JP2021155616A - Resin composition for reflective material and reflective material - Google Patents

Abstract

To provide a resin composition for a reflective material having higher fluidity and a reflective material using the resin composition for the reflective material.SOLUTION: There is provided a resin composition for a reflective material comprising: a thermoplastic resin (A) having a melting point (Tm) or a glass transition temperature (Tg) of 250°C or higher as measured by a differential scanning calorimeter (DSC) of 30 pts.mass or more and 80 pts.mass or less; and a crystalline resin (B) having a melting point (Tm) or a glass transition temperature (Tg) of 50°C or higher and lower than 250°C as measured by the differential scanning calorimeter (DSC) of 5 pts.mass or more and 30 pts.mass or less (however, the total mass of the resin composition for the reflective material is 100 pts.mass).SELECTED DRAWING: None

Description

The present invention relates to a resin composition for a reflective material and a reflective material.

Light sources such as light emitting diodes (LEDs) and organic ELs are widely used for lighting and display backlights by taking advantage of their features such as low power consumption and long life. Reflective materials are used in various aspects in order to efficiently utilize the light from these light sources.

For example, the LED element has a housing portion formed on a substrate having a space for mounting the LED, an LED mounted in the space, and a sealing member for sealing the LED. Such an LED element is, for example, 1) a step of molding the reflective material of the present invention on a substrate to manufacture the housing portion, and 2) arranging an LED inside the housing portion, and connecting the LED and the substrate. It is manufactured by a method including a step of electrically connecting and 3) a step of sealing the LED with a sealant. At this time, in the step of 3) sealing, the sealing agent is heated at a temperature of 100 to 200 ° C. for thermosetting. Since this heat extends to the reflective material, the reflective material is required to be able to maintain the reflectance even under the above temperature. Further, in the reflow soldering process when mounting the LED element on the printed circuit board, the LED package is exposed to a high temperature of 250 ° C. or higher. The reflective material is required to be able to maintain the reflectance even under the above temperature. Further, the reflective material is required to be able to maintain the reflectance even when exposed to heat or light generated from the LED for a long period of time in the usage environment.

A composition in which titanium oxide is added to a heat-resistant polyester resin such as polycyclohexylene dimethylene terephthalate (PCT), which is a type of thermoplastic polyester resin, in order to suppress a decrease in the reflectance of the reflective material due to exposure to heat or light. It is being considered to use an object as a material for a reflective material. Further, with respect to the composition containing the heat-resistant polyester resin and titanium oxide, a device for further suppressing a decrease in reflectance due to exposure to heat or light is being studied.

For example, Patent Document 1 discloses a polyester resin composition containing a polyester such as PCT, titanium oxide, a filler, and a phosphorus-containing compound. Further, Patent Document 2 discloses a polyester resin composition containing a polyester such as PCT, titanium oxide, a filler and magnesium oxide. Further, Patent Document 3 discloses a polyester resin composition containing PCT, titanium oxide, a filler, a silicone compound and a nucleating agent.

As described in Patent Document 4, these polyester resin compositions are produced by melt-kneading each of the above materials.

Japanese Unexamined Patent Publication No. 2014-105336 Japanese Unexamined Patent Publication No. 2013-127067 Special Table 2016-504459 Japanese Unexamined Patent Publication No. 2013-227455

As described in Patent Documents 1 to 4, various methods for suppressing a decrease in the reflectance of a reflective material due to exposure to heat or light have been studied.

On the other hand, the resin composition for a reflective material is required to be capable of molding at a lower temperature in order to suppress deterioration of each component due to heat history during molding. Then, in order to perform molding at a lower temperature, it is required to further increase the fluidity of the resin composition.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition for a reflective material having higher fluidity and a reflective material using the resin composition for the reflective material. And.

The resin composition for a reflective material according to one aspect of the present invention for solving the above problems is a heat having a melting point (Tm) or a glass transition temperature (Tg) of 250 ° C. or higher as measured by a differential scanning calorimeter (DSC). A crystalline resin having a plastic resin (A) of 30 parts by mass or more and 80 parts by mass or less and a melting point (Tm) or glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 50 ° C. or more and less than 250 ° C. B) Includes 5 parts by mass or more and 30 parts by mass or less (however, the total mass of the resin composition for the reflective material is 100 parts by mass).

A reflective material according to another aspect of the present invention for solving the above problems is a reflective material containing the polyester resin composition for a reflective material.

According to the present invention, there is provided a resin composition for a reflective material having higher fluidity, and a reflective material using the resin composition for the reflective material.

1. 1. Resin Composition for Reflective Material In one embodiment of the present invention, 30 mass of thermoplastic resin (A) having a melting point (Tm) or a glass transition temperature (Tg) of 250 ° C. or higher as measured by a differential scanning calorimeter (DSC). 5 parts by mass or more and 30 parts by mass or more of the crystalline resin (B) whose melting point (Tm) or glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) is 50 ° C. or more and less than 250 ° C. The present invention relates to a resin composition for a reflective material (hereinafter, also simply referred to as a “resin composition”), which includes, and is included (however, the total mass of the resin composition for a reflective material is 100 parts by mass).

The melting point (Tm) and glass transition temperature (Tg) of the thermoplastic resin (A) and the crystalline resin (B) were measured by a differential scanning calorimeter (DSC) in accordance with JIS K 7121 (2012). sell. Specifically, X-DSC7000 (manufactured by SII) is prepared as a measuring device. A DSC measurement pan containing a sample of the thermoplastic resin (A) or the crystalline resin (B) is set in this device, and the temperature is raised to 320 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. After holding at the temperature for 5 minutes, the temperature is lowered to 30 ° C. by measuring the temperature lowering at 10 ° C./min. Then, the temperature at the top of the endothermic peak at the time of temperature rise is defined as the "melting point". The temperature at the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the gradient of the curve of the stepwise change part of the glass transition is maximized is called the "glass transition temperature". do.

The content of the thermoplastic resin (A) in the resin composition is 30 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the total mass of the resin composition. More preferably, it is more preferably 40 parts by mass or more and 60 parts by mass or less. When the content of the thermoplastic resin (A) is in the above range, it is easy to obtain a resin composition having heat resistance without impairing moldability.

1-1. Thermoplastic resin (A)
The thermoplastic resin (A) is a thermoplastic resin having a melting point (Tm) or a glass transition temperature (Tg) measured by DSC of 250 ° C. or higher. The melting point (Tm) or glass transition temperature (Tg) of the thermoplastic resin (A) is preferably 270 ° C. or higher, more preferably 290 ° C. or higher, and even more preferably 330 ° C. or higher. On the other hand, the upper limit of the melting point (Tm) or the glass transition temperature (Tg) of the thermoplastic resin (A) is not particularly limited, but is, for example, 350 ° C., preferably 335 ° C. When the melting point or the glass transition temperature is 250 ° C. or higher, discoloration or deformation of the molded product of the resin composition due to heating or the like is suppressed. When the upper limit melting point or the glass transition temperature is 350 ° C. or lower, decomposition of the thermoplastic resin (A) is suppressed, which is preferable. The thermoplastic resin (A) may have a melting point of 250 ° C. for a resin having both a melting point (Tm) and a glass transition temperature (Tg).

For example, the melting point (Tm) or glass transition temperature (Tg) of the thermoplastic resin (A) is preferably in the range of 250 ° C. to 350 ° C., and more preferably in the range of 270 ° C. to 350 ° C. , 290 to 335 ° C., more preferably.

The resin type of the thermoplastic resin (A) is not particularly limited, but a thermoplastic polyester resin and a polyamide resin are preferable.

1-1-1. Thermoplastic Polyester Resin The thermoplastic polyester resin has a plurality of ester structures represented by − (C = O) −O− in the molecule, and has a melting point (Tm) or a melting point (Tm) measured by a differential scanning calorimeter (DSC). As long as the glass transition temperature (Tg) is 250 ° C. or higher, the type is not particularly limited.

From the viewpoint of further enhancing the heat resistance of the resin composition, the thermoplastic polyester resin has a dicarboxylic acid component unit (Aa1) having a component unit derived from an aromatic dicarboxylic acid and a component derived from a dialcohol having an alicyclic skeleton. It is preferable to include a dialcohol component unit (Aa2) having a unit.

From the viewpoint of further enhancing the heat resistance of the resin composition, the dicarboxylic acid component unit (Aa1) has 30 to 100 mol% of a component unit derived from terephthalic acid and is derived from an aromatic dicarboxylic acid other than terephthalic acid. It preferably has 0 to 70 mol% of component units. The proportion of the component unit derived from terephthalic acid contained in the dicarboxylic acid component unit (Aa1) is more preferably 40 to 100 mol%, and further preferably 60 to 100 mol%. The higher the content of the component unit derived from terephthalic acid, the higher the heat resistance of the resin composition. The proportion of the component unit derived from the aromatic dicarboxylic acid other than terephthalic acid contained in the dicarboxylic acid component unit (Aa1) is more preferably 0 to 60 mol%, and further preferably 0 to 40 mol%.

The component unit derived from terephthalic acid may be a component unit derived from terephthalic acid or a terephthalic acid ester. The terephthalic acid ester is preferably an alkyl ester having 1 to 4 carbon atoms of terephthalic acid, and examples thereof include dimethyl terephthalate.

Preferred examples of component units derived from aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid and component units derived from combinations thereof, and aromatic dicarboxylic acids thereof. It contains a component unit derived from an ester (preferably an alkyl ester having 1 to 4 carbon atoms of an aromatic dicarboxylic acid).

The total amount of the component unit derived from the terephthalic acid and the component unit derived from the aromatic dicarboxylic acid is preferably 100 mol%. However, depending on the desired properties, the dicarboxylic acid component unit (Aa1) is a polyvalent substance having a small amount of a component unit derived from an aliphatic dicarboxylic acid or 3 or more carboxylic acid groups in the molecule together with the above component unit. It may further contain a component unit derived from a carboxylic acid. The ratio of the component unit derived from the aliphatic dicarboxylic acid and the component unit derived from the polyvalent carboxylic acid contained in the dicarboxylic acid component unit (Aa1) can be, for example, 10 mol% or less in total.

The number of carbon atoms of the component unit derived from the aliphatic dicarboxylic acid is not particularly limited, but is preferably 4 to 20, and more preferably 6 to 12. Examples of the aliphatic dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, undecandicarboxylic acid and dodecanedicarboxylic acid. Of these aliphatic dicarboxylic acids, adipic acid is preferable. Examples of component units derived from the polyvalent carboxylic acid include trimellitic acid and tribasic acid containing pyromellitic acid, and polybasic acid.

From the viewpoint of further enhancing the heat resistance of the resin composition, the dialcohol component unit (Aa2) is a component unit derived from an alicyclic dialcohol having 4 to 20 carbon atoms, or 2 to 20 carbon atoms. It is preferable to have a component unit derived from the aliphatic dialcohol of.

The component unit derived from the alicyclic dialcohol can increase the heat resistance of the resin composition and reduce the water absorption. Examples of the alicyclic dialcohol include dialcohols having an alicyclic hydrocarbon skeleton having 4 to 20 carbon atoms, for example, 1,3-cyclopentanediol, 1,3-cyclopentanedimethanol, 1, Includes 4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cycloheptanediol and 1,4-cycloheptanedimethanol. Among them, the alicyclic dialcohol is a compound having a cyclohexane skeleton from the viewpoints that the heat resistance of the resin composition is further increased, the water absorption is further reduced, and the resin composition is easily available. It is preferably 1,4-cyclohexanedimethanol, more preferably.

The alicyclic dialcohol has isomers such as a cis / trans structure, but from the viewpoint of further enhancing the heat resistance of the resin composition, the thermoplastic polyester resin is derived from the alicyclic dialcohol having a trans structure. It is preferable to contain more component units. Therefore, the cis / trans ratio of the component unit derived from the alicyclic dialcohol is preferably 50/50 to 0/100, more preferably 40/60 to 0/100.

The component unit derived from the aliphatic dialcohol further enhances the melt fluidity of the resin composition. Examples of the aliphatic dialcohols include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol and dodecamethylene glycol.

The dialcohol component unit (Aa2) may have only one of the component unit derived from the alicyclic dialcohol and the component unit derived from the aliphatic dialcohol, or may have both. May be good. The dialcohol component unit (Aa2) is a component unit derived from the alicyclic dialcohol (preferably a component unit derived from dialcohol having a cyclohexane skeleton, more preferably a component unit derived from cyclohexanedimethanol). It is preferable to have 30 to 100 mol% and 0 to 70 mol% of the component unit derived from the above aliphatic dialcohol. A component unit derived from the alicyclic dialcohol contained in the dialcohol component unit (Aa2) (preferably a component unit derived from a dialcohol having a cyclohexane skeleton, more preferably a component unit derived from cyclohexanedimethanol. ) Is more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%. The proportion of the component unit derived from the aliphatic dialcohol contained in the dialcohol component unit (Aa2) is more preferably 0 to 50 mol%, still more preferably 0 to 40 mol%.

The total amount of the component unit derived from the alicyclic dialcohol and the component unit derived from the aliphatic dialcohol is preferably 100 mol%. However, depending on the desired properties, the dialcohol component unit (Aa2) may further contain a small amount of a component unit derived from an aromatic dialcohol in addition to the component unit. Examples of the aromatic dialcohols include bisphenol, hydroquinone, and 2,2-bis (4-β-hydroxyethoxyphenyl) propane. The ratio of the component unit derived from the aromatic dialcohol contained in the dialcohol component unit (Aa2) can be, for example, 10 mol% or less.

The intrinsic viscosity [η] of the thermoplastic polyester resin is preferably 0.3 to 1.5 dl / g. When the intrinsic viscosity is in the above range, the fluidity of the polyester resin composition for a reflective material during molding is further increased. The intrinsic viscosity of the thermoplastic polyester resin can be adjusted within the above range by adjusting the molecular weight of the thermoplastic polyester resin. Examples of methods for adjusting the molecular weight of the thermoplastic polyester resin include known methods including a method for adjusting the progress of the polycondensation reaction and a method for adding an appropriate amount of a monofunctional carboxylic acid or a monofunctional alcohol.

The intrinsic viscosity of the thermoplastic polyester resin can be measured by the following procedure.
The thermoplastic polyester resin is dissolved in a mixed solvent of 50/50% by mass of phenol and tetrachloroethane to prepare a sample solution. The number of seconds of flow of the obtained sample solution is measured using an Ubbelohde viscometer under the conditions of 25 ° C. ± 0.05 ° C., and the intrinsic viscosity [η] is calculated by applying the following formula.
[Η] = ηSP / [C (1 + kηSP)]

In the above equation, each algebra or variable represents:
[Η]: Intrinsic viscosity (dl / g)
ηSP: Specific viscosity C: Sample concentration (g / dl)
k: Constant (slope obtained by measuring the specific viscosities of samples with different solution concentrations (3 points or more) and plotting the solution concentration on the horizontal axis and ηsp / C on the vertical axis)

The above ηSP is calculated by the following formula.
ηSP = (t−t0) / t0

In the above equation, each variable represents the following.
t: Number of seconds (seconds) of flow of the sample solution
t0: Number of seconds for solvent to flow (seconds)

The thermoplastic polyester resin may be produced by a known method, or a commercially available product may be purchased. The preferred thermoplastic polyester resin can be produced, for example, by blending a molecular weight regulator or the like in a reaction system and reacting a dicarboxylic acid component unit (Aa1) with a dialcohol component unit (Aa2). As described above, the intrinsic viscosity of the thermoplastic polyester resin can be adjusted by blending the molecular weight adjusting agent in the reaction system.

Examples of the molecular weight modifier include monocarboxylic acids and monoalcohols. Examples of the monocarboxylic acid include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, aromatic monocarboxylic acids, and alicyclic monocarboxylic acids. The aromatic monocarboxylic acid and the alicyclic monocarboxylic acid may have a substituent in the cyclic structure portion. Examples of the aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. included. Examples of the aromatic monocarboxylic acids include benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid. Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid.

The amount of the molecular weight adjusting agent added is 0 to 0.07 with respect to 1 mol of the total amount of the dicarboxylic acid component unit (Aa1) when the dicarboxylic acid component unit (Aa1) and the dialcohol component unit (Aa2) are reacted. It can be mol, preferably 0-0.05 mol.

1-1-2. Polyamide resin The polyamide resin preferably has a melting point (Tm _A ) of 290 ° C. or higher as measured by a differential scanning calorimeter (DSC). The melting point (Tm _A) is preferably 290 ° C. or higher 340 ° C. or less, more preferably 290 ° C. or higher 330 ° C. or less, more preferably 325 ° C. 290 ° C. or higher, 290 ° C. or higher 310 ° C. The following is particularly preferable.

From the viewpoint of achieving the above melting point (Tm _A ), the polyamide resin is preferably a semi-aromatic polyamide resin. Incidentally, the semi-aromatic polyamide resin is usually the melting point (Tm _A) does not exceed the number of cases 340 ° C.. On the other hand, polyamide resin, from the viewpoint of its melting point (Tm _A) a 290 ° C. or higher, the main structural unit is, because the specific diamine component units [Bb] with a specific dicarboxylic acid component unit of the following [Ba] It is preferably a semi-aromatic polyamide resin composed of repeating units.

As for the dicarboxylic acid component unit [Ba], the terephthalic acid component unit (Ba1) is 20 to 100 mol%, preferably 45 to 100 mol%, when the total number of moles of the dicarboxylic acid component unit contained in the polyamide resin is 100 mol%. %, More preferably 50 to 90 mol%, still more preferably 60 to 80 mol%. The dicarboxylic acid component unit [Ba] is a total of 0 to 80 mol% of an aromatic dicarboxylic acid component unit (Ba2) other than terephthalic acid or an aliphatic dicarboxylic acid component unit (Ba3) having 4 to 20 carbon atoms. It is preferably contained in an amount of 0 to 55 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%. Both the aromatic dicarboxylic acid component unit (Ba2) other than terephthalic acid and the aliphatic dicarboxylic acid component unit (Ba3) having 4 to 20 carbon atoms may be contained, or only one of them is contained. You may. For example, when the dicarboxylic acid component unit [Ba] contains a small amount of the aliphatic dicarboxylic acid component unit (Ba3), the moldability of the polyamide resin can be further improved. If the total content of the aromatic dicarboxylic acid component unit (Ba2) other than terephthalic acid and the aliphatic dicarboxylic acid component unit (Ba3) having 4 to 20 carbon atoms is 55 mol% or less, it is inevitably terephthalic acid. will be the content of the component unit exceeds 45 mol%, the resulting polyamide resin has a melting point (Tm _a) tends to be 290 ° C. or higher.

More specifically, the dicarboxylic acid component unit [Ba] contains 20 to 100 mol% of the terephthalic acid component unit (Ba1) and terephthalic acid, where the total number of moles of the dicarboxylic acid component unit [Ba] is 100 mol%. It is preferable to contain 0 to 80 mol% of an aromatic dicarboxylic acid component unit (Ba2) other than, 55 to 80 mol% of a terephthalic acid component unit (Ba1), and an aromatic dicarboxylic acid component unit (Ba2) other than terephthalic acid. It is more preferable to contain 20 to 45 mol%, more preferably 60 to 85 mol% of the terephthalic acid component unit (Ba1), and further preferably 15 to 40 mol% of the aromatic dicarboxylic acid component unit (Ba2) other than terephthalic acid. When the dicarboxylic acid component unit [Ba] contains an aromatic dicarboxylic acid component unit (Ba2) other than terephthalic acid, the thermal conductivity of the molded product is likely to increase.

Alternatively, the dicarboxylic acid component unit [Ba] has a terephthalic acid component unit (Ba1) of 40 to 80 mol% and a carbon atom number of 4 to 20 when the total number of moles of the dicarboxylic acid component unit [Ba] is 100 mol%. It is preferable to contain 20 to 60 mol% of the aliphatic dicarboxylic acid component unit (Ba3). When the dicarboxylic acid component unit [Ba] contains the aliphatic dicarboxylic acid component unit (Ba3), the thermal conductivity and heat resistance of the molded product tend to increase.

Examples of aromatic dicarboxylic acid component units (Ba2) other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid component units and the like. Among these, the isophthalic acid component unit is preferable.

The aliphatic dicarboxylic acid component unit (Ba3) is derived from an aliphatic dicarboxylic acid having an alkylene group having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Examples of such an aliphatic dicarboxylic acid component unit (Ba3) include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-. Includes dimethylglutaric acid, 3,3-diethylsuccinic acid, adipic acid, sebacic acid, pimelic acid component units and the like. Among these, adipic acid component unit and sebacic acid component unit are preferable.

In addition to the above-mentioned terephthalic acid component unit (Ba1), aromatic dicarboxylic acid component unit (Ba2) other than terephthalic acid, and aliphatic dicarboxylic acid component unit (Ba3), the polyamide resin contains a small amount of trimellitic acid or pyromerit. It may further contain a trimellitic or higher polyvalent carboxylic acid component unit such as an acid. Such a polyvalent carboxylic acid component unit may be contained in an amount of 0 to 5 mol% with respect to a total of 100 mol% of the dicarboxylic acid component unit [Ba].

The diamine component unit [Bb] preferably contains a linear alkylene diamine component unit (Bb1) having 4 to 18 carbon atoms, and has a side chain alkyl group and has an alkylene diamine component unit (Bb2) having 4 to 18 carbon atoms. ) And the alicyclic diamine component unit (Bb3) having 4 to 20 carbon atoms may be further contained.

The diamine component unit [Bb] is a linear alkylenediamine component unit (Bb1) having 4 to 18 carbon atoms in an amount of 55 to 100 mol, when the total number of moles of the diamine component unit contained in the polyamide resin is 100 mol%. %, preferably 55 to 99 mol%, more preferably 70 to 98 mol%, still more preferably 80 to 95 mol%, and particularly preferably 85 to 93 mol%. Further, the diamine component unit [Bb] is an alkylene diamine component unit (Bb2) having a side chain alkyl group having 4 to 18 carbon atoms or an alicyclic diamine component unit (Bb3) having 4 to 20 carbon atoms. It is contained in an amount of ~ 45 mol%, preferably 1 to 45 mol%, more preferably 2 to 30 mol%, further preferably 5 to 20 mol%, and particularly preferably 7 to 15 mol%. Incidentally, the diamine component unit [Bb] is, two kinds of particular when the alkylenediamine component unit in an amount as described above, the polyamide resin melting point (Tm _A), semi-aromatic polyamide resin composition during molding is gas It can be reduced to the extent that it does not cause burning.

Examples of linear alkylenediamine component units (Bb1) having 4 to 18 carbon atoms include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, Includes component units derived from 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like. Among these, component units derived from 1,6-diaminohexane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane and 1,12-diaminododecane are preferable, and 1,6-diaminodecane is preferable. The diaminohexane component unit is more preferable. A plurality of types of these component units may be contained in the polyamide resin.

Examples of the alkylenediamine component unit (Bb2) having 4 to 18 carbon atoms having a side chain alkyl group include 1-butyl-1,2-diamino-ethane and 1,1-dimethyl-1,4-diamino-butane. , 1-Ethyl-1,4-diamino-butane, 1,2-dimethyl-1,4-diamino-butane, 1,3-dimethyl-1,4-diamino-butane, 1,4-dimethyl-1,4 -Diamino-butane, 2,3-dimethyl-1,4-diamino-butane, 2-methyl-1,5-diaminopentane, 2,5-dimethyl-1,6-diamino-hexane, 2,4-dimethyl- 1,6-diamino-hexane, 3,3-dimethyl-1,6-diamino-hexane, 2,2-dimethyl-1,6-diamino-hexane, 2,2,4-trimethyl-1,6-diamino- Hexane, 2,4,4-trimethyl-1,6-diamino-hexane, 2,4-diethyl-1,6-diamino-hexane, 2,3-dimethyl-1,7-diamino-heptane, 2,4- Dimethyl-1,7-diamino-heptane, 2,5-dimethyl-1,7-diamino-heptane, 2,2-dimethyl-1,7-diamino-heptane, 2-methyl-4-ethyl-1,7- Diamino-heptane, 2-ethyl-4-methyl-1,7-diamino-heptane, 2,2,5,5-tetramethyl-1,7-diamino-heptane, 3-isopropyl-1,7-diamino-heptane , 3-Ioctyl-1,7-diamino-heptane, 1,3-dimethyl-1,8-diamino-octane, 1,4-dimethyl-1,8-diamino-octane, 2,4-dimethyl-1,8 -Diamino-octane, 3,4-dimethyl-1,8-diamino-octane, 4,5-dimethyl-1,8-diamino-octane, 2,2-dimethyl-1,8-diamino-octane, 3,3 -Dimethyl-1,8-diamino-octane, 4,4-dimethyl-1,8-diamino-octane, 3,3,5-trimethyl-1,8-diamino-octane, 2,4-diethyl-1,8 Includes component units derived from -diamino-octane and 5-methyl-1,9-diamino-nonane. Among these, a component unit derived from a side chain alkyldiamine having 1 to 2 side chain alkyl groups having 1 to 2 carbon atoms and having 4 to 10 carbon atoms in the main chain is preferable, and 2- Methyl-1,5-diaminopentane component units are more preferred. A plurality of types of these component units may be contained in the polyamide resin.

Examples of alicyclic diamine component units (Bb3) having 4 to 20 carbon atoms include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, and 1,4-. Bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazin, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4'-diamino-3,3'-dimethyl Dicyclohexylpropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'-diamino-3 , 3'-dimethyl-5,5'-dimethyldicyclohexylpropane, α, α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) -m-diisopropylbenzene , Α, α'-bis (4-aminocyclohexyl) -1,4-cyclohexane, α, α'-bis (4-aminocyclohexyl) -1,3-cyclohexane. Among these, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane. Component units derived from are preferred, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 1,3-bis (aminocyclohexyl) methane, and 1,3-bis ( A component unit derived from (aminomethyl) cyclohexane is more preferred.

In the present specification, the number of carbon atoms in the alkylenediamine component unit having a side chain alkyl group is the total of the number of carbon atoms of the main chain alkylene group and the number of carbon atoms of the side chain alkyl group unless otherwise specified. ..

The polyamide resin has the above-mentioned linear alkylenediamine component unit (Bb1) having 4 to 18 carbon atoms, an alkylenediamine component unit (Bb2) having 4 to 18 carbon atoms having a side chain alkyl group, and 4 carbon atoms. In addition to the alicyclic diamine component unit (Bb3) of ~ 20, other diamine component units such as a small amount of metaxylylenediamine component unit may be contained. The content of the component units derived from such other diamines may be 50 mol% or less, preferably 40 mol% or less, based on the total amount of the diamine component units [Bb].

The intrinsic viscosity [η] of the polyamide resin measured at a temperature of 30 ° C. in concentrated sulfuric acid is usually 0.5 to 3.0 dl / g, preferably 0.5 to 2.8 dl / g, and more preferably 0. It is in the range of 6 to 2.5 dl / g.

The polyamide resin may be a combination of two or more semi-aromatic polyamide resins having different intrinsic viscosities. For example, the polyamide resin has a semi-aromatic polyamide resin (A1) having an intrinsic viscosity [η] of 0.9 dl / g or more and an intrinsic viscosity [η] of 0.7 dl / g or more and less than 0.9 dl / g. It may be a mixture with a semi-aromatic polyamide resin (A2). Such a mixture may contain 35 to 100 parts by mass of the semi-aromatic polyamide resin (A1) and 0 to 65 parts by mass of the semi-aromatic polyamide resin (A2) with respect to 100 parts by mass of the total amount of the polyamide resin. When the content ratio of the semi-aromatic polyamide resin (A1) and the semi-aromatic polyamide resin (A2) is within the above range, the melt fluidity of the semi-aromatic polyamide resin composition can be increased without impairing the mechanical strength. Therefore, it is easy to suppress mold contamination to a higher degree. The intrinsic viscosity [η] of the polyamide resin can be adjusted mainly by the molecular weight.

The intrinsic viscosity [η] of the polyamide resin can be measured in the same manner as the intrinsic viscosity of the thermoplastic polyester resin.

The polyamide resin can be produced by polycondensation of a dicarboxylic acid component and a diamine component. Specifically, the polyamide resin contains terephthalic acid, an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid other than (arbitrary) terephthalic acid, and an alkylenediamine having a linear dialkylenediamine and a side chain alkyl group. The above-mentioned amount is blended in an aqueous medium and heated while pressurizing in the presence of a catalyst such as sodium hypophosphate to produce a polyamide precursor, which is then melt-kneaded to produce the polyamide precursor. be able to. When producing the polyamide precursor, a molecular weight modifier such as benzoic acid can be added.

Further, in the polyamide resin, the blending amounts of at least two types of polyamides having different compositions are adjusted so that the dicarboxylic acid component unit [Ba] and the diamine component unit [Bb] are within the above ranges, and the polyamide resin is melt-kneaded. It can also be manufactured by.

The polyamide resin may be a copolymer of the above-mentioned semi-aromatic polyamide resin and another polyamide resin. Examples of other copolymerized polyamide resins include carboxylic acids including oxalic acid, adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid and 1,4-cyclohexanedicarboxylic acid, as well as ethylenediamine and tetramethylenediamine. , Pentamethylenediamine, 2-methylpentamethylenediamine, hexamethylenediamine, decamethylenediamine, polycondensate with diamine including 1,4-cyclohexyldiamine and m-xylylenediamine, ε-caprolactam, ω-laurolactham Cyclic lactam ring-opening polymer such as, 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and other polycondensates of aminocarboxylic acids, and the cyclic lactam, dicarboxylic acid and diamine. Copolymers and the like are included.

1-2. Crystalline resin (B)
The crystalline resin (B) is a crystalline resin having a melting point (Tm) or a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 50 ° C. or higher and lower than 250 ° C. The crystalline resin (B) improves the fluidity of the resin composition and further improves the flexural modulus of the resin composition.

Examples of the crystalline resin (B) include a crystalline polystyrene resin, a crystalline polyester resin, and the like. Of these, crystalline polyester resins are preferable from the viewpoint of further enhancing compatibility with thermoplastic polyester resins.

Examples of the crystalline polyester resin include aliphatic polyesters containing polylactic acid, polyglucolic acid, polycaprolactone, polyethylene succinate and the like, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT). ) Etc., as well as liquid crystal polymers and the like. Of these, semi-aromatic polyesters are preferred, and polybutylene terephthalate is more preferred.

The content of the crystalline resin (B) in the resin composition is 5 parts by mass or more and 30 parts by mass or less, and 8 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the total mass of the resin composition. It is preferable, and it is more preferable that it is 12 parts by mass or more and 20 parts by mass or less. When the content of the crystalline resin (B) is 5 parts by mass or more, the effect of improving the fluidity and flexural modulus of the resin composition is remarkable, and the improvement of the fluidity enables molding at a low temperature. Become. When the content of the crystalline resin (B) is 30 parts by mass or less, the shrinkage rate is unlikely to decrease.

1-3. Other Components The resin composition may contain other components including a white pigment (C), an inorganic filler (D), an antioxidant, a lubricant, a crystal nucleating agent and the like.

1-3-1. White pigment (C)
The white pigment (C) may be any as long as it can whiten the resin composition and improve the light reflection function. Specifically, the white pigment (C) is preferably a pigment having a refractive index of 2.0 or more. The upper limit of the refractive index of the white pigment (C) can be, for example, 4.0. Examples of such a white pigment (C) include titanium oxide, zinc oxide, zinc sulfide, white lead, zinc sulfate, barium sulfate, calcium carbonate, alumina oxide and the like. These white pigments (C) may be used alone or in combination of two or more. Of these, titanium oxide is preferable because it is easy to increase the reflectance and hiding power of the molded product.

The titanium oxide is preferably of the rutile type.

The white pigment (C) may be treated with a coupling agent such as a silane coupling agent or a titanium coupling agent. For example, the white pigment (C) may be surface-treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, or 2-glycidoxypropyltriethoxysilane.

The white pigment (C) preferably has a small aspect ratio, that is, is close to a spherical shape, from the viewpoint of making the reflectance uniform.

From the viewpoint of further increasing the reflectance of the reflective material obtained from the resin composition of the present invention, the average particle size of the white pigment (C) is preferably 0.1 μm or more and 0.5 μm or less, preferably 0.15 μm or more. It is more preferably 0.3 μm or less. The average particle size of the white pigment (C) is a distribution curve obtained by plotting the particle size (%) of the primary particles in each particle size section using an image diffractometer (Luzex IIIU) based on a transmission electron micrograph. Ask for. Then, the cumulative distribution curve can be obtained from the obtained distribution curve, and the value when the cumulative degree of the cumulative distribution curve is 50% can be used as the average particle size.

The content of the white pigment (C) is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, based on the total mass of the resin composition. It is more preferably 10 parts by mass or more and 40 parts by mass or less, and particularly preferably 10 parts by mass or more and 37 parts by mass or less. When the content of the white pigment (C) is 5 parts by mass or more, the whiteness of the reflective material obtained from the resin composition tends to increase, and the reflectance tends to increase. On the other hand, when the content of the white pigment (C) is 50 parts by mass or less, the fluidity of the resin composition tends to increase and the moldability becomes good.

1-3-2. Inorganic filler (D)
The inorganic filler (D) enhances the mechanical strength of the resin composition.

The shape of the inorganic filler (D) may be spherical, fibrous, or plate-like, and is preferably fibrous from the viewpoint of easily imparting good strength and toughness to the molded product.

Examples of the fibrous inorganic filler (D) include glass fibers, wallastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, sepiolites, zonotrites, zinc oxide whiskers, milled fibers, etc. Includes cut fiber and the like. One of these may be used alone, or two or more thereof may be used in combination. Among them, at least one selected from the group consisting of wallastnite, glass fiber and potassium titanate whisker is preferable because the average fiber diameter is relatively small and the surface smoothness of the molded product can be easily improved. Glass fiber is more preferred. Wallastnite is preferable in terms of high light shielding effect, and glass fiber is preferable in terms of high mechanical strength.

The average fiber length (l) of the fibrous inorganic filler (D) in the polyester resin composition for a reflective material is usually preferably 2 μm to 5 mm. When the average fiber length (l) is 5 mm or less, not only the fibrous inorganic filler (D) is hard to break during molding, but also the fibrous inorganic filler (D) is finely dispersed in the resin, so that the surface surface is Smoothness tends to increase. Further, when the average fiber length (l) is 2 μm or more, good strength can be imparted to the molded product. The average fiber length (l) of the fibrous inorganic filler (D) is preferably 8 μm to 300 μm, more preferably 8 μm to 100 μm, and even more preferably 8 μm to 50 μm.

The average fiber diameter (d) of the fibrous inorganic filler (D) in the polyester resin composition for a reflective material facilitates fine dispersion of the fibrous inorganic filler (D) during molding, and the surface of the molded product. From the viewpoint of enhancing smoothness, it is preferably not more than a certain level, and specifically, it is preferably 0.05 to 30 μm. By setting the average fiber diameter (d) to 0.05 μm or more, it is easy to prevent the fibrous inorganic filler (D) from breaking during molding, and by setting it to 30 μm or less, the surface smoothness of the molded product is improved. It is easy to obtain high reflectance. The average fiber diameter (d) of the fibrous inorganic filler (D) is more preferably 2 to 7 μm.

The average fiber length (l) and average fiber diameter (d) of the fibrous inorganic filler (D) in the polyester resin composition for a reflective material (for example, a compound such as pellets) can be measured by the following methods.
1) The polyester resin composition for a reflective material is dissolved in a hexafluoroisopropanol / chloroform solution (0.1 / 0.9% by volume), and then the filtered product obtained by filtration is collected.
2) Observe any 100 fibrous inorganic fillers (D) in the obtained filtered material with a scanning electron microscope (SEM) (magnification: 50 times), and measure the fiber length and fiber diameter of each. do. The average value of the fiber lengths may be the average fiber length (l); the average value of the fiber diameters may be the average fiber diameter (d).

The aspect ratio (l / d) obtained by dividing the average fiber length (l) of the fibrous reinforcing material by the average fiber diameter (d) is preferably 2 to 20, more preferably 7 to 12. preferable. When the aspect ratio is a certain level or more, it is easy to impart a certain level of strength or rigidity to the molded product.

The content of the inorganic filler (D) in the resin composition is preferably 1 part by mass or more and 50 parts by mass or less, and 5 parts by mass or more and 50 parts by mass or less, based on the total mass of the resin composition. More preferably, it is more preferably 5 parts by mass or more and 40 parts by mass or less. When the content of the inorganic filler (D) is 1 part by mass or more, the heat resistance of the reflective material obtained from the resin composition tends to increase, and the surface tends to be smooth. On the other hand, when the content of the inorganic filler (D) is 50 parts by mass or less, the fluidity of the resin composition becomes high and the moldability is not easily impaired.

1-3-3. Antioxidants Antioxidants enhance the heat resistance and weather resistance of resin compositions.

The antioxidant may be any of various antioxidants such as phosphorus-based, hindered phenol-based, amine-based and sulfur-based, and benzotriazole-based, triazine-based, benzophenone-based, hindered amine-based, ogizanylide-based and the like. It may be a light stabilizer of. Of these, phosphorus-based antioxidants and hindered amine-based light stabilizers are preferred. The phosphorus-based antioxidant is preferably an antioxidant having _{a P (OR) 3 structure.} R is an alkyl group, an alkylene group, an aryl group, an arylene group or the like, and the three Rs may be the same or different, and the two Rs may form a ring structure.

Examples of phosphorus-based antioxidants include triphenylphosphine, diphenyldecylphosphine, phenyldiisodecylphosphine, tri (nonylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritoldi. Phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and the like are included. The phosphorus-based antioxidant has a remarkable effect of suppressing the decomposition reaction of the thermoplastic resin (A) under a high temperature atmosphere (particularly, under conditions exceeding 250 ° C. as in a reflow step). Therefore, the phosphorus-based antioxidant has a remarkable effect of suppressing discoloration of the reflective material obtained by molding the resin composition.

The content of the antioxidant in the resin composition is preferably 0.1 part by mass or more and 2.5 parts by mass or less, and 0.1 part by mass or more and 1 part by mass with respect to the total mass of the resin composition. More preferably: When the content is 0.1 parts by mass or more, the weather resistance and heat resistance of the resin composition can be easily enhanced. When the content is 2.5 parts by mass or less, it is easy to suppress coloring and a decrease in reflectance due to decomposition products of the antioxidant.

1-3-4. Lubricants Lubricants increase the fluidity of the resin composition.
Examples of lubricants include modified or unmodified polyolefin waxes. Examples of the unmodified polyolefin wax include polyolefins (for example, ethylene (co) polymer, propylene (co) polymer, etc.), and examples of the modified polyolefin wax include unsaturated carboxylic acids of the above-mentioned unmodified polyolefin wax. It may be a modified product (for example, maleic anhydride), a styrene-based product (and styrene), or an oxidation-modified product due to air oxidation. The lubricant enhances the fluidity of the resin composition during molding and also improves the mold releasability. Examples of lubricants include high wax 1120H (manufactured by Mitsui Chemicals, Inc.) and the like.

The total mass of the resin composition in the resin composition is 0.3 parts by mass or more and 1.5 parts by mass or less, preferably 0.5 parts by mass or more and 1.3 parts by mass or less, and 0. More preferably, it is 5.5 parts by mass or more and 1.1 parts by mass or less. When the content is 0.3 parts by mass or more, it is easy to increase the fluidity of the resin composition at the time of molding, and it is easy to improve the mold releasability from the mold. When the content is 1.5 parts by mass or less, the dispersibility of the lubricant becomes more sufficient.

1-3-5. Crystal nucleating agent The crystal nucleating agent increases the crystallinity of the resin composition and enhances the mechanical strength of the resin composition.

Examples of crystal nucleating agents include metals containing 2,2-methylenebis (4,6-di-t-butylphenyl) phosphate, tris (pt-butylbenzoic acid) aluminum, stearate and the like. Includes sorbitol-based compounds including salt-based compounds, bis (p-methylbenzylidene) sorbitol, bis (4-ethylbenzylidene) sorbitol and the like, and inorganic substances including talc, calcium carbonate, hydrotalcite and the like. Of these, talc is preferable because it is easy to increase the crystallinity of the molded product. One type of these crystal nucleating agents may be used alone, or two or more types may be used in combination.

The content of the crystal nucleating agent (G) is preferably 0.1 part by mass or more and 5 parts by mass or less, and is 0.1 part by mass or more and 3 parts by mass or less, based on the total mass of the resin composition. Is more preferable. When the content of the crystal nucleating agent is within the above range, it is easy to sufficiently increase the crystallinity of the molded product, and it is easy to obtain sufficient mechanical strength.

1-3-6. Other Additives Resin compositions include heat-resistant stabilizers (lactone compounds, vitamin Es, hydroquinones, copper halides, iodine compounds, etc.) and other polymers (polyformates, ethylene / propylene copolymers, ethylene / 1). -Olefin copolymers such as butene copolymers, olefin copolymers such as propylene / 1-butene copolymers, polystyrenes, polyamides, polycarbonates, polyacetals, polysulphons, polyphenylene oxides, fluororesins, silicone resins, LCPs, etc.) , Flame retardant (bromine-based, chlorine-based, phosphorus-based, antimony-based, inorganic-based, etc.) Even if it further contains additives such as fluorescent whitening agents, plasticizers, thickeners, antistatic agents, mold release agents, and pigments. good.

The total content of these additives is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on the total mass of the resin composition.

1-4. Physical Properties The resin composition preferably has a reflectance of light having a wavelength of 450 nm of 90% or more, and more preferably 94% or more. The reflectance can be measured using a molded product obtained by molding a polyester resin composition for a reflective material as a test piece, and the reflectance of the test piece can be measured using CM3500d manufactured by Konica Minolta Co., Ltd. The thickness of the test piece can be 0.5 mm.

2. Method for Producing Resin Composition The above resin composition can be produced by a known method. Examples of the above known methods include mixing the above components with a Henschel mixer, V blender, ribbon blender or tumbler blender, and after the above mixing, further uniaxial extruder, multiaxial extruder, kneader or Banbury. A method of melt-kneading with a mixer and then granulating or pulverizing after the above-mentioned melt-kneading is included.

The melt-kneading is preferably performed at a temperature 5 to 30 ° C. higher than the melting point of the thermoplastic resin (A). The temperature of the melt-kneading is preferably 255 ° C. or higher, more preferably 275 ° C. or higher, and even more preferably 295 ° C. or higher. The temperature of the melt-kneading is preferably 360 ° C. or lower, more preferably 340 ° C. or lower.

3. 3. Reflective material The reflective material of the present invention can be produced by molding the resin composition of the present invention. The above-mentioned resin composition has good molding processability and a sufficiently long flow length. Therefore, it is possible to obtain a reflective material having a desired shape by molding.

The above molding can be performed by a known molding method for producing a reflective material from the resin composition. Examples of the known molding method include a known heat molding method. Examples of the known heat molding methods include injection molding, insert molding including hoop molding, melt molding, extrusion molding, inflation molding, and blow molding.

The reflective material of the present invention produced in this manner contains each of the above-mentioned components in the above-mentioned composition ratio.

The reflector preferably has a reflectance of light having a wavelength of 450 nm of 90% or more, and more preferably 93% or more. The reflectance may be a value measured by a known method, and can be a value obtained by measuring a molded product having a thickness of 0.5 mm using, for example, CM3500d manufactured by Konica Minolta Co., Ltd. The reflectance of the reflective material can be adjusted by, for example, the amount of white pigment. Further, it is preferable that the reflectance of light having a wavelength of 450 nm after the reflow test is 89% or more. Further, the reflectance of light having a wavelength of 450 nm after a long-term heating test (for example, 500 hours) is preferably 85% or more, and more preferably 86% or more. Further, the reflectance of light having a wavelength of 450 nm of the reflector, which is measured after irradiating ultraviolet rays at 16 mW / cm ^{2 for 500 hours, is preferably 87% or more.}

The reflector can be a casing or housing with a surface that reflects light. At this time, the shape of the surface that reflects the light may be flat, curved, or spherical. For example, the shape of the reflector can be box-shaped, funnel-shaped, bowl-shaped, parabolic-shaped, columnar, conical, and honeycomb-shaped.

The reflector can be used, for example, in an element having a light source. Examples of devices include organic EL devices and light emitting diode (LED) devices. The LED is preferably a surface mountable LED. In these elements, the reflector reflects the light emitted from the light source.

A light emitting diode (LED) element having a reflective material has, for example, a housing portion having a space for mounting the LED, an LED mounted in the space, and a sealing member for sealing the LED. Such an LED element can be manufactured by a known method. For example, 1) a step of molding a reflective material on a substrate to manufacture the housing portion, 2) a step of arranging an LED inside the housing portion, and a step of electrically connecting the LED and the substrate, and 3) the above. A method including a step of sealing the LED with a sealing agent can be used.

In such an LED element, the reflective material is exposed to high-temperature heat in the above steps 2) and 3), and receives light including visible light and ultraviolet light generated from the LED or the like during use, and heat for a long time. Or something.

Such a reflective material can be used for various purposes. Examples of the above applications include various electrical and electronic parts, indoor lighting, outdoor lighting, automobile lighting and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the description of Examples.

1. 1. Material synthesis / preparation 1-1. Synthesis of Thermoplastic Resin (A) 0.0037 mass in a mixture of l06.2 parts by mass of dimethyl terephthalate and 94.6 parts by mass of 1,4-cyclohexanedimethanol (cis / trans ratio: 30/70). A portion of tetrabutyl titanate was added, and the temperature was raised from 150 ° C. to 260 ° C. over 3 hours and 30 minutes to allow a transesterification reaction. At the end of the transesterification reaction, 0.0165 parts by mass of manganese acetate / tetrahydrate dissolved in 1,4-cyclohexanedimethanol was added, and 0.0299 parts by mass of tetrabutyl titanate was subsequently introduced to carry out a polycondensation reaction. Was done.

The polycondensation reaction was gradually depressurized from normal pressure to 1 Torr over 85 minutes, and at the same time, the temperature was raised to a predetermined polymerization temperature of 300 ° C. The reaction was terminated when the temperature and pressure were maintained and the predetermined stirring torque was reached. The obtained polymer (thermoplastic polyester resin) had an intrinsic viscosity [η] of 0.6 dl / g and a melting point (Tm) of 290 ° C.

The intrinsic viscosity [η] and melting point (Tm) of the thermoplastic polyester resin were measured by the following methods, respectively.

[Intrinsic viscosity [η]]
0.5 g of resin was dissolved in 50 ml of 96.5% sulfuric acid solution. The number of seconds of flow of the obtained solution under the condition of 25 ° C. ± 0.05 ° C. was measured using an Ubbelohde viscometer, and "Formula: [η] = ηSP / (C (1 + 0.205ηSP)). It was calculated based on.
[Η]: Intrinsic viscosity (dl / g)
ηSP: Specific viscosity C: Sample concentration (g / dl)
t: Number of seconds (seconds) of flow of the sample solution
t ₀ : Number of seconds (seconds) of blank sulfuric acid flowing down
ηSP = (t−t ₀ ) / t ₀

[Melting point (Tm) and melting enthalpy (ΔH)]
The melting point (Tm) was measured according to JIS K 7121 (2012). Specifically, using DSC7 manufactured by Perkin Elemer, about 5 mg of each resin was sealed in an aluminum pan for measurement, and heated from room temperature to 340 ° C. at 10 ° C./min. To completely melt each resin, it was held at 340 ° C. for 5 minutes and then cooled to 30 ° C. at 10 ° C./min. After standing at 30 ° C. for 5 minutes, the second heating was performed at 10 ° C./min to 340 ° C. The melting enthalpy (ΔH) of the resin composition was calculated based on the melting point (Tm) of the resin and the endothermic peak as the peak temperature (° C.) in this second heating.

1-2. Preparation of Crystalline Resin (B) Polybutylene terephthalate (Toray Industries, Inc. Trecon 1401X06 (“Trecon” is a registered trademark of Toray Industries, Inc.)) was used as the crystalline resin (B). The melting point (Tm) of the polybutylene terephthalate was 224 ° C.

1-3. White pigment (C)
Titanium oxide: powder, average particle size 0.21 μm

The average particle size of titanium oxide was determined by image analysis with an image diffractometer (Luzex IIIU) based on a transmission electron micrograph.

1-4. Inorganic filler (D)
Glass fiber: average fiber length (l) 3 mm, average fiber diameter (d) 6.5 μm (ECS03T-171DE / P9W manufactured by Nippon Electric Glass Co., Ltd., silane compound treated product)

1-5. Antioxidant Phosphorus-based antioxidant: Hostabin N30 (manufactured by Clariant Chemicals)
Hindered amine-based light stabilizer (HALS): Hostanox P-EPQ (manufactured by Clariant Chemicals)

1-6. Lubricants High Wax 1120H (manufactured by Mitsui Chemicals, Inc.)

2. Preparation of Resin Composition The above-mentioned materials were prepared in an addition amount having the composition shown in Table 1, and these were mixed using a tumbler blender. The obtained mixture was melt-kneaded with a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 300 ° C., and then extruded into a strand shape. After cooling the extruded product in a water tank, the strands were taken up with a pelletizer and cut to obtain a pellet-shaped thermoplastic polyester resin composition. It was confirmed that the compounding property was good.

3. 3. Measurement of physical properties 3-1. Fluidity The obtained resin composition was injection-molded using a bar flow mold having a width of 10 mm and a thickness of 0.5 mm under the following conditions, and the flow length (mm) of the resin in the mold was measured.
Injection molding machine: Sodick Plustech Co., Ltd., Tupearl TR40S3A
Injection set pressure: 2000 kg / cm ²
Cylinder set temperature: Melting point (Tm) + 10 ° C
Mold temperature: 30 ° C

3-2. Bending Elastic Modulus The obtained resin composition was molded using the following molding machine under the following molding conditions to obtain a test piece. The test piece had a length of 64 mm, a width of 6 mm, and a thickness of 0.8 mm.
Molding machine: Injection molding machine (Sodick Plustech Co., Ltd., Tupearl TR40S3A)
Cylinder temperature: 300 ° C
Mold temperature: 150 ° C

The obtained test piece was allowed to stand in a nitrogen atmosphere at a temperature of 23 ° C. for 24 hours. Next, a bending test was performed in an atmosphere of a temperature of 23 ° C. and a humidity of 50% Rh at a bending tester: AB5 manufactured by NTESCO, a span of 26 mm, and a bending speed of 5 mm / min, and the elastic modulus at this time was measured.

Table 1 shows the measurement results of the composition and physical properties of the resin composition.

As shown in Table 1, the resin composition containing the thermoplastic polyester resin and the crystalline resin (B) had improved both fluidity and flexural modulus.

According to the present invention, there is provided a resin composition that can be molded into a reflective material at a low temperature. The resin composition of the present invention is very useful not only as an LED element but also as a reflective material for various lighting devices and the like.

Claims (8)

Thermoplastic resin (A) having a melting point (Tm) or glass transition temperature (Tg) of 250 ° C. or higher as measured by a differential scanning calorimeter (DSC) is 30 parts by mass or more and 80 parts by mass or less.
Crystalline resin (B) having a melting point (Tm) or glass transition temperature (Tg) of 50 ° C. or higher and lower than 250 ° C. measured by a differential scanning calorimeter (DSC) is 5 parts by mass or more and 30 parts by mass or less.
(However, the total mass of the resin composition for the reflective material is 100 parts by mass).
Resin composition for reflective materials. The resin composition for a reflective material according to claim 1, wherein the crystalline resin (B) is polybutylene terephthalate. The resin composition for a reflective material according to claim 1 or 2, wherein the thermoplastic resin (A) is a thermoplastic polyester resin. The polyester resin (A) contains a component unit derived from a dicarboxylic acid (Aa1) and a component unit derived from a dialcohol (Aa2).
The component unit derived from the dicarboxylic acid (Aa1) is 30 mol% or more and 100 mol% or less of the component unit derived from terephthalic acid with respect to a total of 100 mol% of the component unit derived from the dicarboxylic acid (Aa1). , Contains 0 mol% or more and 70 mol% or less of component units derived from aromatic dicarboxylic acids other than terephthalic acid.
The component unit derived from the dialcohol (Aa2) includes at least one of a component unit derived from an alicyclic dialcohol having 4 to 20 carbon atoms and a component unit derived from an aliphatic dialcohol.
The resin composition for a reflective material according to claim 3. The component unit derived from the dialcohol (Aa2) includes a component unit derived from an alicyclic dialcohol having a cyclohexane skeleton.
The resin composition for a reflective material according to claim 4. The component unit derived from the dialcohol (Aa2) is 30 mol% or more of the component unit derived from 1,4-cyclohexanedimethanol with respect to a total of 100 mol% of the component unit derived from the dialcohol (Aa2). It contains 100 mol% or less and 0 mol% or more and 70 mol% or less of the component unit derived from the aliphatic dialcohol.
The resin composition for a reflective material according to claim 4 or 5. The resin composition for a reflective material according to any one of claims 1 to 6 is included.
Reflective material. A reflective material for light emitting diode (LED) elements,
The reflective material according to claim 7.