WO2023120303A1

WO2023120303A1 - Light-emitting molded body and wavelength conversion member

Info

Publication number: WO2023120303A1
Application number: PCT/JP2022/045854
Authority: WO
Inventors: 敦史酒井; 勇希佐藤
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2021-12-22
Filing date: 2022-12-13
Publication date: 2023-06-29
Also published as: TW202337962A

Abstract

A light-emitting molded body including a polyimide resin (A) that includes repeating structural units represented by formula (1) and repeating structural units represented by formula (2) (R₁ is a C6-22 divalent group including at least one alicyclic hydrocarbon structure, R₂ is a C5-16 divalent chain aliphatic group, and X₁ and X₂ each independently are a C6-22 tetravalent group including at least one aromatic ring), the content ratio of the repeating structural units of formula (1) being 20-70 mol% relative to the total of the repeating structural units of formula (1) and the repeating structural units of formula (2), wherein the amount of active protons in the molded body is 0.01 mol% or greater, where the total of the repeating structural units of formula (1) and the repeating structural units of formula (2) is 100 mol%.

Description

Light-emitting molded article and wavelength conversion member

The present invention relates to a luminescent molded article and a wavelength conversion member.

Due to the rigidity of the molecular chain, resonance stabilization, and strong chemical bonding, polyimide resin is a useful engineering plastic with high thermal stability, high strength, and high solvent resistance, and is applied in a wide range of fields. Polyimide resins having crystallinity can further improve their heat resistance, strength and chemical resistance, and thus are expected to be used as metal substitutes. However, although the polyimide resin has high heat resistance, it does not show thermoplasticity and has a problem of low moldability.

As polyimide molding materials, highly heat-resistant resin Vespel (registered trademark) and the like are known (Patent Document 1). Since it is necessary to perform molding, it is also disadvantageous in terms of cost. On the other hand, a resin such as a crystalline resin that has a melting point and is fluid at high temperatures can be molded easily and inexpensively.

Therefore, in recent years, polyimide resins with thermoplasticity have been reported. Thermoplastic polyimide resins are excellent in moldability in addition to the inherent heat resistance of polyimide resins. Therefore, thermoplastic polyimide resins can also be applied to moldings used in harsh environments where general-purpose thermoplastic resins such as nylon and polyester could not be applied.

By the way, as a luminescent material, inorganic luminescent materials such as phosphors have hitherto been mainstream (Patent Document 2).
However, although inorganic light-emitting materials have excellent light-emitting properties, they are expensive in terms of raw materials and manufacturing costs, making it difficult to use them in large amounts depending on the application. Also, luminescent materials such as phosphors are generally pulverized into particles by pulverizing sintered materials and then dispersed in resin or glass for molding. Molding was difficult.

JP 2005-28524 A JP 2017-155098 A

Therefore, in recent years, the development of organic luminescent materials to replace inorganic luminescent materials has been awaited. Organic light-emitting materials can be produced in large quantities at a lower cost than inorganic light-emitting materials. Therefore, it is possible to use a large amount without worrying about the cost, and it is possible to secure a good light emitting space in a wide range. In addition, since the organic material itself can be made into a film, the selectivity of the shape to be used is remarkably improved.

While organic light-emitting materials are thus very promising, it has been difficult to find a substitute for inorganic light-emitting materials from among the many existing organic materials. In particular, among organic materials, there are not many materials that exhibit luminous properties, and when considering application to wavelength conversion materials, etc., it is assumed that they will be used in harsh environments, so high weather resistance and However, it has been difficult to achieve these requirements with organic materials.

Accordingly, an object of the present invention is to provide a luminescent molded article and a wavelength conversion member which are composed of an organic material and have excellent luminescent properties and heat resistance.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a light-emitting molded article that contains a predetermined polyimide resin and satisfies predetermined requirements, and has completed the present invention.

That is, the gist and configuration of the present invention are as follows.
[1] A repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2):

(R ₁ is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure. R ₂ is a C 5-16 divalent chain aliphatic group. _{X 1} and X ₂ are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.)
and the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural units of the formula (1) and the repeating structural unit of the formula (2) is 20 to 70 mol%. Polyimide resin (A) A luminescent molded article comprising
The amount of active protons in the luminescent molded product is 0.01 mol% or more when the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is 100 mol%. Luminous molding.
[2] The above [ 1].
[3] The luminescent molded article according to the above [1], wherein the molded article consists only of the polyimide resin (A).
[4] The luminescent molded article according to any one of [1] to [3] above, which is obtained by compression-molding the powder containing the polyimide resin (A).
[5] A wavelength conversion member comprising the luminescent molded product according to any one of [1] to [4] above.

According to the present invention, it is possible to provide a luminescent molded article and a wavelength conversion member that are composed of an organic material and have excellent luminescent properties and heat resistance.

FIG. 1 shows three-dimensional data of excitation wavelength vs. emission wavelength vs. fluorescence intensity, prepared by excitation-emission matrix (EEM) measurement for the powder of Reference Example 1. FIG. FIG. 2 is three-dimensional data of excitation wavelength vs. emission wavelength vs. fluorescence intensity, which was created by performing EEM measurement for Comparative Molded Body 1 of Comparative Example 1. FIG. FIG. 3 shows three-dimensional data of excitation wavelength vs. emission wavelength vs. fluorescence intensity, which was created by performing EEM measurement for molded body 1 of Example 1. FIG.

Embodiments of the luminescent molded article and the wavelength conversion member according to the present invention are described in detail below.
In this specification, the term "A to B" regarding numerical values means "A or more and B or less" (when A<B) or "A or less than B" (when A>B). . Moreover, in the present invention, a combination of preferred aspects is a more preferred aspect.

[Light emitting molding]
The luminescent molding of the present invention comprises a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2):

(R ₁ is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure. R ₂ is a C 5-16 divalent chain aliphatic group. _{X 1} and X ₂ are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.)
and the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural units of the formula (1) and the repeating structural unit of the formula (2) is 20 to 70 mol%. Polyimide resin (A) and the amount of active protons in the luminescent molded product is 0.01 mol% or more when the total of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) is 100 mol%. is.

The luminescent molded article of the present invention (hereinafter sometimes simply referred to as ``molded article'') has the above-described structure, so that it exhibits excellent luminescent properties and heat resistance while being composed of an organic material.
Although the reason why the luminescent molded article of the present invention exhibits the above effects is not clear, it is speculated as follows.
The polyimide resin (A) has an aliphatic skeleton in the diamine part of the polyimide, and the carbonyl part has an electronic state from the keto type (NC=O part) to the enol type (N=C-OH part). It is thought that it has a structure that is easily changed. Therefore, by setting the amount of active protons in the molded body to a predetermined amount or more, the active protons can easily approach the carbonyl portion of the polyimide, the contribution of the enol type in the chemical skeleton of the polyimide increases, and thermal energy due to molecular motion is generated. It is considered that the deactivation of is suppressed and the luminous properties are improved. Moreover, it is considered that a lone pair of electrons exists on the nitrogen atoms of the polyimide, which makes it less susceptible to resonance stabilization and more likely to cause ESIPT than when an aromatic amine is used.
Furthermore, since the polyimide resin (A) has a predetermined structure, it is also excellent in heat resistance.

<Active proton>
In the present specification, the active proton is hydrogen contained in the structure of the polyimide resin (A), and hydrogen contained in the structure of components other than the polyimide resin (A) that are optionally blended, It refers to hydrogen (active hydrogen) that can replace deuterium contained in the solvent when the molded piece is dissolved in a solvent containing a heavy solvent in which the active hydrogen of the solvent is replaced with deuterium.
The active hydrogen contained in the structure of the polyimide resin (A) and the active hydrogen contained in the structure of components other than the polyimide resin (A) to be blended as needed include the polyimide resin (A) or other Active hydrogen derived from the component itself (for example, resin skeleton, etc.), active hydrogen derived from unreacted raw materials remaining in the polyimide resin (A) or other components, polyimide resin (A), or other components deteriorated and active hydrogen generated by the reaction. Specific examples of these active hydrogens include hydrogen such as amino group, acetyl group, amic acid, hydroxy group, and mercapto group contained in the structure of the polyimide resin (A) or other components.

The amount of active protons in the light-emitting molded article of the present invention is 0.01 mol% or more when the total of the repeating structural units of the above formula (1) and the repeating structural units of the above formula (2) is 100 mol%. Yes, preferably 0.05 mol % or more, more preferably 0.10 mol % or more, and still more preferably 0.20 mol % or more. If the amount of active protons in the molded product is less than 0.01 mol %, sufficient light emission characteristics cannot be obtained.
Further, the upper limit of the active proton amount is not particularly limited. When the total of the repeating structural unit of (1) and the repeating structural unit of the above formula (2) is 100 mol%, it is preferably 10.0 mol% or less, more preferably 5.0 mol% or less, and still more preferably It is 1.0 mol % or less. Functional groups corresponding to the active protons (for example, amino groups, hydroxy groups, etc.) are highly polar and highly hydrophilic. Therefore, as the number of such functional groups increases in the luminescent molded article, the water absorption rate of the luminescent molded article tends to increase. By setting the amount of active protons within the above range, the water absorption rate of the luminescent molding does not become too high, and deterioration of the water absorption can be suppressed.
Specifically, from the viewpoint of sufficient light emission characteristics and suppression of deterioration of water absorption, the amount of active protons is the sum of the repeating structural unit of the above formula (1) and the repeating structural unit of the above formula (2). When 100 mol%, preferably 0.01 to 10.0 mol%, more preferably 0.05 to 10.0 mol%, still more preferably 0.10 to 5.0 mol%, still more It is preferably 0.20 to 1.0 mol %.
The amount of active protons in the compact can be measured by the method described in Examples.

The active proton preferably contains hydrogen of the terminal amino group contained in the structure of the polyimide resin (A), more preferably hydrogen of the terminal amino group. Hydrogen of the terminal amino group contained in the structure of the polyimide resin (A) is preferable in that the content can be controlled by the heating temperature at the time of molding the light-emitting molded article, and thus the amount of active protons can also be controlled.
The amount of amino groups in the molded article is preferably 0.01 mol% or more when the total of the repeating structural unit of the above formula (1) and the repeating structural unit of the above formula (2) is 100 mol%. , more preferably 0.03 mol % or more, still more preferably 0.05 mol % or more.
In addition, from the viewpoint of suppressing the deterioration of water absorbency due to active protons, the amount of amino groups is 100 mol% when the total of the repeating structural units of the above formula (1) and the repeating structural units of the above formula (2) is , preferably 10.0 mol % or less, more preferably 5.0 mol % or less, still more preferably 1.0 mol % or less. Specifically, from the viewpoint of sufficient light emission characteristics and the viewpoint of suppressing deterioration of water absorption due to active protons, the amount of amino groups is the repeating structural unit of the above formula (1) and the repeating structural unit of the above formula (2). When the total of 100 mol%, preferably 0.01 to 10.0 mol%, more preferably 0.03 to 5.0 mol%, still more preferably 0.05 to 1.0 mol% .
The amount of amino groups in the molded article can be measured by the method described in Examples.

The active protons may also be active hydrogens (hereinafter sometimes referred to as "externally active protons") contained in the structures of components other than the polyimide resin (A) that are blended as needed. Components having externally active protons include, for example, resins having active hydrogens in their structures. By further including a resin having active hydrogen in the structure of the molded article, the amount of active protons in the molded article can be increased. Examples of such resins include resins having an acetyl group, an amic acid group, an amino group, a hydroxy group, a mercapto group, or the like in their structure.

<Polyimide resin (A)>
The polyimide resin (A) used in the present invention is a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2):

(R ₁ is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure. R ₂ is a C 5-16 divalent chain aliphatic group. _{X 1} and X ₂ are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.)
and the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is 20 to 70 mol%.

The polyimide resin (A) used in the present invention is a crystalline thermoplastic resin. The thermoplastic polyimide resin is a polyimide resin having no glass transition temperature (Tg), or a glass transition temperature lower than the glass transition temperature, which is formed by closing the imide ring after molding in the state of a polyimide precursor such as polyamic acid. It is distinguished from polyimide resin, which decomposes at temperature.

The repeating structural unit of formula (1) is described in detail below.
R ₁ is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure. Here, the alicyclic hydrocarbon structure means a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and It may be cyclic or polycyclic.
Examples of the alicyclic hydrocarbon structure include, but are not limited to, cycloalkane rings such as cyclohexane ring, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane ring, and bicycloalkene rings such as norbornene. Do not mean. Among these, a cycloalkane ring is preferred, a cycloalkane ring having 4 to 7 carbon atoms is more preferred, and a cyclohexane ring is even more preferred.
R ₁ has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms.
R ₁ contains at least one, preferably 1 to 3, alicyclic hydrocarbon structures.

R ₁ is preferably a divalent group represented by the following formula (R1-1) or (R1-2).

(m ₁₁ and m ₁₂ are each independently an integer of 0 to 2, preferably 0 or 1; m ₁₃ to m ₁₅ are each independently an integer of 0 to 2, preferably 0 or 1.)

R ₁ is particularly preferably a divalent group represented by the following formula (R1-3).

In the divalent group represented by the above formula (R1-3), the positional relationship of the two methylene groups with respect to the cyclohexane ring may be cis or trans, and the ratio of cis to trans may be can be any value.

X ₁ is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, tetracene ring and perylene ring. Among these, benzene ring, naphthalene ring and perylene ring are preferred, and benzene ring is more preferred.
X ₁ has 6 to 22 carbon atoms, preferably 6 to 20 carbon atoms.
X ₁ contains at least one, preferably 1 to 3, aromatic rings.

X ₁ is preferably a tetravalent group represented by any one of formulas (X-1) to (X-6) below.

(R ₁₁ to R ₂₄ are each independently an alkyl group having 1 to 4 carbon atoms; p ₁₁ to p ₁₃ and p ₁₉ to p ₂₄ are each independently an integer of 0 to 2, preferably 0. p ₁₄ , p ₁₅ , p ₁₆ and p ₁₈ are each independently an integer of 0 to 3, preferably 0. p ₁₇ is an integer of 0 to 4, preferably 0. Each of L ₁₁ to L ₁₃ is independently a single bond, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.)
Since X ₁ is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, R ₁₂ , R ₁₃ , p ₁₂ and p ₁₃ in formula (X-2) are represented by formula (X- The number of carbon atoms in the tetravalent group represented by 2) is selected within the range of 10 to 22.
Similarly, L ₁₁ , R ₁₄ , R ₁₅ , p ₁₄ and p ₁₅ in formula (X-3) are in the range of 12 to 22 carbon atoms in the tetravalent group represented by formula (X-3). L ₁₂ , L ₁₃ , R ₁₆ , R ₁₇ , R ₁₈ , p ₁₆ , p ₁₇ and p ₁₈ in formula (X-4) are selected to contain tetravalent is selected so that the number of carbon atoms in the group falls within the range of 18 to 22, and R ₁₉ , R ₂₀ , p ₁₉ and p ₂₀ in formula (X-5) are tetravalent represented by formula (X-5) is selected so that the number of carbon atoms in the group is within the range of 10 to 22, and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , p ₂₁ , p ₂₂ , p ₂₃ and p ₂₄ in formula (X-6) are It is selected so that the number of carbon atoms in the tetravalent group represented by formula (X-6) falls within the range of 20-22.

X ₁ is particularly preferably a tetravalent group represented by any one of the following formulas (X-7) to (X-10).

Next, the repeating structural unit of formula (2) will be described in detail below.
R ₂ is a divalent chain aliphatic group having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, still more preferably 8 to 10 carbon atoms. Here, the chain aliphatic group means a group derived from a chain aliphatic compound, the chain aliphatic compound may be saturated or unsaturated, straight-chain It may be branched or branched.
R ₂ is preferably an alkylene group having 5 to 16 carbon atoms, more preferably an alkylene group having 6 to 14 carbon atoms, still more preferably an alkylene group having 7 to 12 carbon atoms, and most preferably an alkylene group having 8 to 10 carbon atoms. It is an alkylene group. The alkylene group may be a straight-chain alkylene group or a branched alkylene group, but is preferably a straight-chain alkylene group.
R ₂ is preferably one or more selected from the group consisting of octamethylene group and decamethylene group, particularly preferably octamethylene group.

_X2 is defined in the same manner as _X1 in Formula (1), and the preferred embodiments are also the same.

The content ratio of the repeating structural unit of formula (1) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is 20 to 70 mol %. When the content ratio of the repeating structural unit of formula (1) is within the above range, it is possible to sufficiently crystallize the polyimide resin. When the content ratio is less than 20 mol %, moldability is deteriorated, and when it exceeds 70 mol %, crystallinity is deteriorated, resulting in deterioration of heat resistance.
The content ratio of the repeating structural unit of formula (1) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 65 mol% or less from the viewpoint of expressing high crystallinity. More preferably 60 mol % or less, still more preferably 50 mol % or less, still more preferably less than 40 mol %.
When the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is 20 mol% or more and less than 40 mol%, the polyimide resin (A) The crystallinity of is increased, and a resin molding having more excellent heat resistance can be obtained. The content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, and still more preferably 32 mol% or more from the viewpoint of moldability, and is even more preferable from the viewpoint of expressing high crystallinity. is 35 mol % or less. Specifically, from the viewpoint of moldability and high crystallinity, the content ratio is preferably 25 to 35 mol%, more preferably 30 to 35 mol%, and still more preferably 32 to 35 mol%. is.

The total content ratio of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) with respect to all repeating structural units constituting the polyimide resin (A) is preferably 50 to 100 mol%, more preferably 75 ~100 mol%, more preferably 80 to 100 mol%, still more preferably 85 to 100 mol%.

Polyimide resin (A) may further contain a repeating structural unit of the following formula (3). In that case, the content ratio of the repeating structural unit of formula (3) to the sum of the repeating structural units of formula (1) and the repeating structural units of formula (2) is preferably 25 mol % or less. On the other hand, the lower limit is not particularly limited as long as it exceeds 0 mol %.
When the repeating structural unit of formula (3) is contained, the content ratio of the repeating structural unit of formula (3) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is From the viewpoint of improvement, it is preferably 5 mol% or more, more preferably 10 mol% or more, while from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more preferably 15 mol% or less. . Specifically, from the viewpoint of improving heat resistance and maintaining crystallinity, the content ratio is preferably 5 to 20 mol %, more preferably 10 to 15 mol %.

(R ₃ is a C 6-22 divalent group containing at least one aromatic ring. X ₃ is a C 6-22 tetravalent group containing at least one aromatic ring.)

R ₃ is a C 6-22 divalent group containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and tetracene ring. Among these, benzene ring and naphthalene ring are preferred, and benzene ring is more preferred.
R ₃ has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
R ₃ contains at least one, preferably 1 to 3, aromatic rings.

R ₃ is preferably a divalent group represented by the following formula (R3-1) or (R3-2).

(m ₃₁ and m ₃₂ are each independently an integer of 0 to 2, preferably 0 or 1; m ₃₃ and m ₃₄ are each independently an integer of 0 to 2, preferably 0 or 1. R ₂₁ , R ₂₂ and R ₂₃ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. p ₂₁ , p ₂₂ and p ₂₃ are integers of 0 to 4, preferably 0. L ₂₁ is a single bond, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.)
Since R ₃ is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, m ₃₁ , m ₃₂ , R ₂₁ and p ₂₁ in formula (R3-1) are represented by formula (R3- It is selected so that the number of carbon atoms of the divalent group represented by 1) falls within the range of 6-22.
Similarly, L ₂₁ , m ₃₃ , m ₃₄ , R ₂₂ , R ₂₃ , p ₂₂ and p ₂₃ in formula (R3-2) have It is chosen to fall within the range of 12-22.

_X3 is defined in the same manner as _X1 in Formula (1), and the preferred embodiments are also the same.

The terminal structure of the polyimide resin (A) is not particularly limited, but from the viewpoint of increasing the amount of active protons, it is preferable to have an amino group at the terminal, and from the viewpoint of improving heat aging resistance, it has 5 to 5 carbon atoms. It is preferably terminated with 14 chain aliphatic groups.
The chain aliphatic group may be saturated or unsaturated, linear or branched. When the polyimide resin (A) has the above specific group at its terminal, a resin composition having excellent heat aging resistance can be obtained.
Examples of saturated chain aliphatic groups having 5 to 14 carbon atoms include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, Lauryl group, n-tridecyl group, n-tetradecyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 2-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, isooctyl group, 2-ethylhexyl group , 3-ethylhexyl group, isononyl group, 2-ethyloctyl group, isodecyl group, isododecyl group, isotridecyl group, isotetradecyl group and the like.
Examples of unsaturated chain aliphatic groups having 5 to 14 carbon atoms include 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, 1- octenyl group, 2-octenyl group, nonenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group and the like.
Among them, the chain aliphatic group is preferably a saturated chain aliphatic group, and more preferably a saturated straight chain aliphatic group. From the viewpoint of obtaining heat aging resistance, the chain aliphatic group preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms, more preferably 12 or less carbon atoms. has 10 or less carbon atoms, more preferably 9 or less carbon atoms. Only one type of chain aliphatic group may be used, or two or more types thereof may be used.
The chain aliphatic group is particularly preferably one or more selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group. more preferably one or more selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group and isononyl group, most preferably n-octyl group and isooctyl group , and 2-ethylhexyl group.
Moreover, from the viewpoint of heat aging resistance, the polyimide resin (A) preferably has only chain aliphatic groups having 5 to 14 carbon atoms at its terminals in addition to terminal amino groups and terminal carboxy groups. When a group other than the above is present at the terminal, the content thereof is preferably 10 mol % or less, more preferably 5 mol % or less, relative to the chain aliphatic group having 5 to 14 carbon atoms.

From the viewpoint of exhibiting excellent heat aging resistance, the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) is 100 in total of all repeating structural units constituting the polyimide resin (A). It is preferably 0.01 mol % or more, more preferably 0.1 mol % or more, and still more preferably 0.2 mol % or more based on mol %. In addition, in order to secure a sufficient molecular weight and obtain good mechanical properties, the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) is Preferably 10 mol% or less, more preferably 6 mol% or less, still more preferably 3.5 mol% or less, even more preferably 2.0 mol% or less, more preferably 100 mol% or less of all repeating structural units More preferably, it is 1.2 mol % or less.
The content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) can be determined by depolymerizing the polyimide resin (A).

Polyimide resin (A) preferably has a melting point of 360° C. or lower and a glass transition temperature of 150° C. or higher.
The melting point of the polyimide resin (A) is preferably 280° C. or higher, more preferably 290° C. or higher, from the viewpoint of heat resistance, and is preferably 345° C. or lower, more preferably 345° C. or lower, from the viewpoint of achieving high moldability. is 340° C. or less, more preferably 335° C. or less. Specifically, from the viewpoint of heat resistance and high molding processability, the melting point of the polyimide resin (A) is preferably 280 to 345° C., more preferably 280 to 340° C., still more preferably 290 to 345° C. 335°C.
Further, the glass transition temperature of the polyimide resin (A) is more preferably 160° C. or higher, more preferably 170° C. or higher from the viewpoint of heat resistance, and preferably 250° C. from the viewpoint of expressing high moldability. Below, more preferably 230° C. or less, and still more preferably 200° C. or less. Specifically, from the viewpoint of heat resistance and high moldability, the glass transition temperature of the polyimide resin (A) is preferably 160 to 250°C, more preferably 160 to 230°C, and still more preferably 170°C. ~200°C.
In addition, from the viewpoint of improving the crystallinity, heat resistance, mechanical strength, and chemical resistance, the polyimide resin (A) is measured by a differential scanning calorimeter, and after melting the polyimide resin, the temperature is lowered at a rate of 20 ° C./min. The heat quantity at the crystallization exothermic peak observed upon cooling (hereinafter also simply referred to as “crystallization exothermic value”) is preferably 5.0 mJ/mg or more, more preferably 10.0 mJ/mg or more. More preferably, it is 17.0 mJ/mg or more. Although the upper limit of the crystallization heat value is not particularly limited, it is usually 45.0 mJ/mg or less.
The melting point, glass transition temperature, and crystallization heat value of the polyimide resin (A) can all be measured by a differential scanning calorimeter, and specifically by the methods described in Examples.

The weight average molecular weight Mw of the polyimide resin (A) is preferably 40,000 to 150,000, more preferably 40,000 to 100,000, still more preferably 42,000 to 80,000, still more preferably 45,000 to 70,000, more preferably 45,000 to 65,000. When the weight average molecular weight Mw of the polyimide resin (A) is 40,000 or more, the heat distortion temperature (HDT) under low load environment is improved and the mechanical strength is also improved. Further, when Mw is 150,000 or less, moldability is good.
The weight average molecular weight Mw of the polyimide resin (A) can be measured by a gel permeation chromatography (GPC) method using polymethyl methacrylate (PMMA) as a standard sample, and specifically can be measured by the method described in Examples. .

The logarithmic viscosity at 30° C. of a 0.5% by mass concentrated sulfuric acid solution of the polyimide resin (A) is preferably in the range of 0.8 to 2.0 dL/g, more preferably 0.9 to 1.8 dL/g. . When the logarithmic viscosity is 0.8 dL/g or more, it becomes easy to form a microphase-separated structure in the resulting resin molding, and sufficient mechanical strength can be obtained. When the logarithmic viscosity is 2.0 dL/g or less, molding processability and handleability are improved. The logarithmic viscosity μ is obtained from the following formula by measuring the flow times of concentrated sulfuric acid and the polyimide resin solution at 30° C. using a Canon Fenske viscometer. Specifically, it can be measured by the method described in Examples.
μ = ln [(ts/t ₀ )/C]
t ₀ : Flow time of concentrated sulfuric acid ts: Flow time of polyimide resin solution C: 0.5 (g/dL)

(Method for producing polyimide resin (A))
Polyimide resin (A) can be produced by reacting a tetracarboxylic acid component and a diamine component. The tetracarboxylic acid component contains a tetracarboxylic acid and/or derivative thereof containing at least one aromatic ring, and the diamine component contains a diamine containing at least one alicyclic hydrocarbon structure and a linear aliphatic diamine. .

The tetracarboxylic acid containing at least one aromatic ring is preferably a compound in which four carboxy groups are directly bonded to the aromatic ring, and may contain an alkyl group in its structure. The tetracarboxylic acid preferably has 6 to 26 carbon atoms. Examples of the tetracarboxylic acid include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, and 3,3′,4,4′-biphenyl. Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like are preferred. Among these, pyromellitic acid is more preferable.

Derivatives of tetracarboxylic acids containing at least one aromatic ring include anhydrides or alkyl esters of tetracarboxylic acids containing at least one aromatic ring. The tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms. Anhydrides of tetracarboxylic acids include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3′,4,4′-diphenyl sulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride and the like are included. Examples of alkyl esters of tetracarboxylic acids include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylate, 3,3′,4 ,4′-diphenylsulfonetetracarboxylate dimethyl, 3,3′,4,4′-benzophenonetetracarboxylate dimethyl, 3,3′,4,4′-biphenyltetracarboxylate dimethyl, 1,4,5,8 -Naphthalenetetracarboxylate dimethyl and the like. In the above alkyl ester of tetracarboxylic acid, the alkyl group preferably has 1 to 3 carbon atoms.

As the tetracarboxylic acid and/or derivative thereof containing at least one aromatic ring, at least one compound selected from the above may be used alone, or two or more compounds may be used in combination.

The diamine containing at least one alicyclic hydrocarbon structure preferably has 6 to 22 carbon atoms, such as 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4- Bis(aminomethyl)cyclohexane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine) , carvonediamine, limonenediamine, isophoronediamine, norbornanediamine, bis(aminomethyl)tricyclo[5.2.1.0 ^2,6 ]decane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4'-Diaminodicyclohexylpropane and the like are preferred. These compounds may be used alone, or two or more compounds selected from these may be used in combination. Among these, 1,3-bis(aminomethyl)cyclohexane can be preferably used. Diamines containing an alicyclic hydrocarbon structure generally have structural isomers, but the ratio of cis/trans isomers is not limited.

The chain aliphatic diamine may be linear or branched, and preferably has 5 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 7 to 12 carbon atoms. In addition, if the chain portion has 5 to 16 carbon atoms, an ether bond may be included therebetween. Chain aliphatic diamines such as 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-hepta methylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-trideca Methylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, 2,2'-(ethylenedioxy)bis(ethyleneamine) and the like are preferred.
Chain aliphatic diamines may be used singly or in combination. Among these, chain aliphatic diamines having 8 to 10 carbon atoms can be preferably used, and one or more selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine is particularly preferable. can be used for

When producing the polyimide resin (A), the molar amount of the diamine charged containing at least one alicyclic hydrocarbon structure with respect to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine The ratio is preferably 20-70 mol %. The molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 32 mol% or more, and from the viewpoint of expressing high crystallinity, preferably 60 mol% or less, more preferably 50 mol% or more. mol % or less, more preferably less than 40 mol %, more preferably 35 mol % or less.

In addition, the diamine component may contain a diamine containing at least one aromatic ring. The diamine containing at least one aromatic ring preferably has 6 to 22 carbon atoms, such as orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-diethynylbenzenediamine, 1,3-diethynyl. Benzenediamine, 1,4-diethynylbenzenediamine, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4 ,4'-diaminodiphenylmethane, α,α'-bis(4-aminophenyl)1,4-diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,4-diisopropylbenzene, 2,2- bis[4-(4-aminophenoxy)phenyl]propane, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene and the like.

In the above, the molar ratio of the charged amount of the diamine containing at least one aromatic ring to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is 25 mol% or less. It is preferably 20 mol % or less, still more preferably 15 mol % or less.
Although the lower limit of the molar ratio is not particularly limited, it is preferably 5 mol % or more, more preferably 10 mol % or more, from the viewpoint of improving heat resistance.
On the other hand, from the viewpoint of reducing the coloring of the polyimide resin, the molar ratio is more preferably 12 mol% or less, even more preferably 10 mol% or less, even more preferably 5 mol% or less, and even more preferably 0 mol %.

When producing the polyimide resin (A), the charged amount ratio of the tetracarboxylic acid component and the diamine component is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component. .

Moreover, when producing the polyimide resin (A), a terminal blocking agent may be mixed in addition to the tetracarboxylic acid component and the diamine component. As the terminal blocking agent, one or more selected from the group consisting of monoamines and dicarboxylic acids is preferable. The amount of the terminal blocking agent used may be an amount that can introduce a desired amount of terminal groups into the polyimide resin (A), and is 0.0001 to 0.001 to 0.001 to 1 mol of the tetracarboxylic acid and/or derivative thereof. 1 mol is preferable, 0.001 to 0.06 mol is more preferable, 0.002 to 0.035 mol is more preferable, 0.002 to 0.020 mol is even more preferable, 0.002 to 0.012 mol is even more preferred.
Among them, a monoamine terminal blocking agent is preferable as the terminal blocking agent, and from the viewpoint of improving heat aging resistance by introducing the chain aliphatic group having 5 to 14 carbon atoms described above at the end of the polyimide resin (A). , monoamines having a chain aliphatic group of 5 to 14 carbon atoms are more preferred, and monoamines having a saturated linear aliphatic group of 5 to 14 carbon atoms are even more preferred.
The terminal blocking agent is particularly preferably one or more selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine. more preferably one or more selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably n-octylamine and isooctyl One or more selected from the group consisting of amines and 2-ethylhexylamine.

As a polymerization method for producing the polyimide resin (A), a known polymerization method can be applied, and the method described in International Publication No. 2016/147996 can be used.

The luminescent molded article of the present invention can be formed, for example, by compression molding. More specifically, it is preferable to compress and mold a powder containing the polyimide resin (A).
Moreover, the molded article preferably consists of the polyimide resin (A) only, and such a molded article is preferably formed by compression-molding a powder consisting of the polyimide resin (A) only.

again. The luminescent molded article of the present invention may further contain other resins than the polyimide resin (A), if necessary.
Other resins include, for example, amorphous thermoplastic resins, crystalline thermoplastic resins, and thermosetting resins.
Examples of amorphous thermoplastic resins include polystyrene resin; polyvinyl chloride; polyvinylidene chloride; polymethyl methacrylate; acrylonitrile-butadiene-styrene resin; polycarbonate resin; Ether resins; polyethersulfone resins; polyetherimide resins; polyamideimide resins; polyurethane resins; These can be used individually by 1 type or in combination of 2 or more types.
Examples of crystalline thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, and cyclic polyolefins; polyamide resins; polyacetal resins; polyphenylene sulfide resins; polyester resin; liquid crystal polymer; fluorine resin such as polytetrafluoroethylene and polyvinylidene fluoride; polymethylpentene resin; polyurethane resin; Alternatively, a resin having a melting point lower than the melting point of the polyimide resin (A) may be used. These can be used individually by 1 type or in combination of 2 or more types.
The thermosetting resin is not particularly limited as long as it is a thermosetting resin capable of dispersing the polyimide resin (A). Examples include epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyimide resin, silicone resin, One or more selected from the group consisting of urethane resins, casein resins, furan resins, alkyd resins, and xylene resins can be used. Among these, the thermosetting resin is composed of epoxy resin and urethane resin from the viewpoint of containing the polyimide resin (A) to be used in the molded body while maintaining the shape thereof, and from the viewpoint of the dispersibility of the polyimide resin (A). One or more selected from the group are preferred, and epoxy resins are more preferred.
Moreover, from the viewpoint of obtaining a molded article having excellent light emitting properties, the other resin is preferably a resin capable of supplying external active protons to the polyimide resin (A). Specifically, it is a resin having active hydrogen in its structure, and more specifically, it includes polyamide resin, polyamideimide resin, epoxy resin, urethane resin, urea resin, phenol resin, cyanate resin, and the like. Here, the active hydrogen that the resin has in the structure includes active hydrogen derived from the resin itself (resin skeleton), active hydrogen derived from unreacted raw materials remaining in the resin, and active hydrogen generated due to deterioration of the resin. etc. For example, in the case of polyamide resin, it is the hydrogen of the amide group contained in the structure, and in the case of phenol resin, it is the hydrogen of the hydroxyl group contained in the structure.

<Resin (B)>
The molded article of the present invention is one selected from the group consisting of polyamide resins, polyamideimide resins, epoxy resins, urethane resins, urea resins, phenol resins and cyanate resins, from the viewpoint of obtaining molded articles having excellent light emitting properties. It is preferable that the above resin (B) is included. The resin (B) is a resin having active hydrogen in its structure, and by compounding with a polyimide resin (A) having a predetermined structure, the amount of active protons in the resulting molded product can be increased, and light emission can be achieved. characteristics can be improved. Moreover, when the resin (B) is added, a molded product can be obtained not only by compression molding but also by injection molding, and the degree of freedom in designing the shape of the molded product is improved.

Resin (B) is one or more selected from the group consisting of polyamide resins, polyamideimide resins, epoxy resins, urethane resins, urea resins, phenol resins and cyanate resins, and among them from the group consisting of polyamide resins and epoxy resins. One or more selected are preferred, and polyamide resins are more preferred.
Polyamide resins include polyamide 6 (PA6), polyamide 66, polyamide 66/6, polyamide 46, polyamide 11, polyamide 12, MXD6, polyamide 9T and the like, and polyamideimide resins include Torlon (manufactured by Solvay) and the like. Epoxy resins include bisphenol A type epoxy resins, urethane resins include thermoplastic urethane resins, and urea resins include pure polyurea, hybrid polyurea, urea urethane, and the like. Phenolic resins include novolac type phenolic resins and resol type phenolic resins, and cyanate resins include CYTESTER (manufactured by Mitsubishi Gas Chemical Company, Inc.).
One of the above resins (B) may be used alone, or two or more thereof may be used in combination.

Since the resin (B) is a resin having active hydrogen in its structure, a molded body containing the resin (B) can have an increased amount of active protons compared to a molded body made of only the polyimide resin (A). It is possible to improve the light emission characteristics.
When the molded body contains the resin (B), the amount of active protons in the molded body is 100 mol% of the repeating structural unit of the above formula (1) and the repeating structural unit of the above formula (2). , preferably 0.01 to 100,000 mol %, more preferably 1 to 10,000 mol %, still more preferably 100 to 2,000 mol %.

When the molded article contains the resin (B), the mass ratio (A/B) of the polyimide resin (A) and the resin (B) in the molded article is preferably 1/99 to 99/1, more preferably It is in the range of 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 10/90 to 85/15. Within the above range, the dispersibility between the resins is improved, and a decrease in the mechanical strength of the molded article can be suppressed.

In addition, the total content of the polyimide resin (A) and the resin (B) in the molded body is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass, from the viewpoint of obtaining the effects of the present invention. % or more. Moreover, an upper limit is 100 mass %.

<Additive>
The luminescent molded article of the present invention contains a filler, a delustering agent, a nucleating agent, a plasticizer, an antistatic agent, an anti-coloring agent, an anti-gelling agent, a flame retardant, a coloring agent, a slidability improver, an antioxidant, Additives such as a conductive agent and a resin modifier may be contained as necessary.
When the molded article contains an additive, the content of the additive in the molded article is not particularly limited, but from the viewpoint of expressing the effect of the additive while maintaining the physical properties derived from the polyimide resin (A), it is usually 50 % by mass or less, preferably 0.0001 to 30% by mass, more preferably 0.0001 to 15% by mass, still more preferably 0.001 to 10% by mass, still more preferably 0.01 to 8% by mass be.

[Method for producing light-emitting molding]
Since the polyimide resin (A) contained in the luminescent molded article of the present invention has thermoplasticity, the luminescent molded article can be easily produced by thermoforming a resin composition containing the polyimide resin (A).
Thermoforming methods include compression molding, injection molding, extrusion molding, blow molding, laser molding, ultrasonic thermoforming, welding, and welding. is. Thermoforming is preferred because molding can be performed without setting the molding temperature to a high temperature exceeding, for example, 400°C. Among them, when performing compression molding or injection molding, molding is possible without setting the molding temperature and the mold temperature at the time of molding to a high temperature, which is preferable.

In particular, as a method for producing the light-emitting molded article of the present invention, <1> when producing a molded article consisting only of the polyimide resin (A), it is preferable to compress the powder of the polyimide resin (A). 2> When producing a molded article containing the polyimide resin (A) and the resin (B), it is preferable to carry out injection molding by the following method. A detailed description will be given below.

<1> Compression molding In the case of producing a molded body consisting only of the polyimide resin (A), it is more preferable to carry out compression molding from the viewpoint of increasing the amount of active protons in the molded body to a predetermined amount or more.
In the case of a molded article made of only polyimide resin (A), the amount of active protons is determined by the amount of hydrogen in terminal amino groups contained in the structure of polyimide resin (A). Normally, the amount of terminal amino groups contained in the structure of the polyimide resin (A) is the largest in the powder state immediately after synthesis, and tends to decrease as the polyimide resin (A) is exposed to higher temperatures in subsequent processing steps. be. Therefore, from the viewpoint of appropriately leaving the terminal amino groups of the polyimide resin (A) in the molded body, the molded body is produced by compression molding, which has a smaller number of heat treatments involving melting and less processing time than injection molding. is preferred.

As a method for producing a molded body by compression molding, a known method can be used, but it is preferable to use, for example, the following method.

(preforming)
First, powder of polyimide resin (A) is put into a mold and compressed to perform preforming.

The powder of the polyimide resin (A) is preferably washed and dried as appropriate after synthesizing the resin.
Drying can be performed by a known method using a hot air dryer, a dehumidifying dryer, or the like. The drying temperature is preferably 80-160°C, more preferably 120-150°C. Also, the drying time is preferably 6 to 24 hours, more preferably 8 to 16 hours. By performing a drying treatment as a pretreatment of the polyimide resin (A) powder, it is possible to obtain a molded article having excellent bending strength and heat resistance.

The volume average particle diameter (D50) of the polyimide resin (A) powder is preferably 10 to 100 μm. Within the above range, the polyimide resin (A) powder can be easily handled, and workability and moldability are improved. Therefore, the polyimide resin (A) may be pulverized or granulated before molding so as to have the above volume average particle size, if necessary.
The volume average particle diameter (D50) of the polyimide resin (A) powder can be measured by the method described in Examples.

The mold may be appropriately selected according to the shape of the molded body and molding conditions, and known molds can be used. Moreover, it is preferable to apply a release agent to the mold in advance.

A device for preforming includes, for example, a cooling press device.
Preferred conditions for preforming include, for example, gauge pressure of 20 to 25 MPa, normal temperature (15 to 25° C.), and forming in an inert gas atmosphere.

(thermoforming)
After preforming, thermoforming is performed while compressing to obtain a molded body.
Apparatus for thermoforming includes, for example, a vacuum press apparatus, an autoclave apparatus, a double belt press apparatus, and the like.

The temperature during thermoforming is preferably 335-385°C, more preferably 350-370°C. By setting the amount within the above range, a good molded product can be obtained while controlling the active protons to a predetermined amount or more.
The atmosphere during thermoforming includes, for example, an air atmosphere, an inert gas atmosphere, a vacuum atmosphere, and the like. Among them, thermoforming in a vacuum atmosphere (-0.1 bar or less) is preferable from the viewpoint of preventing coloration of the molded body due to heating and exhibiting good light emitting properties.
The pressure during thermoforming is preferably 5-30 MPa, and the treatment time is preferably 10-20 minutes.

(cooling)
After the heat treatment, the compact is removed from the mold and compressed and cooled.
As an apparatus for compressing and cooling, for example, a cooling press apparatus and the like can be mentioned.
As conditions for compression cooling, for example, it is preferable to carry out at normal temperature (15 to 25° C.) in an atmospheric atmosphere under the same pressure and processing time as in thermoforming.

<2> Injection molding When producing a molded article containing the polyimide resin (A) and the resin (B), it is more preferable to perform injection molding from the viewpoint of obtaining a molded article having a uniform composition.

In the case of injection molding, the resin is once melted and pelletized, and the pellets are introduced into various molding machines to produce a molded body. There is a tendency for the base amount to decrease. However, when the resin (B) is blended, the resin (B) serves as a source of externally active protons, so the amount of active protons in the molded body can be increased to a predetermined amount or more, and excellent light emission characteristics can be achieved. It is possible to obtain a molded body having.

As a method for producing a molded body by injection molding, a known method can be used, but it is preferable to use, for example, the following method.

First, the polyimide resin (A), the resin (B), and, if necessary, after adding and dry blending various optional components, this is introduced into an extruder, preferably melted at 290 to 350 ° C. After melt-kneading and extruding in an extruder and cooling the extruded strand, pellets are produced by a pelletizer. Alternatively, the polyimide resin (A) is introduced into the extruder, preferably melted at 290 to 350 ° C., and the resin (B) and various optional components are introduced here, and the polyimide resin (A ), extruded, and after cooling the extruded strand, pellets may be produced by a pelletizer.

After drying the pellets, they can be introduced into various molding machines and thermoformed preferably at 290 to 350°C to produce a resin molded body having a desired shape. The temperature during thermoforming is more preferably 310 to 350°C.

[Use]
INDUSTRIAL APPLICABILITY The luminescent molded article of the present invention is excellent in luminescent properties and heat resistance, and thus can be applied to applications such as wavelength conversion members, fluorescent inks, and white luminescent materials. Among them, it can be suitably used as a wavelength conversion member.

<Wavelength conversion member>
The wavelength conversion member is preferably made of the luminescent molded article of the present invention. Examples of the wavelength conversion member include wavelength conversion films for various uses.
Since the wavelength conversion member made of the luminescent molded article of the present invention is made of an organic material, it can be used in large quantities without worrying about the cost, so it is possible to secure a good luminescent space over a wide range. In addition, the wavelength conversion member made of the luminescent molded article of the present invention has a high degree of freedom in shape design at the time of molding, and can be molded into a sheet shape or a film shape, which is difficult with inorganic materials, and is particularly suitable as a wavelength conversion film. is. In addition, since the wavelength conversion member made of the luminescent molded article of the present invention is excellent in heat resistance, it is expected to be used in a harsh environment such as outdoors, and is used as a wavelength conversion film for agriculture and gardening, and for SI solar cells. It is suitable as a wavelength conversion film.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these. In addition, various measurements and evaluations in each Production Example, Example, Comparative Example and Reference Example were carried out as follows.

<Infrared spectroscopic analysis (IR measurement)>
The IR measurement of the polyimide resin was performed using "JIR-WINSPEC50" manufactured by JEOL Ltd.

<Logarithmic Viscosity μ>
After drying the polyimide resin at 190 to 200 ° C. for 2 hours, the polyimide resin 0.100 g was dissolved in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Chemical Co., Ltd.) as a measurement sample, Canon Fenske viscometer. was used at 30°C. The logarithmic viscosity μ was determined by the following formula.
μ=ln(ts/ _t0 )/C
t ₀ : Flow time of concentrated sulfuric acid ts: Flow time of polyimide resin solution C: 0.5 g/dL

<Melting point, glass transition temperature, crystallization temperature, crystallization heat value>
The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and crystallization heat value ΔHc of the polyimide resin were measured using a differential scanning calorimeter (“DSC-6220” manufactured by SII Nano Technology Co., Ltd.).
A polyimide resin was subjected to a thermal history under the following conditions in a nitrogen atmosphere. The conditions for the thermal history were as follows: first temperature rise (up to 380°C, temperature increase rate 10°C/min), then cooling (up to 40°C, temperature decrease rate 20°C/min), and then temperature increase second time (up to 380°C, temperature increase rate 10°C/min) temperature rate of 10° C./min).
The melting point Tm was determined by reading the peak top value of the endothermic peak observed the second time the temperature was raised. The glass transition temperature Tg was determined by reading the value observed at the second heating. The crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling. For Tm, Tg and Tc, when multiple peaks were observed, the peak top value of each peak was read.
The crystallization heat value ΔHc (mJ/mg) was calculated from the area of the exothermic peak observed during cooling.

<Semi-crystallization time>
The semi-crystallization time of the polyimide resin was measured using a differential scanning calorimeter ("DSC-6220" manufactured by SII Nanotechnology Co., Ltd.).
The semi-crystallization time was measured under nitrogen atmosphere at 420°C for 10 minutes to completely melt the polyimide resin, followed by rapid cooling at a cooling rate of 70°C/min. The time taken from the appearance of the peak to the peak top was calculated and determined. In addition, in Table 1, when the semi-crystallization time was 20 seconds or less, it was described as "<20".

<Weight average molecular weight>
The weight average molecular weight (Mw) of the polyimide resin was measured under the following conditions using a gel permeation chromatography (GPC) measuring device ("Shodex GPC-101" manufactured by Showa Denko KK).
Column: Shodex HFIP-806M
Mobile phase solvent: HFIP containing 2 mM sodium trifluoroacetate
Column temperature: 40°C
Mobile phase flow rate: 1.0 mL/min
Sample concentration: about 0.1% by mass
Detector: IR detector Injection volume: 100 μm
Calibration curve: standard PMMA

<Volume average particle size (D50)>
The D50 of the polyimide resin particles was determined by laser diffraction particle size distribution measurement.
A laser diffraction light scattering type particle size distribution analyzer (“LMS-2000e” manufactured by Malvern) was used as a measuring device. The D50 measurement of the resin particles was carried out using water as a dispersing medium under ultrasonic conditions so that the resin particles are sufficiently dispersed. The measurement range was 0.02 to 2000 μm.

<Amount of active protons>
A 40 mg sample was collected in a vial, 5 mL of HFIP (hexafluoroisopropanol) was added, and the sample was allowed to stand overnight for dissolution. 0.2 mL of heavy chloroform was added to the sample after dissolution and mixed, and the mixed liquid was used as a sample for NMR measurement.
NMR measurement was performed at room temperature (23° C.) using a nuclear magnetic resonance apparatus (NMR, “Avance-5003” manufactured by Bruker). A 5 mmΦ BBO Cryo Probe was used as the probe.
A faint signal was detected between 6.1 and 7.1 ppm in approximately 7/3 samples of HFIP/deuterochloroform. These signals were assigned to active protons since they were not observed with heavy HFIP.

<Amount of terminal amino groups>
The amount of terminal amino groups was calculated from the amount of active protons measured by the NMR measurement.
Since the molded bodies produced in Example 1 and Comparative Example 1 and the powder of Reference Example 1 do not contain a resin other than the polyimide resin (A), the observed active protons are within the structure of the polyimide resin (A). It is speculated that it corresponds to the hydrogen of the terminal amino group contained in.

<Luminous characteristics>
The molded bodies produced in Examples 1 to 6 and Comparative Example 1, and the powder of Reference Example 1 were visually evaluated for the presence or absence of light emission. The evaluation criteria were as follows.
(Evaluation criteria)
A: Sufficient light emission B: Light emission C: No light emission

<Excitation-Emission Matrix (EEM) Measurement>
EEM measurement was performed on the compacts produced in Example 1 and Comparative Example 1 and the powder of Reference Example 1.
For the samples for measurement, the molded bodies of Example 1 and Comparative Example 1 were used as they were, and measurements were made on a surface with a diameter of 100 mm. As for the powder of Reference Example 1, a sample was packed in a powder holder attached to the apparatus and set in a holder for solids to prepare a sample for measurement.
The measurement was performed using a fluorescence spectrophotometer (manufactured by Horiba, Ltd., "Duetta, Fluorolog-3") under the following conditions.
(excitation side)
Excitation measurement wavelength: 250-850 nm
Slit width: 2 mm (band pass)
Send wavelength: 5 nm
Excitation side filter: none (emission side)
Emission measurement wavelength: 250-850 nm
Slit width: 2 mm (band pass)
Send wavelength: 5 nm
Emission side filter: None Detector Integration time: 0.1 sec/step
Sample mounting angle: 0deg FF

<Appearance of compact>
The external appearance of the molded bodies produced in Examples 1 to 5 was visually evaluated. The evaluation criteria were as follows.
(Evaluation criteria)
A: No yellowing B: Slight yellowing, no practical problem C: Significant yellowing, practical problem

<Bending strength and bending elastic modulus>
Three specimens of 80 mm × 10 mm × thickness 4 mm defined by ISO 316 were cut out from the compacts produced in Examples 1 to 5 and used for measurement. Using a bending tester “Bendgraph” (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a bending test was performed at a temperature of 23° C. and a test speed of 2 mm/min according to ISO178 to measure bending strength and bending elastic modulus. The flexural strength and flexural modulus of each compact were average values calculated from the measured values of three test pieces.

<Heat distortion temperature (HDT)>
Three specimens of 80 mm × 10 mm × thickness 4 mm defined by ISO 316 were cut out from the compacts produced in Examples 1 to 5 and used for measurement.
The measurement was carried out flatwise in accordance with JIS K7191-1,2:2015. Specifically, using an HDT tester "Auto-HDT3D-2" (manufactured by Toyo Seiki Seisakusho Co., Ltd.), thermal deformation was performed under the conditions of a distance between fulcrums of 64 mm, a load of 1.80 MPa, and a heating rate of 120 ° C./hour. Temperature was measured. The heat distortion temperature of each compact was the average value calculated from the measured values of three test pieces.

<Compressive strength measurement>
Five MD test pieces of 10 mm × 10 mm × 4 mm thickness and five TD direction test specimens of 10 mm × 10 mm × 4 mm thickness are cut out from the molded bodies produced in Examples 1 to 5, used for the measurements.
Measurement was performed in accordance with JIS K7181: 2011 using a universal material testing machine 59R5582 (manufactured by Instron) at a temperature of 23 ± 1 ° C and a humidity of 50 ± 5% RH at a test speed of 1 mm / min. It was carried out by creating a compressive stress-strain curve under the conditions.
Compressive strength generally refers to the maximum strength of a material at which it fails under compression. However, since the molded piece of this example was not destroyed, in this measurement, the value of the gradient threshold value of 2% was read as the "apparent yield point" from the compressive stress-strain curve, and the value of the compressive strain of 20% was ""compressive yield stress".
Each value in the MD direction and the TD direction was the average value calculated from the measured values of five test pieces.

[Production Example 1] Production of polyimide resin 1 Dean-Stark apparatus, Liebig condenser, thermocouple, 2-(2-methoxyethoxy) ethanol (manufactured by Nippon Nyukazai Co., Ltd.) in a 2 L separable flask equipped with four paddle blades. 500 g and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Company, Inc.) were introduced, nitrogen flowed, and then stirred at 150 rpm to form a uniform suspension solution. On the other hand, using a 500 mL beaker, 49.79 g (0.35 mol) of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, cis/trans ratio = 7/3), 1,8-octa A mixed diamine solution was prepared by dissolving 93.77 g (0.65 mol) of methylenediamine (manufactured by Kanto Kagaku Co., Ltd.) in 250 g of 2-(2-methoxyethoxy)ethanol. The mixed diamine solution was added slowly using a plunger pump. Heat was generated by the dropwise addition, but the internal temperature was adjusted to be within the range of 40 to 80°C. During the dropwise addition of the mixed diamine solution, nitrogen flow was maintained and the rotation speed of the stirring blade was 250 rpm. After the dropwise addition was completed, 130 g of 2-(2-methoxyethoxy)ethanol and 1.284 g (0.0100 mol) of n-octylamine (manufactured by Kanto Kagaku Co., Ltd.) as a terminal blocker were added and further stirred. At this stage, a pale yellow polyamic acid solution was obtained. Next, after setting the stirring speed to 200 rpm, the polyamic acid solution in the 2-L separable flask was heated to 190°C. In the process of increasing the temperature, deposition of polyimide resin powder and dehydration due to imidization were confirmed when the liquid temperature was 120 to 140°C. After holding at 190° C. for 30 minutes, it was allowed to cool to room temperature (23° C.) and filtered. The obtained polyimide resin powder was washed with 300 g of 2-(2-methoxyethoxy)ethanol and 300 g of methanol, filtered, and then dried in a dryer at 150° C. for 12 hours to obtain 317 g of polyimide resin 1 powder. rice field.
When the IR spectrum of polyimide resin 1 was measured, characteristic absorption of the imide ring was observed at ν(C═O) 1768, 1697 (cm ⁻¹ ). The logarithmic viscosity μ is 1.30 dL/g, the melting point Tm is 323° C., the glass transition temperature Tg is 184° C., the crystallization temperature Tc is 266° C., the heat of crystallization ΔHc is 21.0 mJ/mg, and the half-crystallization time is 20. Seconds or less, the weight average molecular weight (Mw) was 55,000, and the volume average particle diameter (D50) was 17 μm.

Table 1 shows the composition and evaluation results of the polyimide resin in Production Example 1. The mol % of the tetracarboxylic acid component and the diamine component in Table 1 are values calculated from the amount of each component charged during the production of the polyimide resin.

Abbreviations in Table 1 are as follows.
・PMDA; pyromellitic dianhydride ・1,3-BAC; 1,3-bis(aminomethyl)cyclohexane ・OMDA; 1,8-octamethylenediamine

(Reference example 1)
Using the powder of polyimide resin 1 obtained in Production Example 1, the luminous properties were evaluated by the method described above. Table 2 shows the results.

(Example 1)
100 g of the polyimide resin 1 powder obtained in Production Example 1 was introduced into a pressing mold (φ100 mm) previously coated with a release agent. A cold press was used to compress and preform the powder in the mold. Then, using a manual hydraulic vacuum press device (IMC-1AEA type, manufactured by Imoto Seisakusho Co., Ltd.), in a vacuum atmosphere (-0.1 bar), at 350 ° C., contact the press upper plate for 7 minutes (preheating process), gradually and held at 10 MPa for 10 minutes (pressurization process), removed from the mold and cooled with a cooling press at room temperature (23 ° C.) in an air atmosphere at 10 MPa for 10 minutes and cooled (cooling process ), and a molded body 1 (diameter: 100 mm, thickness: 10 mm) made of polyimide resin was manufactured. Using the molded article 1 thus produced, the emission characteristics were evaluated by the method described above. Table 2 shows the results.

(Comparative example 1)
The powder of polyimide resin 1 obtained in Production Example 1 was introduced into an extruder, melted at 350° C. and extruded to prepare pellets. The obtained pellets were introduced into an injection molding machine (“Roboshot α-S30iA” manufactured by FANUC CORPORATION) and injection molded at a barrel temperature of 350° C. and a mold temperature of 195° C. to obtain Comparative molded product 1 made of polyimide resin. manufactured. Using the manufactured comparative molded article 1, the emission characteristics were evaluated by the method described above. Table 2 shows the results.

As shown in Table 2, even with the molded body containing the predetermined polyimide resin (A), the molded body of Comparative Example 1, in which the amount of active protons was below the detection limit, hardly emitted light. On the other hand, the molded article of Example 1, which contains a predetermined polyimide resin (A) and has a predetermined amount of active protons, was observed to emit sufficient light, and had better light emission characteristics than Reference Example 1, which is a powder. was confirmed. From these results, while maintaining the amount of active protons in the polyimide resin (A) before thermoforming, by forming a molded body having a structure with a harder molecular skeleton than the powder, the heat after absorbing light It is presumed that the deactivation can be effectively suppressed and the luminous properties can be improved.

The above results also correspond to the excitation-emission matrix (EEM) measurements shown in FIGS. FIG. 1 shows the powder of Reference Example 1, FIG. 2 shows the comparative compact 1 of Comparative Example 1, and FIG. 3 shows the compact 1 of Example 1, respectively. 3D data of vs. fluorescence intensity.
As shown in FIG. 2, almost no emission peak was observed in the molded article of Comparative Example 1. On the other hand, as shown in FIGS. 1 and 3, the powder of Reference Example 1 and the molded body of Example 1 were irradiated with excitation light of different excitation wavelengths (λ _EX ) of 300 nm and 500 nm, respectively, to obtain a wavelength of about 430 nm. and an emission peak at an emission wavelength (λ _EX ) of about 550 nm was confirmed. In particular, the emission peak at an emission wavelength (λ _EX ) of about 550 nm was stronger in the molded article of Example 1 than in the powder of Reference Example 1, corresponding to the difference in emission characteristics visually observed.

(Examples 2-4)
In Examples 2 to 4, compacts were produced in the same manner as in Example 1, except that the compression molding conditions were changed as shown in Table 3, and various evaluations were performed by the above methods. Table 3 shows the results.

(Example 5)
In Example 5, a molded body was produced in the same manner as in Example 1, except that the polyimide resin powder washed and filtered in Production Example 1 was not dried and was introduced into the pressing mold in an undried state. Then, various evaluations were performed by the above methods. Table 3 shows the results.

As shown in Table 3, the molded bodies of Examples 2 to 5 containing the predetermined polyimide resin (A) and having the predetermined amount of active protons were also observed to emit sufficient light. In particular, the molded bodies of Examples 1, 3 and 4 have a bending strength of 100 MPa or more, an HDT of 160° C. or more, a good appearance, and are materials that are difficult to break during compression, so they have high strength and heat resistance. , flexibility and compression characteristics were also confirmed to be excellent.

(Example 6)
The polyimide resin 1 obtained in Production Example 1 and the polyamide resin PA6 ("UBE nylon 1030B" manufactured by Ube Industries, Ltd., melting point 215 to 225 ° C., glass transition temperature 50 ° C.) are in a mass ratio of 10:90. prepared to be Next, PA6 is introduced from the hopper on the root side of a co-rotating twin-screw kneading extruder ("HK-25D" manufactured by Parker Corporation), and the powder of polyimide resin 1 is introduced into the extruder from the side feeder, The mixture was kneaded under conditions of a set cylinder temperature of 260° C., a feed amount of 6 kg/h, and a screw rotation speed of 200 rpm, and the strand was extruded.
The strand extruded from the extruder was cooled with water, pelletized by a pelletizer ("Fan Cutter FC-Mini-4/N" manufactured by Hoshi Plastics Co., Ltd.), and used for injection molding.
After drying the obtained pellets in a dryer at 80 ° C. for 6 hours, an injection molding machine ("Roboshot α-S30iA" manufactured by Fanuc Co., Ltd.) was used to set the cylinder temperature to 250 ° C. and the mold temperature to 80. °C and an injection speed of 62.5 mm/s to produce a molded body (diameter: 100 mm, thickness: 10 mm). Using the produced compact, the amount of active protons was measured and the emission characteristics were evaluated by the methods described above. The amount of active protons was 812 mol % when the sum of the repeating structural units of formula (1) and the repeating structural units of formula (2) was taken as 100 mol %, and the emission characteristic was A.

From the results of Example 6, the amount of active protons in the molded product obtained by compounding the polyamide resin PA6, which is a resin having active hydrogen in the structure as the resin (B), and a predetermined polyimide resin (A) can be increased, and it was confirmed that the molded product exhibits good luminescence.

The light-emitting molded article of the present invention is composed of an organic material and has excellent light-emitting properties and heat resistance, so it can be applied to applications such as wavelength conversion members.

Claims

A repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2):

(R 1 is a C 6-22 divalent group containing at least one alicyclic hydrocarbon structure. R 2 is a C 5-16 divalent chain aliphatic group. X 1 and X 2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.)
and the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural units of the formula (1) and the repeating structural unit of the formula (2) is 20 to 70 mol%. Polyimide resin (A) A luminescent molded article comprising
The amount of active protons in the luminescent molded product is 0.01 mol% or more when the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is 100 mol%. Luminous molding.
2. The molded article according to claim 1, further comprising one or more resins (B) selected from the group consisting of polyamide resins, polyamideimide resins, epoxy resins, urethane resins, urea resins, phenol resins and cyanate resins. luminescent molding.
The luminescent molded article according to claim 1, wherein the molded article consists of the polyimide resin (A) only.
The luminescent molded article according to any one of claims 1 to 3, which is obtained by compression-molding a powder containing the polyimide resin (A).
A wavelength conversion member comprising the luminescent molding according to any one of claims 1 to 4.