm, 50φ, and a width of 20mm, a length of 20mm, a depth of 1mm, and a thickness of A box shape with a length of 2111 m was created. For comparison, currently commercially available resin compositions for LED reflectors, i.e., resin compositions such as ABS and modified polyphenylene oxide containing 25% by weight of rutile titanium oxide (Comparative Example 1, 1° to 2.2')
The same disk and box shapes as above were also created. Optical properties (reflectance, light shielding) and printability are 2@II or [
Heat resistance and boxy adhesion were evaluated using a box-type disc using a disc of No. I. In addition, productivity is improved using the twin-screw extruder PCM-30.
(Ikegai Tekko ■) was used to evaluate the retractability. The results are shown in Table 1.

Judgment was made based on the following criteria.

艮11 ◎Very good O good ∆Slightly poor take-up x poor take-up Appearance Visual evaluation Evaluated by Y (%) using a color difference meter (Nippon Heavy Industries ■).

A fiber illumination device for optical microscopes (Nippon Kogaku ■) was used as a surreptitious light source, and the degree of light transmission was visually observed in a dark room by bringing the light source into contact with the light source.

◎ Not transmitted at all O hardly transmitted ∆ Slightly transmitted × Precept to be transmitted” 11 Evaluation was made under the following molding conditions using Toshiba 15-80.

Molding temperature = 240°C Injection pressure: 1000g/ctl Mold temperature = 50°C Cooling time: 10 seconds Cycle time: 30 seconds ◎ Very good O Good Δ Slightly poor mold release × Poor mold release 1 Natural box-shaped The molded product was left in a hot air dryer at 150°C for 1 hour, and then the degree of deformation was visually evaluated.

◎ Not deformed at all Δ Not deformed at all Δ Slightly deformed × Significantly deformed Using Zentex (black) (Daido Paint ■) as a counterbalanced ink 20
Apply using a 0 mesh screen printing plate and heat at 90°C.
Force drying was performed for 20 minutes.

Furthermore, the coated plate was subjected to dry heat treatment at 130°C for 2 weeks.

The adhesion of the coating film after durability was evaluated by a cellophane tape base peel test.

◎No peeling at all O: Hardly peeling ΔSlight peeling ×Most of the parts peeling off Koko Donodara 1 Using two-component thermosetting type NT-8006 (Nitto Denko ■) as epoxy resin It was poured into a box shape and cured at 135° C. for 9 hours.

Furthermore, it was subjected to dry heat treatment at 130'C for 2 weeks, and the adhesion to the cured epoxy resin after durability was evaluated by breaking and peeling off the filled product.

O-broken x Interfacial peeled Examples 2, 2'' to 4, 4', Comparative Examples 3, 3'' to 9, 9'' Same as Example 1, except that polyester resin, polyamide resin, titanium oxide, and modified polyolefin were used.

The results shown in Table 2 were obtained by changing the blending amounts of finely powdered silica and carbon black.

PET and N-6 in Table 2 are abbreviations for polyethylene terephthalate polycabramide.

Each component used was the same as that used in Example 1.1°.

Comparative example 3, 3°, 4.4', 5.5', 7.7°, 8
．． The resin compositions prepared in 8' and 9.9' had an appearance of 9.
Reflectance, light blocking properties.

Any of the characteristics necessary for a resin composition for a reflective plate, such as heat resistance, was insufficient, and as a result, it could not be put to practical use.

Furthermore, with the formulations of Comparative Examples 6 and 6'', it was not possible to form continuous strings during melt extrusion from an extruder, and chips could not be formed.

Examples 5,5'' to 6,6', Comparative Examples 10,10' to 11
．． 11゜Polybutylene terephthalate (East I) 111
005) 70 parts by weight, 30 parts by weight of polyhexamethylene adipamide (ICI Maranyl A125), rutile type titanium oxide (Teikoku Kako J R-600E) 2
5% by weight, glycidyl methacrylate modified polypropylene (Sumitomo Chemical Bondfirth G) 5% by weight, and finely powdered silica (Nippon Aerosil - Aerosil 200) 5
Parts by weight were mixed and stirred in a blender, dried in the same manner as in Examples 1 and 1, and then melt-extruded to obtain chips.

The chips were molded in the same manner as in Example 1.1'' to obtain samples and evaluated in the same manner as in Examples 1 and 1. (Example 5.5
') Furthermore, in place of BOND FAST 05% by weight used in Examples 5 and 5°, glycidyl methacrylate modified polyethylene (Sumitomo Chemical Bond FAST 1-E)
In addition, as a comparative example, Example 5, When 5 parts of unmodified general-purpose polypropylene (Mitsui Petrochemical Highball) was used instead of 65 parts of Bond First used in 5" (Comparative Example 8.8") and Himic anhydride modified ethylene-propylene copolymer A case (Comparative Example 9.9') in which 5 parts of Coagulation (Tonen Petrochemical ■CMP) was used was evaluated.The results are shown in Table 3.As can be seen from the following, Example 5.5'
, 6.6'' is found to be a useful material for LED reflectors.

Furthermore, when unmodified polypropylene is used (Comparative Example 8, 8°), not only is the productivity poor, but also the light-shielding properties and printability required as a material for an LED reflecting plate are poor.

When the anhydrous Himic acid-modified olefin copolymer was used (Comparative Example 9, 9°), the optical properties were excellent, but the moldability and printability were poor.

Examples 7 and 8. Comparative Example 12.13 [In 1 [1', light shielding property 2 reflectance 1 color tone was evaluated by changing the amount of carbon black added. For color tone 0, the b value (yellowness ) was evaluated. The results are shown in Table 4, and as can be seen from the table, it can be seen that the light-shielding properties are significantly improved by incorporating carbon black. It can also be seen that as the amount of carbon black added increases, the color tone improves, while the 1-reflectance decreases.

(Effects of the Invention) The resin composition that satisfies the requirements of the present invention has excellent optical properties (reflectance, light shielding properties) and heat resistance, and also has an excellent appearance, and is suitable for use in LED reflectors, lighting reflectors, etc. This is an extremely effective resin composition for reflective plates.

Claims (1)

[Claims] (1) (A) Blend resin composition consisting of 10 to 90 parts by weight of polyester resin and 90 to 10 parts by weight of polyamide resin, (B) 10 to 50% by weight of titanium oxide, (C) α
- A modified polyolefin obtained by grafting or copolymerizing an olefin or an olefin copolymer with an α,β-unsaturated dicarboxylic acid anhydride, or an α-olefin or an olefin copolymer and a glycidyl ester of an α,β-unsaturated acid. 0.3 to 30% by weight of at least one modified polyolefin; (D) 0.3 to 30% by weight of a silicon compound;
A resin composition consisting of 30% by weight. (2) (A) 10 to 90 parts by weight of polyester resin and 90 to 1 part by weight of polyamide resin
(B) 10 to 50% by weight of titanium oxide, (C) α-olefin or olefin copolymer with α,β-unsaturated dicarboxylic acid anhydride grafted or copolymerized. modified polyolefin,
or α-olefin or olefin copolymer;
0.3 to 30% by weight of at least one modified polyolefin consisting of glycidyl ester of an α,β-unsaturated acid, 0.3 to 30% by weight of (D) a silicon compound, and (
E) A resin composition containing 3 to 25 ppm of carbon black.