阅读说明：本技术 树脂组合物，成型品，电子部件和电子设备 (Resin composition, molded article, electronic component, and electronic device ) 是由 松本光代 关口良隆 小池菜月 于 2021-06-09 设计创作，主要内容包括：本发明涉及树脂组合物,成型品,电子部件和电子设备。本发明的目的在于,提供一种含有β-1,3-葡聚糖衍生物树脂的树脂组合物,该树脂组合物能够兼具机械强度和阻燃性。本发明的树脂组合物的特征在于,至少包含具有以下结构式(1)表示的结构为主链的β-1,3-葡聚糖衍生物树脂和磷系阻燃剂,上述磷系阻燃剂在树脂中的平均粒径为5μm以下,[化学式1]式中,R分别独立地表示氢原子或羰烷基,R的至少一部分为羰烷基,n为自然数。(The present invention relates to a resin composition, a molded article, an electronic component and an electronic device. The purpose of the present invention is to provide a resin composition containing a beta-1, 3-glucan derivative resin, which resin composition can achieve both mechanical strength and flame retardancy. The resin composition of the present invention is characterized by comprising at least a resin having the following structural formula(1) A beta-1, 3-glucan derivative resin having a main chain structure and a phosphorus flame retardant having an average particle diameter of 5 μm or less in the resin [ chemical formula 1]])

1. A resin composition comprising at least a beta-1, 3-glucan derivative resin having a main chain of a structure represented by the following structural formula (1) and a phosphorus flame retardant, wherein the phosphorus flame retardant has an average particle diameter of 5 μm or less in the resin,

[ chemical formula 1]

Wherein R independently represents a hydrogen atom or a carbonylalkyl group, at least a part of R is a carbonylalkyl group, and n is a natural number.

2. The resin composition according to claim 1, wherein the content of the phosphorus-based flame retardant is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin contained in the resin composition.

3. The resin composition according to claim 1 or 2, wherein the Charpy impact strength at 23 ℃ is 4.0kJ/m²The above.

4. A molded article comprising the resin composition according to any one of claims 1 to 3.

5. An electronic component comprising the molded article according to claim 4.

6. An electronic device comprising the molded article according to claim 4.

Technical Field

The present invention relates to a resin composition, a molded article, an electronic component and an electronic device.

Background

In recent years, bio-based polymers synthesized from renewable resources have attracted attention. Euglena sugar produced by photosynthesis of microalgae such as Euglena (Euglena) and curdlan produced by fermentation of bacteria in a medium are linear high molecular polysaccharides composed of β -1, 3-glucan. In the past, it has been known that an ester group is introduced for the purpose of application of plastics, and a novel fiber is obtained by synthesizing an euglena derivative through chemical modification.

Patent document 1 discloses an euglena derivative characterized in that at least one of a plurality of hydroxyl groups in euglena is esterified and substituted with a carbonylalkyl group in order to provide a novel fiber composed of the euglena derivative.

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2017-218566

Disclosure of Invention

The purpose of the present invention is to provide a resin composition containing a beta-1, 3-glucan derivative resin, which resin composition can achieve both mechanical strength and flame retardancy.

The resin composition of the present invention which solves the above problems is as follows:

a resin composition characterized by comprising at least a beta-1, 3-glucan derivative resin having a main chain of a structure represented by the following structural formula (1) and a phosphorus flame retardant, wherein the phosphorus flame retardant has an average particle diameter of 5 [ mu ] m or less in the resin.

[ chemical formula 1]

(wherein R independently represents a hydrogen atom or a carbonylalkyl group, at least a part of R is a carbonylalkyl group, and n is a natural number.)

The effects of the present invention are explained below:

according to the present invention, a resin composition containing a β -1, 3-glucan derivative resin having both mechanical strength and flame retardancy can be provided.

Detailed description of the preferred embodiments

The present invention has the following characteristics in developing a flame retardant resin formulation for a beta-1, 3-glucan derivative resin:

that is, the present invention is characterized in that the dispersibility of the flame retardant is improved and the flame retardant effect and mechanical strength are improved by adding the flame retardant to the β -1, 3-glucan derivative resin (glucan derivative resin) to set the average particle size of the phosphorus-based flame retardant to 5 μm or less.

Embodiments of the present invention will be described in detail below.

Hereinafter, the "β -1, 3-glucan" may be referred to as "glucan", and the "β -1, 3-glucan derivative resin" may be referred to as "β -1, 3-glucan derivative" or "glucan derivative".

[ description of raw materials ]

(beta-1, 3-glucan)

Beta-1, 3-glucan is a polysaccharide mainly produced by algae, fungi and the like.

The bonding of β -1, 3-glucan by β -1, 3-linkages to glucose is similar to the bonding of cellulose and glucose by β -1, 4-linkages to glucose. And likewise no thermoplasticity. However, β -1, 3-glucan may have a triple helix structure of a polymer chain, unlike cellulose having a sheet structure in terms of the structure of the polymer chain.

Due to this structural difference, β -1, 3-glucan has unique physical properties and reaction characteristics different from cellulose. The beta-1, 3-glucan is easy to purify, and the purification process can be carried out under milder conditions than cellulose.

That is, plant cellulose exists as being strongly bound to lignin and hemicellulose, and a complicated and intensive purification step using a strong acid or the like is required to separate cellulose. In contrast, the β -1, 3-glucan of algae and fungi exists alone in many cases, and therefore, it is easy to purify, and it is not necessary to use a strong acid or the like. Therefore, the β -1, 3-glucan is difficult to depolymerize even after passing through a purification step, and can be separated in a monodisperse state in which the distribution of the molecular chain lengths unique to natural polymers is substantially maintained narrow.

This monodispersity is a major feature when β -1, 3-glucan is used as a raw material for the resin. That is, since the monodispersity is maintained by the acylation reaction, the β -1, 3-glucan derivative obtained is less likely to have defects due to differences in melting points. In addition, since β -1, 3-glucan can be isolated at higher purity than cellulose, the obtained β -1, 3-glucan derivative tends to have higher transmittance or the like than a cellulose derivative.

The beta-1, 3-glucan may or may not have a side chain. Examples of the β -1, 3-glucan having a side chain include Schizophyllum commune polysaccharide, lentinan and the like. Examples of the β -1, 3-glucan having no side chain include curdlan, euglena, and the like.

The beta-1, 3-glucan may be either biologically derived or synthetic. From the viewpoint of reducing environmental load, it is preferably derived from a biological source, and more preferably from a plant. Among them, from the viewpoint of easy separation and purification of β -1, 3-glucan, β -1, 3-glucan separated from microalgae which synthesize β -1, 3-glucan in cells is preferable.

The microalgae is preferably Euglena (Euglena) (microalgae belonging to Euglena phylum).

Euglena is easy to culture, has a rapid growth cycle, and accumulates a large amount of euglena sugar particles as a photosynthetic product in cells. Euglena synthesized and accumulated euglena is beta-1, 3-glucan formed by beta-1, 3-bonding of generally 1500-2000 glucose. Can be isolated from microalgae such as beta-1, 3-glucan like euglena by a conventional method.

(beta-1, 3-glucan derivative)

The beta-1, 3-glucan derivative is obtained by acylating a part of the hydroxyl groups in glucose constituting the beta-1, 3-glucan main chain with acyl groups. That is, the β -1, 3-glucan derivative has an acyl group. Due to the presence of acyl groups, (i) interactions between molecular chains are weakened due to disorder of the arrangement of the molecular chains, while (ii) interactions between molecular chains are weakened due to the reduction of the formation of hydrogen bonds between main chains due to hydroxyl groups. As a result, the thermoplastic resin composition is excellent in thermoplasticity and exhibits adhesiveness and adhesion.

As an example of the β -1, 3-glucan derivative, a β -1, 3-glucan mixed ester represented by the following structural formula (2) can be cited.

[ chemical formula 2]

(wherein R independently represents a hydrogen atom or a carbonylalkyl group, at least a part of R is a carbonylalkyl group, and n is a natural number.)

The carboalkyl group consisting of R₁C (O) -represents (wherein R₁Is a hydrocarbyl group).

Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group may be linear, branched, or have a cyclic structure. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group (alkenyl group or alkynyl group). R as an aliphatic hydrocarbon group, easily synthesized₁From the viewpoint of high degree of freedom of (3), an alkyl group is preferable, a linear or branched alkyl group is more preferable, and a linear alkyl group is further preferable.

Examples of the carbonylalkyl group include an acetyl group, a propionyl group, an isopropionyl group, a butyryl group, an isobutyryl group, a valeryl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a lauroyl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oleoyl group, a linoleoyl group, and a linolenoyl group.

The mass average molecular weight Mw of the beta-1, 3-glucan derivative is preferably 2.0X 10³Da or more and 1.0X 10⁶Da or less, more preferably 5.0X 10³Above Da, 5.0 × 10⁵Da or less. The number average molecular weight Mn of the beta-1, 3-glucan derivative is preferably 2.0X 10³Da or more and 1.0X 10⁶Da or less, more preferably 5.0X 10³Da or more and 5.0X 10⁵Da or less.

The carboxylic acid represented by the following structural formula (3) can be used for the esterification. The carboxylic acid may be a synthetic product, but from the viewpoint of reducing environmental load, a biologically derived carboxylic acid is preferable, and a plant-derived carboxylic acid is more preferable.

[ chemical formula 3]

(phosphorus flame retardant)

The phosphorus-based flame retardant is a flame retardant containing a phosphorus component. Examples of the phosphorus-based flame retardant include phosphate ester compounds, phosphazene compounds, phosphaphenanthrene compounds, phosphinic acid metal salts, ammonium polyphosphates, melamine polyphosphates, phosphate ester amides, and red phosphorus. One kind may be used, or two or more kinds may be used in combination.

The phosphorus-based flame retardant may be added when the β -1, 3-glucan derivative is kneaded, or the phosphorus-based flame retardant may be previously kneaded with a part of the β -1, 3-glucan derivative or another resin to obtain a mixture, and the mixture may be added when the β -1, 3-glucan derivative is kneaded.

The average particle diameter of the phosphorus-containing compound in the β -1, 3-glucan derivative is preferably 5 μm or less.

If the average particle diameter is more than 5 μm, dispersibility is deteriorated, and flame retardancy and impact strength are deteriorated.

The amount of the phosphorus flame retardant added is preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin.

When it is 10 parts by mass or more, sufficient flame retardancy is exhibited, and when it is 50 parts by mass or less, sufficient impact resistance is exhibited.

(other resins and additives)

The resin composition of one embodiment of the present invention may contain a PP resin, a PE resin, a PC resin, a PS resin, an ABS resin, etc., within a range where flame retardancy, impact resistance, etc. are not significantly reduced.

The content of the other resin may be 5 to 50 parts by mass with respect to 100 parts by mass of the resin contained in the resin composition.

The resin composition of one embodiment of the present invention may contain other additives such as a phosphorus stabilizer, a phenol stabilizer, a dye pigment, and a filler, within a range where flame retardancy, impact resistance, and the like are not significantly reduced.

(regarding the molded article)

An example of the present invention is a molded article (hereinafter, also referred to as "example molded article") containing the flame-retardant resin composition of the present invention.

Examples of the molded articles (molded articles) include components of information and mobile devices such as computers, notebook personal computers, tablet terminals, smart phones, and cellular phones, and OA devices such as printers and copiers. Particularly, it is preferably used for exterior members requiring heat resistance.

An example of the molded article can be obtained by, for example, injection molding an example of the resin composition according to a conventional method.

(electronic parts)

An electronic component according to an embodiment of the present invention includes the molded article according to the present invention.

Examples of the electronic components include electronic components for information and mobile devices such as computers, notebook personal computers, tablet terminals, smart phones, and mobile phones, and 0A devices such as printers and copiers.

(electronic apparatus)

An electronic device according to an embodiment of the present invention includes the molded article according to the present invention.

Examples of the electronic devices include information and mobile devices such as a computer, a notebook personal computer, a tablet terminal, a smart phone, and a mobile phone, 0A devices such as a printer and a copier, and home electric appliances such as a television, a refrigerator, and a vacuum cleaner.

In the resin composition of the present invention, the Charpy impact strength at 23 ℃ of the molded test piece is preferably 4.0kJ/m²Above, more preferably 6.0kJ/m²The above.

Charpy impact strength was measured at 23 ℃ using a Charpy impact tester in accordance with IS0179-1 for the notched impact test piece prepared.

(method for producing resin composition)

The resin composition of the present invention is obtained by kneading a β -1, 3-glucan derivative with a phosphorus flame retardant.

The blending ratio of the glucan derivative and the phosphorus-based flame retardant is preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the glucan derivative.

An example of the method for producing the resin composition of the present invention (hereinafter, also referred to as "an example production method") includes, for example, a melt-kneading step of melt-kneading a glucan derivative, a phosphorus-based flame retardant, optionally added components, and other additives as needed.

< melt kneading step >

In one example of the production method, first, the components essential to the present invention, the components optionally added, and other additives added as needed are melt-kneaded (melt-kneading step).

Each component can be uniformly mixed by the above procedure.

In this step, the above components are kneaded by using kneading equipment known in the art such as a drum mixer, a henschel mixer, a banbury mixer, a roll, a braker machine, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader, under conditions such as a kneading speed, a kneading temperature, and a kneading time, which are appropriately adjusted.

For example, the above components are preliminarily premixed with a tumbler mixer, a henschel mixer, or the like, and then melt-kneaded by a kneading device such as a banbury mixer, a roll, a braker machine, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. Further, for example, it is also possible to melt-knead the components in the extruder using a feeder without previously mixing the components. Further, for example, it is also possible to melt-knead the master batch and the remaining components again by premixing only a part of the components, and thereafter, using the resin composition obtained by melt-kneading as a master batch.

Here, in this step, there is no particular limitation, and it is preferable that arbitrarily selected components are previously melt-mixed in advance and then added to a twin-screw kneading extruder.

In particular, the kneading temperature is determined according to the melting temperature (Tm) of the glucan derivative. The Tm can be measured by using a viscoelastic apparatus capable of changing the temperature, such as DSC, TMA, or DTA, and any of the measured values can be used, similarly to the glass transition temperature (Tg), and kneading the mixture at a temperature near the Tm temperature measured by these apparatuses, whereby the resin composition of the present invention can be easily obtained.

It is known that Tm and Tg vary somewhat depending on the measurement method. In the present invention, Tm and Tg values measured by DSC are preferably used.

The present invention relates to a resin composition described in the following (1), including the following (2) to (6) as embodiments of the present invention.

(1) A resin composition characterized by comprising at least a beta-1, 3-glucan derivative resin having a main chain of a structure represented by the following structural formula (1) and a phosphorus flame retardant, wherein the phosphorus flame retardant has an average particle diameter of 5 [ mu ] m or less in the resin.

[ chemical formula 1]

(wherein R independently represents a hydrogen atom or a carbonylalkyl group, at least a part of R is a carbonylalkyl group, and n is a natural number.)

(2) The resin composition according to the above (1), wherein the content of the phosphorus-based flame retardant is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin contained in the resin composition.

(3) The resin composition according to the above (1) or (2), wherein the Charpy impact strength at 23 ℃ is 4.0kJ/m²The above.

(4) A molded article comprising the resin composition according to any one of the above (1) to (3).

(5) An electronic component comprising the molded article according to the item (4).

(6) An electronic device, comprising the molded article according to the item (4).

[ examples ] A method for producing a compound

The present invention will be described in more detail below by way of examples, but the technical scope of the present invention is not limited to the following examples.

[ raw materials ]

Each component used in producing the resin composition of the present invention will be described.

(raw Material for producing derivative)

β -1, 3-glucan: polysaccharides from Euglena

Propionic acid: deer superfine (manufactured by Kanto chemical Co., Ltd.)

Butyric acid: deer superfine (manufactured by Kanto chemical Co., Ltd.)

Valeric acid: deer superfine (manufactured by Kanto chemical Co., Ltd.)

Caproic acid: deer grade 1 (manufactured by Kanto chemical Co., Ltd.)

(phosphorus flame retardant)

PX-200: aromatic condensed phosphoric ester (manufactured by Daba chemical Co., Ltd.)

0P 1240: aluminum diethylphosphinate (manufactured by Claien Japan Co., Ltd.)

The AP 422: ammonium polyphosphate (made by Claien Japan Co., Ltd.)

SPS 100: phosphazene compound (manufactured by Otsuka chemical Co., Ltd.)

[ production example of dextran derivative ]

(preparation of Glucan derivative 1)

The following steps (1) to (5) were performed to produce a glucan derivative 1.

(1) 200g of beta-1, 3-glucan shown in Table 1, 8000mL of trifluoroacetic anhydride, and 8000mL of carboxylic acid were reacted at 50 ℃ for 2 hours.

(2) Precipitated with a mixed solution of methanol/water.

(3) Washed with a mixed solution of methanol/water.

(4) Washing with ethanol.

(5) Vacuum drying for 24 hours gave the product (dextran derivative 1).

(production of dextran derivatives 1 to 6)

In the preparation of glucan derivative 1, glucan derivatives 2 to 6 were synthesized in the same manner as in the preparation of glucan derivative 1 except that the kind of β -1, 3-glucan or carboxylic acid was changed to the raw materials shown in table 1.

TABLE 1

(example 1)

The raw materials were mixed in accordance with the composition (parts by mass) shown in the following Table 2-1, and kneaded at a temperature of 185 ℃ using a Mini-Labo (manufactured by Thermo Fisher Scientific Co., Ltd.) to obtain a resin composition.

Then, using the obtained resin composition, molding was performed at a set temperature of 200 ℃ to obtain an evaluation sheet.

0P1240 and AP422 were crushed for use prior to mixing.

(examples 2 to 12, comparative examples 1 to 3)

The resin compositions of examples 2 to 12 and comparative examples 1 to 3 and test pieces were prepared in the same manner as in example 1 by mixing the raw materials in the combinations (parts by mass) shown in tables 2-1 and 2-2.

[ evaluation test method ]

(average particle diameter of phosphorus flame retardant)

The average particle diameter of the phosphorus flame retardant was measured by the following method.

The test piece was cut with a microtome manufactured by Leica, and the cut surface was photographed in 5 fields of view at a magnification of 5000 times with a scanning electron microscope Merlin (manufactured by Carl Zeiss). From the photographed image, the average particle diameter of the biaxial average diameter of the entire field of View was calculated using image analysis type particle size distribution measuring software Mac-View (manufactured by Mountech corporation).

The average particle diameter (L [ μm ]) was evaluated according to the following criteria.

Very good: less than 3 μm

O: 3 to 5 μm in thickness

X: over 5 μm

(Charpy impact strength)

According to IS0179-1, impact tests were carried out using a Charpy impact tester.

Cut in the test strip (open).

Evaluation criterion (unit: kJ/m)²)

Very good: 6 or more

O: 4 or more and less than 6

X: less than 4

(Combustion test)

The flame resistance test was conducted in accordance with the UL94 test (burn test for plastic materials used in equipment parts) established by Underwriters Laboratories (UL) in the United states.

The thickness t of the test piece was 1.5 mm.

UL94V testing was performed to determine the ratings "V-0", "V-1", and "V-2".

V-2 or more is defined as pass.

TABLE 2-1

Tables 2 to 2

The preferred embodiments and examples of the present invention have been described above in detail, but the present invention is not limited to these embodiments and examples, and various modifications and changes can be made within the scope of the gist of the present invention described in the scope of claims.