Polymer resin composition and method for producing same

Abstract

The present invention provides a polymer resin composition excellent in strength and glass transition temperature and environmental suitability, and a method for producing the same.　This polymer resin composition is produced by subjecting a mixture obtained by mixing an ether group-containing epoxy resin and a hydroxy group-containing phenolic curing agent to a heating and curing process, and the hydroxy group-containing phenolic curing agent has a hydroxy group content of 9 mmol / g or less.

Description

Polymer resin composition and method for producing same

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

[0002] Efforts aimed at mitigating or reducing the impact of climate change have been ongoing for some time, and research and development into reducing carbon dioxide emissions has been conducted to achieve this. In particular, one technology that can contribute to reducing carbon dioxide emissions is the production of plastic materials used in the manufacture of electronic components, etc., using biomass raw materials. For example, Patent Document 1 discloses a technology for producing a polymer resin composition by blending epoxidized linseed oil, which is a hydrophobic epoxy resin containing an aryl ring skeleton or a long-chain alkyl group as a main component, a plant extract containing tannin as a phenolic hardener, and glycerin polyglycidyl ether, which is an ether group-containing epoxy resin.

[0003] JP 2012-007076 A

[0004] Meanwhile, in reducing carbon dioxide emissions, it is an issue to obtain a polymer resin composition having predetermined physical properties such as strength and glass transition temperature by using raw materials derived from plants.

[0005] In order to solve the above problems, the present application aims to produce a polymer resin composition and a molded article thereof that are excellent in strength, glass transition temperature, and environmental friendliness, and ultimately contribute to mitigating or reducing the impact of climate change.

[0006] In order to achieve the above object, the polymer resin composition of the present invention is produced by mixing an ether group-containing epoxy resin with a hydroxyl group-containing phenolic curing agent, and then subjecting the mixture to a heat curing treatment, and the hydroxyl group amount of the hydroxyl group-containing phenolic curing agent is 9 mmol / g or less.

[0007] According to the present invention, a polymer resin composition having predetermined physical properties can be obtained.

[0008] FIG. 1 is a process diagram showing a method for producing a polymer resin composition.

[0009] [1. Polymer Resin Composition] In recent years, research and development aimed at reducing carbon dioxide emissions has led to the study of biomass-based epoxy resins. However, polymer resin compositions using biomass-based epoxy resins often lack sufficient performance, such as strength and glass transition temperature, compared to petroleum-derived epoxy resins, and do not meet the required standards, so they have rarely been used as insulating materials.

[0010] An example of an electronic material using a polymer resin composition is an FR-4 electronic board, which is widely used in automobiles. FR-4 grade electronic boards, as defined by the ANSI / NEMA standard, require the use of a polymer resin composition that satisfies a glass transition temperature of 120°C or higher, a bending stress (flexural strength) of 50 MPa or higher, and a flexural modulus of 1600 MPa or higher. The GE4F flame-resistant glass cloth-based epoxy resin copper-clad laminate defined by JIS C6484 also requires a similar glass transition temperature. Another application of polymer resin compositions is IC encapsulation resins, which generally require a bending strength of 60 MPa to 70 MPa or higher. The matrix resin used in general structural FRP requires a bending strength of 100 MPa or higher.

[0011] The present inventors have discovered a polymer resin composition that can be applied to various types of electronic components and has a wide range of uses compared to conventional polymer resin compositions, by mixing an epoxy resin having an epoxy equivalent of 192 g / eq or less with a phenolic curing agent having a hydroxyl group amount of 9 mmol / g or less and subjecting the mixture to a heat curing treatment under predetermined conditions.

[0012] Furthermore, the researchers discovered a polymer resin composition that can be used in a wide range of applications, including mixing an epoxy resin with a phenolic curing agent, followed by further mixing in an epoxidized vegetable oil, which has flexibility, and then subjecting the mixture to a heat curing treatment under specified conditions, thereby improving bending stress and making it applicable to a wider variety of electronic components than conventional polymer resin compositions made from bio-based materials.

[0013] The epoxy resin, phenolic curing agent, and epoxidized vegetable oil can all be derived from bio-based raw materials, meaning that it is possible to produce a polymer resin composition that meets predetermined standards and in which 100% of the components are derived from bio-based raw materials.

[0014] The polymer resin composition obtained by this method has a high glass transition temperature and strength, and therefore can be a suitable material for electronic parts and electronic substrates.

[0015] The polymer resin composition produced by the method discovered by the present inventors is a thermosetting resin composition, and has the advantage of having a high glass transition temperature and strength, even though it uses a bio-based epoxy resin. Here, the glass transition temperature is measured by the method described in JIS K7121. In this embodiment, strength refers to bending stress and bending modulus. The bending stress and bending modulus are measured by the method described in JIS K7171.

[0016] 2. Production of Polymer Resin Composition Figure 1 is a process diagram showing a method for producing a polymer resin composition. In the method for producing a polymer resin composition of the present disclosure, a first mixing step S1 is performed in which a first main agent and a curing agent are charged into a mixer, and the first main agent and the curing agent are stirred and mixed in the mixer. In the first mixing step S1, the first main agent and the curing agent are mixed in the mixer to obtain a first mixture.

[0017] The first main component is an ether group-containing epoxy resin having an epoxy equivalent of 192 g / eq or less, which increases the crosslink density of the resulting polymer resin composition, thereby enabling the production of a polymer resin composition having a flexural modulus of 1600 MPa or more.

[0018] Examples of ether group-containing epoxy resins having an epoxy equivalent of 192 g / eq or less include sorbitol glycidyl ether (e.g., Denacol EX-614B (epoxy equivalent: 173 g / eq) manufactured by Nagase ChemteX Corporation) and limonene dioxide (e.g., Celloxide 3000 (epoxy equivalent: 166 g / eq) manufactured by Daicel Corporation).

[0019] The amount of hydroxyl-containing phenolic curing agent used as a curing agent is calculated so that it is equivalent to the epoxy group of the main component. For example, it is preferable to specify that the amount of hydroxyl groups is 9 mmol / g or less. By setting the amount of hydroxyl groups to 9 mmol / g or less, even if a large amount of curing agent is added, raw materials do not remain undissolved or the mixture does not harden properly during the production process of the polymer resin composition, and a polymer resin composition with a glass transition temperature of 120°C or more can be obtained.

[0020] Examples of hydroxyl group-containing phenolic curing agents include polyethylene glycol lignin (e.g., Lignotop manufactured by Lignomateria Co., Ltd.), lignin oligomer (e.g., Bloom Lignin Oligomer manufactured by Bloom Biorenewables SA), and daidzein (e.g., Daidzein manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0021] Subsequently, a second main component made of epoxidized vegetable oil is added to the obtained first mixture, followed by mixing and stirring in a second mixing step S2. In the second mixing step S2, the first mixture and the second main component are mixed to obtain a second mixture.

[0022] The second main component is preferably an epoxidized vegetable oil having flexibility. Furthermore, it is preferable to produce a polymeric resin composition by adding 15% or less of the second main component. This allows the resulting polymeric resin composition to have improved bending stress compared to a polymeric resin composition produced without adding epoxidized vegetable oil. In other words, a polymeric resin composition that can be applied to various types of electronic components and has a wide range of uses can be obtained.

[0023] Alternatively, the polymer resin composition may be produced without adding the second main agent, in which case the second mixing step S2 may be omitted.

[0024] Examples of flexible epoxidized vegetable oils include epoxidized soybean oil (e.g., Adeka Cizer O-130P manufactured by ADEKA Corporation and Sanso Cizer E-2000H manufactured by New Japan Chemical Co., Ltd.), epoxidized castor oil (e.g., EPOX MK R151 manufactured by Printec Co., Ltd.), and epoxidized linseed oil (e.g., Adeka Cizer O-180A manufactured by ADEKA Corporation and Sanso Cizer E-9000H manufactured by New Japan Chemical Co., Ltd.).

[0025] Next, the resulting second mixture is heated at a temperature lower than the heat curing temperature in a heating step S3 to reduce the viscosity of the mixture. For example, the heating step S3 is performed at 100° C. for 10 minutes.

[0026] Subsequently, a casting step S4 is performed in which the second mixture heated in the heating step S3 is poured into a mold.

[0027] After the casting step S4, the second mixture is heated to a heat-hardening temperature in the heat-hardening step S5. In this embodiment, the heat-hardening step S5 involves heating the second mixture at 160°C for two hours to harden the second mixture.

[0028] Thereafter, the second mixture heat-cured in the heat-curing step S5 is released from the mold in a demolding step S6 to obtain a polymer resin composition.

[0029] The polymer resin composition obtained by the manufacturing method of the present disclosure is measured for bending stress and bending modulus according to the method described in JIS K7171. Furthermore, the polymer resin composition obtained by the manufacturing method of the present disclosure is measured for glass transition temperature according to the method described in JIS K7121.

[0030] [3. Examples] Examples of polymer resin compositions produced by the production method of the present disclosure, with the types and amounts of the first main component, curing agent, and second main component being varied, are shown as Examples 1 to 11 and Comparative Examples 1 to 3. The present disclosure is not limited in any way by these Examples.

[0031] In this embodiment, the first main agent was one selected from sorbitol polyglycidyl ether (Denacol EX-614B, manufactured by Nagase ChemteX Corporation) and bisphenol A epoxy resin. The curing agent was one selected from polyethylene glycol lignin (Lignotop SD4, manufactured by Lignomateria Co., Ltd.) and tannic acid (Tannic acid AL, manufactured by Fuji Chemical Industry Co., Ltd.). The second main agent was one selected from epoxidized soybean oil (Adeka Cizer O-130P, manufactured by ADEKA Corporation) and epoxidized linseed oil (Adeka Cizer O-180A, manufactured by ADEKA Corporation).

[0032] The glass transition temperature was measured using a Thermo plus EVO2 manufactured by Rigaku Holdings Corporation under conditions conforming to JIS K7121. The bending stress and bending modulus were measured using an autograph manufactured by Shimadzu Corporation under conditions conforming to JIS K7171.

[0033] Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are examples in which polymer resin compositions were produced by varying the types and amounts of the first main component, curing agent, and second main component. Table 1 shows the bending stress and glass transition temperature of these examples.

[0034] In Examples 1 and 2, sorbitol glycidyl ether was used as the first main agent and polyethylene glycol lignin was used as the hardener. Epoxidized soybean oil was used as the second main agent. In Comparative Examples 1 and 2, the first and second main agents were the same as in Examples 1 and 2, and tannic acid was used as the hardener.

[0035] As shown in Example 2 of Table 1, by adding 40% or more of polyethylene glycol lignin as a curing agent, a polymer resin composition with a glass transition temperature of 120° C. or higher was obtained.

[0036] As shown in Comparative Examples 1 and 2, when tannic acid was used as a curing agent, the glass transition temperature of the polymer resin composition produced with an added amount of tannic acid less than 40% did not exceed 120° C. Furthermore, when a polymer resin composition was produced with an added amount of tannic acid of 40% or more (Comparative Example 2), poor curing (or insoluble residue) occurred, and a cured product could not be produced.

[0037] As shown in Examples 1 and 2 and Comparative Examples 1 and 2, it was revealed that a higher glass transition temperature can be obtained by increasing the addition rate of the curing agent. In other words, by increasing the addition amount of the curing agent, it is possible to produce a polymer resin composition that is applicable to various types of electronic components and can be used in a wide range of applications.

[0038]

[0039] In Examples 3 and 4, polymer resin compositions were produced by varying the amounts of sorbitol glycidyl ether (the first main agent) and polyethylene glycol lignin (the curing agent). Table 2 shows the results of measuring the hydroxyl group content of each. The hydroxyl group content of the curing agent was measured by neutralization titration, NMR spectroscopy, or other known methods. The amounts shown in Table 2 are the amounts added when the amount of hydroxyl groups in the curing agent is equivalent to the epoxy groups in the main agent, and are the upper limit of the amount of each curing agent added.

[0040] As shown in Examples 3 and 4 in Table 2, the lower the hydroxyl group content, the higher the amount of curing agent added. As a result, a polymer resin composition with a high glass transition temperature can be obtained by increasing the amount of curing agent added.

[0041]

[0042] Examples 5 to 7 and Comparative Example 3 compare the flexural modulus of polymer resin compositions when the first main component was changed. The cardanol used in Example 7 was epoxidized cardanol (FE-5130, manufactured by Tohoku Kako Co., Ltd.). The first main components and curing agents used in Examples 5 and 6 were as described above. Comparative Example 3 used a resin material used in commercially available FR-4 substrates. Specifically, bisphenol A-type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) was used as the main component, and dicyandiamide (DICY, manufactured by Nippon Carbide Corporation) was used as the curing agent.

[0043] As shown in Table 3, a lower epoxy equivalent leads to a higher flexural modulus. Specifically, when the epoxy equivalent is 192 g / eq or less, a polymer resin composition having a high flexural modulus of 1600 MPa or more can be obtained.

[0044]

[0045] Examples 8 to 11 are examples in which polymer resin compositions were produced using a bisphenol A epoxy resin (JER828 manufactured by Mitsubishi Chemical Corporation) as the first main agent, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (MHAC-P manufactured by Resonac Corporation) as the curing agent, and epoxidized linseed oil (ADEKA CIZER O-180A manufactured by ADEKA Corporation) as the second main agent. Examples 8 to 11 compare the bending stress of polymer resin compositions when the amount of second main agent added was changed.

[0046] As shown in Table 4, it was found that the smaller the amount of the second main component added, the more the bending stress of the polymer resin composition improved. In other words, the more the amount of the second main component added, the more the bending stress of the polymer resin composition tends to decrease. When the amount of the second main component added is less than 15% of the first main component (8% of the total material), the bending stress of the polymer resin composition increases significantly, and when the amount added is more than 15%, the bending stress tends to decrease significantly.

[0047]

[0048] 4. Other Embodiments The above-described embodiment merely shows one aspect of the present invention, and any modifications and applications are possible within the scope of the present invention.

[0049] In the above-described embodiment, the first mixture is prepared by mixing the first main component and the curing agent, and then the first mixture is mixed with the second main component. However, the second mixture does not necessarily have to be added after the first main component and the curing agent are mixed. In other words, the first main component, the curing agent, and the second main component may be mixed simultaneously, instead of being mixed stepwise as described in the above embodiment.

[0050] The mixers and heaters used in the above-described embodiments are merely examples. That is, the machines and tools used in the method for producing a polymeric resin composition are not limited to those in the above-described embodiments. Similarly, the size and shape of the mold used in the casting step are not particularly limited.

[0051] In the above-described embodiment, the heating step involves heating at 100° C. for 10 minutes and then at 160° C. for 2 hours to harden the mixture. However, the temperatures and times of the heating step and the heat-hardening step are not limited to the conditions of the embodiment. In other words, they can be changed as appropriate depending on the manufacturing method, etc.

[0052] 5. Configurations Supported by the Above-described Embodiments The above-described embodiments support the following configurations.

[0053] (Configuration 1) A polymeric resin composition produced by mixing an ether group-containing epoxy resin and a hydroxyl group-containing phenolic curing agent, followed by a heat curing treatment of the mixture obtained, wherein the hydroxyl group content of the hydroxyl group-containing phenolic curing agent is 9 mmol / g or less. According to this configuration, by setting the hydroxyl group content of the hydroxyl group-containing phenolic curing agent to 9 mmol / g or less, the amount of phenolic curing agent added during production of the polymeric resin composition can be increased, and a polymeric resin composition with desired physical properties can be obtained.

[0054] (Configuration 2) The polymer resin composition according to Configuration 1, wherein the ether group-containing epoxy resin has an epoxy equivalent of 192 g / eq or less. According to this configuration, by adjusting the epoxy equivalent of the ether group-containing epoxy resin to 192 g / eq or less, the flexural modulus of the polymer resin composition can be improved, and a polymer resin composition having desired physical properties can be obtained.

[0055] (Configuration 3) The polymer resin composition according to Configuration 1 or 2, having a glass transition temperature of 120° C. or higher. According to this configuration, since the glass transition temperature is 120° C. or higher, it is possible to obtain a polymer resin composition having a glass transition temperature that is applicable to FR-4 substrates.

[0056] (Configuration 4) The polymeric resin composition according to any one of Configurations 1 to 3, which is produced by adding 40% or more of the hydroxyl group-containing phenolic curing agent. According to this configuration, by adding 40% or more of the hydroxyl group-containing phenolic curing agent, the glass transition temperature of the polymeric resin composition can be increased, and a polymeric resin composition having predetermined physical properties can be obtained.

[0057] (Configuration 5) The polymeric resin composition according to any one of Configurations 1 to 4, which is produced by mixing a flexible epoxidized vegetable oil in addition to the ether group-containing epoxy resin and the hydroxyl group-containing phenolic curing agent. According to this configuration, the addition of the flexible epoxidized vegetable oil can improve the bending stress of the polymeric resin composition, thereby enabling the production of a polymeric resin composition having desired physical properties.

[0058] (Configuration 6) A method for producing a polymeric resin composition, comprising a mixing step of mixing an ether group-containing epoxy resin with a hydroxyl group-containing phenolic curing agent to produce a mixture, and a heat-curing step of heating and curing the mixture. This method makes it possible to obtain a polymeric resin composition having predetermined physical properties.

[0059] (Configuration 7) The method for producing a polymeric resin composition according to claim 6, further comprising a second mixing step of mixing a flexible epoxidized vegetable oil into the mixture by stirring, after the mixing step, a second mixture, and the heat curing step of heating and curing the second mixture. This configuration allows a polymeric resin composition having predetermined physical properties to be obtained.

Claims

1. A polymeric resin composition produced by mixing an ether group-containing epoxy resin with a hydroxyl group-containing phenolic curing agent, followed by heat curing, wherein the hydroxyl group content of the hydroxyl group-containing phenolic curing agent is 9 mmol / g or less.

2. The polymer resin composition according to claim 1, wherein the epoxy equivalent of the ether group-containing epoxy resin is 192 g / eq or less.

3. The polymer resin composition according to claim 1, having a glass transition temperature of 120°C or higher.

4. The polymer resin composition according to claim 1, which is produced by adding 40% or more of the hydroxyl group-containing phenolic curing agent.

5. The polymer resin composition according to claim 1, which is produced by mixing the ether group-containing epoxy resin, the hydroxyl group-containing phenolic curing agent, and a flexible epoxidized vegetable oil.

6. A method for producing a polymeric resin composition, comprising: a mixing step of mixing an ether group-containing epoxy resin with a hydroxyl group-containing phenolic curing agent to produce a mixture; and a heat-curing step of heating the mixture to cure it.

7. The method for producing a polymeric resin composition according to claim 6, further comprising a second mixing step of producing a second mixture by stirring and mixing a flexible epoxidized vegetable oil into the mixture after the mixing step, and the heat curing step is a step of heating and curing the second mixture.

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