Polymer resin material composition and manufacturing method therefor

Abstract

To provide a polymer resin material composition that has a high biomass plastic level and can be manufactured at a low cost, and a manufacturing method for the polymer resin material composition.SOLUTION: A polymer resin material composition is produced by performing heat curing treatment on a mixture obtained by mixing epoxidized linseed oil with polyethylene glycol lignin.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a polymeric resin material composition and a method for producing the same. [Background technology]

[0002] Traditionally, efforts have been made to mitigate or reduce the impact of climate change, and research and development has been conducted to reduce carbon dioxide emissions in order to achieve this. In particular, one technology that can contribute to reducing carbon dioxide emissions is the technology of producing plastic materials used in the manufacture of electronic components, etc., using biomass raw materials.

[0003] For example, Patent Document 1 discloses a technique for producing an insulating polymeric material composition using lignin obtained by crushing a lignin raw material and then extracting it with alcohol, and epoxidized linseed oil. Also, for example, Patent Document 2 discloses a technique for producing an epoxy resin using modified lignin chemically modified with polyethylene glycol. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2008-138061 A [Patent Document 2] JP 2019-108490 A Summary of the Invention [Problem to be solved by the invention]

[0005] The above conventional techniques have the problem that it is difficult to produce a resin material composition having a high degree of biomass plastic at a lower cost. For example, the technique disclosed in Patent Document 1 requires equipment that can withstand high temperature and high pressure reaction conditions in the process of producing lignin by explosion. In addition, the technique obtained by Patent Document 2, for example, has the problem that the degree of biomass is low because modified lignin chemically modified with polyethylene glycol is used. Therefore, an object of the present invention is to provide a polymeric resin material composition that has a high degree of biomass plastic and can be produced inexpensively, and a method for producing the polymeric resin material composition. [Means for solving the problem]

[0006] One aspect of the present invention is a polymeric resin material composition produced by mixing epoxidized linseed oil and polyethylene glycol lignin, and subjecting the mixture to a heat curing treatment.

[0007] Another aspect of the present invention is a method for producing a polymer resin material composition, comprising: a mixing step of mixing epoxidized linseed oil with polyethylene glycol lignin that is not dissolved in a solvent to produce a mixture; and a heat curing step of heating and curing the mixture. Effect of the Invention

[0008] According to the present invention, it is possible to provide a polymeric resin material composition that has a high degree of biomass plastic and can be produced at low cost, and a method for producing the polymeric resin material composition, which in turn contributes to mitigating or reducing the impact of climate change. [Brief description of the drawings]

[0009] [Figure 1] 1 is a process diagram showing a manufacturing procedure of a polymer resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [1. Polymer resin composition] As biomass-based epoxy resins based on vegetable oils, those made by epoxidizing soybean oil or linseed oil are known. Compared to general epoxy resins, these epoxidized oils are often insufficient in terms of reactivity, strength, glass transition temperature, etc., and have rarely been used as insulating materials. However, in recent years, research and development aimed at reducing carbon dioxide emissions has led to the study of biomass-based epoxy resins.

[0011] Lignin has been attracting attention as one of the biomass-based resin materials. Lignin is a major component constituting plant cell walls, and is a compound that accounts for about 30% of wood. For example, cedar is known as a plant that has relatively uniform lignin, and other plants can also be used as raw materials for producing lignin. The explosion method described in Patent Document 1 is sometimes used as a method for producing plant-derived lignin, but polyethylene glycol lignin is a lignin that can be produced under milder reaction conditions. Polyethylene glycol lignin is a relatively homogeneous lignin obtained by subjecting lignin raw materials derived from wood, etc., to acid hydrolysis treatment with polyethylene glycol, and is also called modified lignin.

[0012] The present inventors have found that by mixing epoxidized linseed oil and modified lignin and subjecting the mixture to a heat curing treatment under a specified condition, a polymeric resin composition that is inexpensive and has a high degree of biomass plasticity can be obtained. The polymeric resin material composition obtained by this method has a high glass transition temperature, and therefore can be a suitable material for the manufacture of electronic components and electronic substrates.

[0013] The present inventors have also found that a polymeric resin material composition having more suitable properties can be obtained by further adding a curing accelerator to a mixture of epoxidized linseed oil and modified lignin. As the curing accelerator, amines, imidazoles, etc. can be used. The curing accelerator promotes the chemical reaction between epoxidized linseed oil and modified lignin as a curing agent in the process of curing the mixture of epoxidized linseed oil and modified lignin, and has the effect of accelerating the curing time and increasing the glass transition temperature of the polymeric resin material composition, which is the product. As the curing accelerator, 2-ethyl-4-methylimidazole (hereinafter, 2E4MZ) was particularly suitable.

[0014] The polymer resin material composition produced by the method discovered by the present inventors has the advantage of having a high degree of biomass plastics. Here, the degree of biomass plastics is measured according to the following standard defined by ISO16620: 14 The C concentration of the product was measured. 14 By measuring the C ratio, the amount of carbon derived from biomass can be determined, and this is used to calculate the biomass plastic content.

[0015] [2. Production of polymer resin composition] FIG. 1 is a process diagram showing a manufacturing procedure for a polymer resin composition. In the manufacturing method of the polymer resin composition of the present disclosure, first, a base agent 10 consisting of a biomass-based epoxy resin based on vegetable oil and a curing agent 12 consisting of modified lignin are charged into an agitator 14, and a first mixing step (step S1) is performed in which the base agent 10 and the curing agent 12 are agitated and mixed in the agitator 14.

[0016] In the first mixing step, the base agent 10 and the curing agent 12 made of modified lignin that is not dissolved in a solvent are mixed in the agitator 14 to obtain a mixture. The base agent 10 is, for example, epoxidized linseed oil. The curing agent 12 is, for example, powdered or granular polyethylene glycol lignin that is not dissolved in a solvent. In the first mixing step, 100 parts by mass of polyethylene glycol lignin is put into the agitator 14 and mixed with 100 parts by mass of epoxidized linseed oil. This is one example, and a suitable polymer resin composition can be obtained by mixing 75 parts by mass or more and 125 parts by mass or less of polyethylene glycol lignin with 100 parts by mass of epoxidized linseed oil.

[0017] Next, a heating step (step S2) is performed in which the mixture mixed in the agitator 14 is heated. Furthermore, the base agent 10 and the curing agent 12 that have been melted by heating are further stirred (step S3). The steps S2 and S3 are performed with the mixture in the agitator 14. In the heating step of step S2, a heating device (not shown) is used that is provided in the agitator 14 and heats the inside of the tank of the agitator 14 or the entire agitator 14. The temperature and time for which the mixture is heated in step S2 are set to a temperature and time at which the base agent 10 and the curing agent 12 are entirely melted.

[0018] In addition, 2E4MZ as hardening accelerator 16 is heated and melted in a container separate from mixer 14 (step S4). The melted 2E4MZ is added to the mixture stirred in step S3 (step S5). Step S5 is called an adding step, and in the adding step, for example, 2E4MZ is added to mixer 14 that contains the mixture stirred in step S3.

[0019] After the addition step of step S5, the mixture is further stirred (step S6). Steps S5 and S6 are an example of a second mixing step, and the first and second mixing steps are included in the mixing step of the present disclosure. Step S6 is performed in a stirrer 14. Moreover, all of steps S1 to S6 may be included in the mixing step. Next, the mixture obtained in the second mixing step (steps S5 and S6) is poured into a mold 18 (step S7).

[0020] After the casting process of step S7, the mixture injected into the mold 18 is heated to a curing temperature by heating the mold 18 in an oven (step S8). Step S8 corresponds to an example of a heat curing process. Thereafter, the polymer resin composition heated in step S8 is released from the mold 18 (step S9) to obtain a polymer resin composition with a biomass plastic content of 100% or more.

[0021] In the heat curing step S9, the mixture is heated at a temperature of 160° C. to 200° C. for 17 hours to 24 hours. When the hardening accelerator 16 (2E4MZ or the like) is not added, steps S4, S5, and S6 are omitted. In this case, the heat hardening step is also performed at 170° C. to 200° C. for 17 hours to 24 hours.

[0022] As shown in the examples described below, the polymeric resin material composition obtained by the manufacturing method of the present disclosure has a glass transition temperature Tg of 90° C. or higher as measured by thermomechanical analysis (TMA) according to the method described in ISO11359-2. The glass transition temperature Tg of a resin material used in the manufacture of electronic components or electronic substrates is preferably 90° C. or higher, more preferably 95° C. or higher, and even more preferably 100° C. or higher. Therefore, according to the manufacturing method of a polymeric resin material composition of the present disclosure, a polymeric resin material composition suitable for electronic components and electronic substrates can be inexpensively manufactured under moderate temperature and pressure conditions.

[0023] In the manufacturing method of the polymer resin composition of the present disclosure, the mixing step includes a first mixing step and a second mixing step. In the first mixing step, the base agent 10 and the curing agent 12 that is not dissolved in the solvent are heated and melted to mix them. In the second mixing step, the mixture of the base agent 10 and the curing agent 12 in a heated and melted state is mixed with the curing accelerator 16 that is heated and melted. In the second mixing step, 1 part by mass of the curing accelerator 16 is mixed with 100 parts by mass of the base agent 10. The amount of the curing accelerator 16 can be appropriately changed, but for example, it is preferable to mix 1 part by mass or less of the curing accelerator 16 with 100 parts by mass of the base agent 10. As an example, the base agent 10 is epoxidized linseed oil, and the curing agent 12 is polyethylene glycol lignin that is not dissolved in the solvent.

[0024] 3. Working Examples Next, the polymeric resin material composition of the present disclosure and the method for producing the same will be specifically described based on examples, but the present disclosure is not limited to these examples.

[0025] Examples 1 to 8 show examples of polymer resin material compositions produced by the production method of the present disclosure with variously changing the amounts of the main agent 10, the curing agent 12, and the curing accelerator 16. Table 1 shows the amount of the main agent 10, the amount of the curing agent 12, the amount of the curing accelerator, the curing temperature, the curing time, the curing possibility, and the glass transition temperature Tg for each of Examples 1 to 8. In Table 1, the amount of the curing agent 12 and the amount of the curing accelerator are shown in parts by mass when the amount of the main agent 10 is 100 parts by mass. The curing possibility is shown by ○ and × as to whether or not the practical physical properties as a polymer resin composition are satisfied, with ○ being an example that satisfies the practical physical properties, and × being an example that does not satisfy the practical physical properties. The practical physical properties as a polymer resin composition refer to mechanical strength equivalent to or comparable to that of conventional epoxy resins, and specifically include flexural modulus and flexural strength (flexural stress). The flexural modulus and flexural strength were measured for the polymer resin material compositions produced in each of Examples 1 to 8, and a rating of "O" was given when the measured flexural modulus was equal to or greater than the standard value and the measured flexural strength was equal to or greater than the standard value. The curing temperatures and curing times in Table 1 are those in the heat curing process in step S8 (FIG. 1).

[0026] [Table 1]

[0027] As shown in Table 1, in Examples 1 to 8, 100 parts by mass of the curing agent 12 was used for 100 parts by mass of the base agent 10. Epoxidized linseed oil was used as the base agent 10, specifically, Adeka Cizer O-180 manufactured by ADEKA CORPORATION was used. The curing agent 12 was a powdered or granular polyethylene glycol lignin that was not dissolved in a solvent. Specifically, Lignin SR4 manufactured by Lignomateria Co., Ltd. was used. The curing agent 12 was a powdered or granular lignin with a D50 particle size of 190 μm or more and 290 μm or less.

[0028] In Examples 1 to 4, no curing accelerator 16 was added. In Examples 5 to 8, 2E4MZ (2-ethyl-4-methylimidazole) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. was mixed as the curing accelerator 16. The amount of the curing accelerator 16 was 1 part by mass per 100 parts by mass of the main agent 10.

[0029] The results of Examples 2 to 7 were all evaluated as being curable, and the polymeric resin material compositions produced met the practical physical properties required for a polymeric resin composition. In addition, the polymeric resin material compositions obtained in Examples 2 to 7 all had a glass transition temperature Tg of 90° C. or higher.

[0030] The results of Examples 2 to 7 reveal that it is possible to provide a polymeric resin material composition using biomass raw materials and having mechanical strength comparable to that of conventional epoxy resins.

[0031] From the results of Examples 2 to 7, a curing time of 17 hours or more is sufficient for producing a polymeric resin material composition having a glass transition temperature of 90° C. or more. From the results of Examples 4 and 5, when the curing time is extended, no significant difference in the glass transition temperature Tg is observed up to 24 hours. Therefore, the heating time in the heat curing step is preferably 17 hours or more and 24 hours or less.

[0032] From the results of Examples 3 to 7, it was found that the curing temperature is desirably 160°C or higher, and more preferably 170°C or higher. From the results of Examples 2 to 4, it was found that even when no curing accelerator is added, the conditions of a heating time of 17 hours to 24 hours and a heating temperature of 160°C or higher are favorable. In addition, it was found from Example 7 that a heating temperature of up to 200°C is favorable.

[0033] Furthermore, a comparison of Examples 5, 6, and 7 shows that there is no significant difference in the glass transition temperature Tg up to a heating temperature of 200° C. Therefore, when at least a curing accelerator is added, the curing temperature may be 170° C. or higher and 200° C. or lower.

[0034] If the hardener 12 is in a powder or granular form with a D50 particle size of 290 μm or less, preferably 190 μm or more, it can be mixed normally with the base agent 10 even if it is not dissolved in a solvent.

[0035] The effect of the curing accelerator is clear from the results of Examples 5 to 8. That is, in the example in which 1 part by mass of 2E4MZ was mixed as the curing accelerator 16 with 100 parts by mass of the base agent 10 and 100 parts by mass of the curing agent 12, a particularly good result of a glass transition temperature Tg of 100° C. or higher was obtained.

[0036] Moreover, in Examples 1 and 8, the evaluation of whether or not the composition could be cured was "x", and the physical properties of the resulting polymeric resin material compositions were somewhat inferior. From the results of Examples 1 and 8, it is preferable that the heating temperature in the heat curing step is higher than 140°C, and more preferably, it is 160°C or higher as described above.

[0037] [4. Other embodiments] The above-described embodiment merely shows one aspect of the present invention, and any modification and application are possible within the scope of the present invention.

[0038] In the above-described embodiment, an example of mixing 100 parts by mass of the base agent 10 with 100 parts by mass of the hardener 12 has been described, but this is only one example, and it is possible to adjust the ratio of the base agent 10, the hardener 12, and the hardening accelerator 16 as necessary.

[0039] In the above-described embodiment, an example has been described in which the agitator 14 is used in the process of mixing the base agent 10, the curing agent 12, and the curing accelerator 16. However, for example, each of steps S2, S3, and S6 may be performed using a container or device other than the agitator 14.

[0040] In the heat curing step S8 described in the above embodiment, two-stage heating at different heating temperatures, residual heat treatment, pre-drying, and the like may be appropriately performed.

[0041] [5. Configuration supported by the above embodiment] The above embodiment supports the following configurations.

[0042] (Configuration 1) A polymeric resin material composition produced by mixing epoxidized linseed oil and polyethylene glycol lignin and subjecting the mixture obtained to a heat curing treatment. According to the polymer resin material composition of configuration 1, it is possible to obtain a polymer resin material composition having a biomass plastic degree of 100% or more, using epoxidized linseed oil and lignin, which are biomass raw materials. This polymer resin material composition can be produced without using expensive means such as explosion. Therefore, it is possible to provide a polymer resin material composition that has a high biomass plastic degree and can be produced inexpensively.

[0043] (Configuration 2) The polymeric resin material composition according to configuration 1, having a glass transition temperature Tg of 90° C. or higher. According to the polymer resin material composition of configuration 2, it is possible to provide a polymer resin material composition that has a high degree of biomass plastic, can be produced at low cost, and has a high glass transition temperature Tg suitable for use in electronic components and electronic substrates.

[0044] (Configuration 3) The polymeric resin material composition according to Configuration 1 or 2, wherein the mixture is prepared by mixing the polyethylene glycol lignin in a ratio of 75 parts by weight to 125 parts by weight to 100 parts by weight of the epoxidized linseed oil. According to the polymer resin material composition of configuration 3, it is possible to obtain a polymer resin material composition that has a high degree of biomass plastic, can be produced inexpensively, and has excellent physical properties.

[0045] (Configuration 4) A method for producing a polymer resin material composition, comprising: a mixing step of mixing epoxidized linseed oil with polyethylene glycol lignin that is not dissolved in a solvent to produce a mixture; and a heat curing step of heating and curing the mixture. According to the method for producing a polymeric resin material composition of configuration 4, it is possible to obtain a polymeric resin material composition using epoxidized linseed oil and lignin, which are biomass raw materials, and having a biomass plastic degree of 100% or more. This production method includes a step of mixing lignin with epoxidized linseed oil without dissolving it in a solvent, and uses polyethylene glycol lignin that can be obtained without using expensive means such as explosion. Therefore, it is possible to provide a polymeric resin material composition that has a high biomass plastic degree and can be produced inexpensively.

[0046] (Configuration 5) The method for producing a polymer resin material composition according to Configuration 4, wherein the mixing step includes a first mixing step of heating and melting the epoxidized linseed oil and the polyethylene glycol lignin not dissolved in a solvent to mix them, and a second mixing step of mixing a heated and melted curing accelerator with the mixture of the epoxidized linseed oil and the polyethylene glycol lignin in a heated and melted state, and in the second mixing step, 1 part by mass or less of the curing accelerator is mixed with 100 parts by mass of the epoxidized linseed oil. According to the method for producing a polymeric resin material composition of the fifth aspect, epoxidized linseed oil and polyethylene glycol lignin are mixed without dissolving the polyethylene glycol lignin in a solvent, and the mixture is cured more reliably by a curing accelerator. This makes it possible to produce a polymeric resin material composition that is highly biomass plastic and has excellent physical properties at a lower cost.

[0047] (Configuration 6) The method for producing a polymeric resin material composition according to Configuration 4 or 5, wherein in the heat curing step, the mixture is heated under conditions of 160° C. or higher and 200° C. or lower for 17 hours or higher and 24 hours or lower. According to the method for producing a polymer resin material composition of configuration 6, it is possible to more reliably harden epoxidized linseed oil and polyethylene glycol lignin, and to more inexpensively produce a polymer resin material composition having a high degree of biomass plasticity and excellent physical properties.

[0048] (Configuration 7) The method for producing a polymeric resin material composition according to Configuration 5, wherein the mixture obtained by mixing the curing accelerator in the second mixing step is heated at 170°C or higher and 200°C or lower for 17 hours or higher and 24 hours or lower in the heat curing step. According to the method for producing a polymer resin material composition of configuration 7, the epoxidized linseed oil and the polyethylene glycol lignin can be cured more reliably by the curing accelerator, and a polymer resin material composition having a high degree of biomass plasticity and excellent physical properties can be produced more inexpensively.

[0049] (Configuration 8) The method for producing a polymeric resin material composition according to Configuration 5 or 7, further comprising mixing 2-ethyl-4-methylimidazole as the curing accelerator. According to the method for producing a polymeric resin material composition of aspect 8, a polymeric resin material composition having a high degree of biomass plastic can be produced at a lower cost. [Explanation of symbols]

[0050] 10...base agent, 12...hardener, 14...mixer, 16...hardening accelerator, 18...mold.

Claims

1. A polymeric resin material composition produced by mixing epoxidized linseed oil and polyethylene glycol lignin, and subjecting the mixture obtained to a heat curing treatment.

2. The polymeric resin material composition according to claim 1, having a glass transition temperature Tg of 90° C. or higher.

3. The polymeric resin material composition according to claim 1 , wherein the mixture is prepared by mixing the polyethylene glycol lignin in a ratio of 75 parts by mass or more and 125 parts by mass or less with respect to 100 parts by mass of the epoxidized linseed oil.

4. mixing the epoxidized linseed oil with polyethylene glycol lignin that is not dissolved in a solvent to form a mixture; and a heat curing step of heating the mixture to cure it.

5. The mixing step comprises: A first mixing step of heating and melting the epoxidized linseed oil and the polyethylene glycol lignin not dissolved in a solvent to mix them; A second mixing step of mixing a heat-melted hardening accelerator with the mixture of the epoxidized linseed oil and the polyethylene glycol lignin in a heat-melted state, The method for producing a polymeric resin material composition according to claim 4 , wherein in the second mixing step, 1 part by mass or less of the curing accelerator is mixed with 100 parts by mass of the epoxidized linseed oil.

6. The method for producing a polymeric resin material composition according to claim 4, wherein in the heat curing step, the mixture is heated at 160°C or more and 200°C or less for 17 hours or more and 24 hours or less.

7. The method for producing a polymeric resin material composition according to claim 5 , wherein the mixture into which the curing accelerator is mixed in the second mixing step is heated in the heat curing step at 170° C. or more and 200° C. or less for 17 hours or more and 24 hours or less.

8. The method for producing a polymeric resin material composition according to claim 5, wherein 2-ethyl-4-methylimidazole is mixed as the curing accelerator.

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