WO2022050175A1

WO2022050175A1 - Resin composition and molded body

Info

Publication number: WO2022050175A1
Application number: PCT/JP2021/031405
Authority: WO
Inventors: 友絵田邊; 悠介山縣; 泰典樽谷; 翔一郎矢野; 紗彩塩野
Original assignee: 株式会社ブリヂストン
Priority date: 2020-09-01
Filing date: 2021-08-26
Publication date: 2022-03-10
Also published as: JPWO2022050175A1

Abstract

The present invention provides a resin composition which is capable of achieving a good balance between strength and elongation at higher levels in comparison to conventional epoxy resins.　In order to achieve the above, the present invention is characterized by containing: an epoxy resin; a crystalline copolymer that has a conjugated diene unit and a non-conjugated olefin unit, while having a proportion of a butylene unit of 0 mol%; and a curing agent.

Description

Resin composition and molded product

The present invention relates to a resin composition and a molded product.

Conventionally, epoxy resins are known to have high strength and elastic modulus of their cured products, and are excellent in heat resistance and chemical resistance, and are used for various purposes in the industrial field. On the other hand, the cured product of the epoxy resin has low flexibility and has a problem in fracture characteristics against strain. When a cured epoxy resin is used for automobiles and electric parts, cracks may occur due to the application of vibration or force, and improvement thereof has been desired.

In order to solve such a problem, for example, a technique of adding a rubber material to an epoxy resin (see Patent Document 1) and a technique of modifying the epoxy resin itself (see Patent Document 2) are disclosed.

Japanese Unexamined Patent Publication No. 7-268079 Japanese Unexamined Patent Application Publication No. 2003-246837

However, although the techniques disclosed in Patent Documents 1 and 2 can secure a certain degree of flexibility, none of them can secure sufficient growth, and further improvement is desired.

Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a resin composition capable of achieving both strength and elongation at a high level as compared with the conventional epoxy resin.
Another object of the present invention is to provide a molded product having excellent strength and good flexibility.

The gist structure of the present invention that solves the above problems is as follows.

The resin composition of the present invention is characterized by containing a crystalline copolymer having a conjugated diene unit and a non-conjugated olefin unit and a ratio of butylene units of 0 mol%, and a curing agent. ..
The resin composition of the present invention can achieve both strength and elongation at a high level as compared with the conventional epoxy resin.

Further, the sheet molded product of the present invention is characterized in that the above resin composition is used.
The sheet molded product of the present invention can realize good flexibility while having excellent strength.

According to the present invention, it is possible to provide a resin composition having both strength and elongation at a high level as compared with a conventional epoxy resin.
Further, according to the present invention, it is possible to provide a molded product having excellent strength and good flexibility.

Hereinafter, the resin composition and the sheet molded product of the present invention will be described in detail as examples based on the embodiments thereof.

<Resin composition>
The resin composition of the present invention comprises an epoxy resin and
A crystalline copolymer having a conjugated diene unit and a non-conjugated olefin unit and a proportion of butylene units of 0 mol%.
It is characterized by containing a curing agent.

A crystalline copolymer having a conjugated diene unit and a non-conjugated olefin unit and having a butylene unit ratio of 0 mol% contains a non-conjugated olefin unit and is derived from the non-conjugated olefin unit when it is greatly distorted. The crystal component is disintegrated, and the energy can be dissipated by the melting energy. Therefore, in the resin composition of the present invention, strength and elongation can be achieved at a high level by containing the above-mentioned copolymer in addition to the epoxy resin having excellent hardness.

(Epoxy resin)
The resin composition of the present invention contains an epoxy resin. By containing the epoxy resin in the resin composition, the strength (hardness) of the cured product can be increased.
The state of the epoxy resin, the epoxy equivalent, the molecular weight, the molecular structure and the like are not limited, and can be appropriately selected according to the required performance.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and ring-type aliphatic epoxy. Epoxy and glycidyl of unsaturated polymers such as resin, polyvalent aromatic or aliphatic carboxylic acid polyglycidyl ester, polyvalent phenol polyglycidyl ether, polyhydric alcohol glycidyl ether, nitrogen-containing heterocyclic compound polyglycidyl ether, polybutadiene, etc. Examples thereof include unsaturated monoepoxyd polymers such as methacrylate.

The content of the epoxy resin is not particularly limited, but from the viewpoint of the balance between the strength and elongation of the resin composition, the content of the epoxy resin with respect to the total content of the epoxy resin and the copolymer described later. Is preferably 35 to 65% by mass. By setting the content of the epoxy resin to 35% by mass or more, more excellent strength can be obtained, and by setting the content of the epoxy resin to 65% by mass or less, the content of the copolymer described later will be obtained. Can be secured and the decrease in elongation can be suppressed more reliably.

(Copolymer)
In addition to the above-mentioned epoxy resin, the resin composition of the present invention contains a crystalline copolymer having a conjugated diene unit and a non-conjugated olefin unit and having a ratio of butylene units of 0 mol%.
By including the copolymer, it is possible to impart an energy dispersion effect when stress is applied, and it is possible to enhance the elongation of the resin composition while maintaining the strength at a high level.

The conjugated diene unit in the copolymer is a structural unit derived from the conjugated diene compound as a monomer. The conjugated diene unit can exhibit the elongation and strength of the copolymer. Here, the conjugated diene compound refers to a conjugated diene compound. The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. The conjugated diene compound may be used alone or in combination of two or more.
The conjugated diene compound as a monomer of the multiplex copolymer contains 1,3-butadiene and / or isoprene from the viewpoint of effectively improving the strength of the resin composition using the obtained multiplex copolymer. It is preferably contained, more preferably composed of only 1,3-butadiene and / or isoprene, and even more preferably composed of only 1,3-butadiene. In other words, the conjugated diene unit in the multi-dimensional copolymer preferably contains 1,3-butadiene unit and / or isoprene unit, and may consist only of 1,3-butadiene unit and / or isoprene unit. It is preferable that it consists of only 1,3-butadiene units.

Further, the content of the conjugated diene unit in the copolymer is preferably 3 mol% or more, more preferably 5 mol% or more, and further preferably 6 mol% or more. This is because when the content of the conjugated diene unit is 3 mol% or more of the total amount of the multiple copolymer, a resin composition having excellent elongation can be obtained. Further, the content of the conjugated diene unit is preferably 70 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, still more preferably 30 mol% or less. .. This is because when the content of the conjugated diene unit is 70 mol% or less, the weather resistance is excellent. Therefore, the content of the conjugated diene unit is preferably in the range of 3 to 70 mol% of the entire copolymer, and more preferably in the range of 5 to 60 mol%.

The non-conjugated olefin unit in the copolymer is a structural unit derived from the non-conjugated olefin compound as a monomer. When the non-conjugated olefin unit is greatly distorted, the crystal component derived from the non-conjugated olefin unit dissipates to dissipate energy. Here, the non-conjugated olefin compound refers to an aliphatic unsaturated hydrocarbon having one or more carbon-carbon double bonds. The non-conjugated olefin compound preferably has 2 to 10 carbon atoms. Specific examples of the non-conjugated olefin compound include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, vinyl pivalate and 1-phenylthioethane. , N-vinylpyrrolidone and other heteroatomic substituted alkene compounds and the like. The non-conjugated olefin compound may be used alone or in combination of two or more. The non-conjugated olefin compound as a monomer of the copolymer is a non-cyclical non-conjugated olefin compound from the viewpoint of further improving the weather resistance of the resin composition and tires using the obtained copolymer. The acyclic non-conjugated olefin compound is more preferably α-olefin, further preferably an α-olefin containing ethylene, and particularly preferably composed of ethylene alone. In other words, the non-conjugated olefin unit in the copolymer is preferably an acyclic non-conjugated olefin unit, and the acyclic non-conjugated olefin unit is more preferably an α-olefin unit. It is more preferable that it is an α-olefin unit containing an ethylene unit, and particularly preferably it is composed of only an ethylene unit.

Further, the content of the non-conjugated olefin unit in the copolymer is preferably 25 mol% or more, more preferably 30 mol% or more, further preferably 35 mol% or more, still more preferably 45 mol% or more. Is even more preferable, and 50 mol% or more is particularly preferable. Further, the content of the non-conjugated olefin unit is preferably 97 mol% or less, more preferably 94 mol% or less, still more preferably 90 mol% or less. When the content of the non-conjugated olefin unit is 25 mol% or more of the total amount of the copolymer, as a result, the content of the conjugated diene unit and the aromatic vinyl unit described later is reduced, the weather resistance is improved, and the strength is increased. improves. Further, when the content of the non-conjugated olefin unit is 97 mol% or less, the content of the conjugated diene unit and the aromatic vinyl unit described later increases as a result, and the elongation is improved. Therefore, the content of the non-conjugated olefin unit is preferably in the range of 25 to 97 mol%, more preferably in the range of 25 to 94 mol%, and even more preferably in the range of 35 to 90 mol%.

The copolymer preferably further has an aromatic vinyl unit. The aromatic vinyl unit is a structural unit derived from an aromatic vinyl compound as a monomer. By including the aromatic vinyl unit, the flexibility of the copolymer can be further enhanced. Here, the aromatic vinyl compound refers to an aromatic compound substituted with at least a vinyl group, and is not included in the conjugated diene compound. The aromatic vinyl compound preferably has 8 to 10 carbon atoms. Examples of such aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like. .. The aromatic vinyl compound may be used alone or in combination of two or more.
The aromatic vinyl compound as the monomer of the copolymer preferably contains styrene from the viewpoint of improving the weather resistance of the resin composition using the obtained copolymer, and is composed of only styrene. Is more preferable. In other words, the aromatic vinyl unit in the copolymer preferably contains a styrene unit, and more preferably consists of only a styrene unit.
The aromatic ring in the aromatic vinyl unit is not included in the main chain of the plural copolymer unless it is bonded to an adjacent unit.

The content of the aromatic vinyl unit in the copolymer is preferably 1 mol% or more, and more preferably 2 mol% or more. Further, the content of the aromatic vinyl unit is preferably 30 mol% or less, more preferably 25 mol% or less, and further preferably 20 mol% or less. When the content of the aromatic vinyl unit in the copolymer is 1 mol% or more, the durability at high temperature is improved. Further, when the content of the aromatic vinyl unit is 30 mol% or less, the effect of the conjugated diene unit and the non-conjugated olefin unit becomes remarkable. Therefore, the content of the aromatic vinyl unit is preferably in the range of 1 to 30 mol% of the entire copolymer, and more preferably in the range of 2 to 25 mol%.

The number of types of monomers in the copolymer is not particularly limited except that the copolymer contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit as a suitable component. do not have. The copolymer may have other structural units other than the conjugated diene unit, the non-conjugated olefin unit, and the aromatic vinyl unit, but the content of the other structural units obtains the desired effect. From the viewpoint, it is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, and not contained, that is, the content is 0 mol%. Is particularly preferred.

Here, for the copolymer, the ratio of the butylene unit is 0 mol% (there is no butylene unit). That is, the copolymer A does not contain hydrogenated styrene-butadiene copolymers such as styrene-ethylene / butylene-styrene (SEBS).

In addition, the copolymer has crystallinity. This makes it possible to effectively increase the strength of the resin composition after curing. The adjustment for making the copolymer crystalline is, for example, the ratio of each monomer unit including the non-conjugated olefin unit and the order of charging each monomer when synthesizing the copolymer. Alternatively, it can be carried out by appropriately changing the type of catalyst used for synthesizing the copolymer.
The existence of the "crystallinity" of the copolymer can be confirmed by confirming the melting point in the measurement by a differential scanning calorimeter (DSC) based on JIS K 7121-1987.

The copolymer preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 10,000,000, more preferably 50,000 to 2,000,000. It is more preferably ~ 2,000,000. When the Mw of the copolymer is 10,000 or more, the mechanical strength of the resin composition can be sufficiently secured, and when the Mw is 10,000,000 or less, high flexibility is achieved. Can be retained.

For the above-mentioned weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn), polystyrene is used as a standard substance by gel permeation chromatography (GPC).

In the resin composition of the present invention, the copolymer preferably has a melting point of 30 to 130 ° C., more preferably 30 to 110 ° C., as measured by a differential scanning calorimeter (DSC). When the melting point of the copolymer is 30 ° C. or higher, the crystallinity of the copolymer is high, the wear resistance of the resin composition is further improved, and the durability after crosslinking can be further improved. Further, when the melting point of the copolymer is 130 ° C. or lower, the workability of the resin composition is improved.
Here, the melting point is a value measured by the method described in Examples.

In the resin composition of the present invention, the copolymer preferably has a glass transition temperature (Tg) of 0 ° C. or lower, preferably −100 to −10 ° C., as measured by a differential scanning calorimeter (DSC). More preferred. When the glass transition temperature of the copolymer (a1) is 0 ° C. or lower, the workability of the resin composition is improved.
Here, the glass transition temperature is a value measured by the method described in Examples.

In the resin composition of the present invention, the copolymer preferably has a crystallinity of 0.5 to 50%, more preferably 3 to 45%, and more preferably 5 to 45%. More preferred. When the crystallinity of the copolymer is 0.5% or more, the crystallinity due to the non-conjugated olefin unit can be sufficiently ensured, and the fracture resistance can be further improved. Further, when the crystallinity of the copolymer is 50% or less, the workability at the time of kneading the resin composition is improved, and the tackiness of the resin composition containing the copolymer is improved. Workability when doing this is also improved.
Here, the crystallinity is a value measured by the method described in Examples.

In the resin composition of the present invention, it is preferable that the main chain of the copolymer has only an acyclic structure. Thereby, the strength of the resin composition can be further improved, and the durability after crosslinking can be further improved.
In addition, NMR is used as a main measuring means for confirming whether or not the main chain of the copolymer has a cyclic structure. Specifically, when a peak derived from the cyclic structure existing in the main chain (for example, a peak appearing at 10 to 24 ppm for a three-membered ring to a five-membered ring) is not observed, the main chain of the multipolymer is the main chain. , Indicates that it consists only of a non-cyclic structure.

The copolymer can be produced through a polymerization step using a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound as monomers, and if necessary, a coupling step, a cleaning step, and other steps. It may go through a process.
Here, in the production of the copolymer, it is preferable that only the non-conjugated olefin compound and the aromatic vinyl compound are added without adding the conjugated diene compound in the presence of the polymerization catalyst, and these are first polymerized. In particular, when the catalyst composition described below is used, the reactivity of the conjugated diene compound is higher than that of the non-conjugated olefin compound and the aromatic vinyl compound. Therefore, the non-conjugated olefin compound and / or the aromatic compound is present in the presence of the conjugated diene compound. It tends to be difficult to polymerize vinyl compounds. Further, it is also liable to be difficult due to the characteristics of the catalyst to polymerize the conjugated diene compound first and then additionally polymerize the non-conjugated olefin compound and the aromatic vinyl compound.
As the method for producing the copolymer, for example, the one described in International Publication No. 2015/190072 can be used.

The content of the copolymer is not particularly limited, but from the viewpoint of the balance between the strength and elongation of the resin composition, the content of the copolymer with respect to the total content of the epoxy resin and the copolymer. The ratio is preferably 35 to 65% by mass. By setting the content of the copolymer to 35% by mass or more, more excellent elongation can be realized, and by setting the content of the copolymer to 65% by mass or less, the content of the epoxy resin is secured. However, the decrease in strength can be reliably suppressed.

(Hardener)
The resin composition of the present invention contains a curing agent in addition to the above-mentioned epoxy resin and copolymer.
The curing agent can cure the epoxy resin and increase the strength of the resin composition.
The type of the curing agent is not particularly limited, and can be appropriately selected depending on the required performance. For example, amines, acid anhydrides, phenols, polyamides and the like can be mentioned.

Among these curing agents, it is preferable to use, for example, an acid anhydride having the following structure from the viewpoint of achieving both strength and elongation of the resin composition at a higher level.

The content of the curing agent is not particularly limited, and can be appropriately adjusted according to the type of epoxy resin, the degree of curing, and the like.
For example, from the viewpoint of the balance between the strength and elongation of the resin composition, the content of the curing agent is 100 parts by mass of the epoxy resin (in the case of containing the thermoplastic resin, the total amount of the epoxy resin and the thermoplastic resin). On the other hand, it is preferably 0.1 to 10 parts by mass.

(Other ingredients)
Further, it is preferable that the resin composition of the present invention further contains a thermoplastic resin. This is because the resin composition is given flexibility and more excellent elongation can be realized.
The type of the thermoplastic resin is not particularly limited, but a resin having a hydroxyl group is preferable from the viewpoint of achieving both strength and elongation of the resin composition at a higher level.
Examples of the thermoplastic resin having a hydroxyl group include a phenoxy resin, a dicyclopentadiene resin, a terpene phenol resin, a terpene resin, a rosin resin, and an alkylphenol resin.

The phenoxy resin is a polyhydroxypolyether synthesized from bisphenols and epichlorohydrin, and the phenoxy resin in a broad sense obtained by subjecting a polyfunctional epoxy resin to a polyfunctional phenol by a double addition reaction is also included in the phenoxy resin.
Examples of the phenoxy resin include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A type and bisphenol F type copolymerized phenoxy resin, biphenyl type phenoxy resin, bisphenol S type phenoxy resin, and biphenyl type phenoxy resin. Examples thereof include a phenoxy resin copolymerized with a bisphenol S-type phenoxy resin. Among them, a bisphenol A type phenoxy resin or a copolymerized phenoxy resin of bisphenol A type and bisphenol F type is preferable, and it may be used alone or in combination of two or more.

The dicyclopentadiene resin is a petroleum resin produced by using dicyclopentadiene as a main raw material, which is obtained by dimerizing cyclopentadiene. As the dicyclopentadiene resin, a commercially available product can be used. For example, among the trade names "Quinton (registered trademark) 1000 series", which is an alicyclic petroleum resin manufactured by Nippon Zeon Corporation, "1105, 1325, 1340 "and the like.

The terpene phenol resin can be obtained, for example, by reacting terpenes with various phenols using a Friedel-Crafts type catalyst, or by further condensing with formalin. The raw material terpenes are not particularly limited, and monoterpene hydrocarbons such as α-pinene and limonene are preferable, those containing α-pinene are more preferable, and α-pinene is particularly preferable. Commercially available products can be used as the terpene phenol resin, for example, trade names "Tamanol 803L", "Tamanol 901" (manufactured by Arakawa Chemical Industry Co., Ltd.), and trade name "YS Polystar (registered trademark) U" series. , "YS Polystar (registered trademark) T" series, "YS Polystar (registered trademark) S" series, "YS Polystar (registered trademark) G" series, "YS Polystar (registered trademark) N" series, "YS Polystar (registered trademark)" Examples thereof include the "K" series and the "YS Polystar (registered trademark) TH" series (manufactured by Yasuhara Chemical Co., Ltd.).

The terpene resin is a solid resin obtained by blending turpentine oil obtained at the same time as obtaining rosin from a pine tree or a polymerization component separated from the turpentine and polymerizing using a Friedelcrafts type catalyst. Yes, β-pinene resin, α-pinene resin and the like can be mentioned. Commercially available products can be used as the terpene resin. For example, the product name "YS Resin" series (PX-1250, TR-105, etc.) manufactured by Yasuhara Chemical Co., Ltd. and the product name "Picolite" series manufactured by Hercules Co., Ltd. (A115, S115, etc.) and the like.

The rosin resin is a residue left after collecting balsams such as pine fat (pine Yani), which is the sap of a plant of the Pinaceae family, and distilling terepine essential oil. Natural resins as the main component, modified resins obtained by modifying them, rosin, etc., and hydrogenated resins. Examples thereof include natural resin rosins, their polymerized rosins and partially hydrogenated rosins; glycerin ester rosins, their partially hydrogenated rosins, fully hydrogenated rosins and polymerized rosins; pentaerythritol ester rosins, their partially hydrogenated rosins and polymerized rosins. .. Examples of natural resin rosin include raw pine rosin, gum rosin contained in tall oil, tall oil rosin, and wood rosin. As the rosin resin, a commercially available product can be used, for example, the product name "Neotoll 105" (manufactured by Harima Kasei Co., Ltd.), the product name "SN Tuck 754" (manufactured by San Nopco Ltd.), and the product name "Lime Resin". No. 1 ”,“ Pencel A ”and“ Pencel AD ”(manufactured by Arakawa Chemical Industry Co., Ltd.), product names“ Polypale ”and“ Pentalin C ”(manufactured by Eastman Chemical Co., Ltd.), product name“ Hyrosin (registered trademark) "S" (manufactured by Taisha Matsusei Oil Co., Ltd.) and the like can be mentioned.

The alkylphenol resin is obtained, for example, by a condensation reaction between alkylphenol and formaldehyde under a catalyst. As the alkylphenol resin, a commercially available product can be used. For example, the product name "Hitanol 1502P" (alkylphenol formaldehyde resin, manufactured by Hitachi Kasei Co., Ltd.) and the product name "Tackiroll 201" (alkylphenol formaldehyde resin, Taoka Chemical Industry Co., Ltd.) can be used. Product name "Tackiroll 250-I" (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), Product name "Tackiroll 250-III" (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), Examples thereof include product names "R7521P", "SP1068", "R7510PJ", "R7572P" and "R7578P" (manufactured by SIGROUP INC.).

The content of the thermoplastic resin is not particularly limited, but from the viewpoint of achieving both the strength and elongation of the resin composition at a higher level, the total content of the epoxy resin, the copolymer, and the thermoplastic resin is not limited. The content of the epoxy resin is 15 to 50% by mass, the content of the copolymer is 15 to 50% by mass, and the content of the thermoplastic resin is 30 to 60% by mass with respect to the amount. It is preferable to have.

Further, it is preferable that the resin composition of the present invention further contains an antioxidant. This is to achieve both the strength and elongation of the resin composition at a higher level.
From the same viewpoint, the antiaging agent preferably has two or more phenyl groups containing a branched alkyl group. Examples of such an antioxidant include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds and phosphorus compounds. In particular, as an antiaging agent, it is preferable to contain a compound having two or more phenyl groups having a branched alkyl group. As described above, by using a compound having two or more phenyl groups with a branched alkyl group as an antiaging agent, the dispersibility of the copolymer can be improved and the dispersibility of the copolymer can be improved when kneading at a high temperature in the production of a film. It is possible to suppress gelation of the polymer. The compound having two or more phenyl groups containing a branched alkyl group may be used alone or in combination of two or more.

More specifically, the compound having two or more phenyl groups containing a branched alkyl group is preferably a compound having a structure represented by the following formula (1) or formula (2).

In the above formulas (1) and (2), R ¹ to R ⁸ , R ¹¹ to R ¹⁸ , and R ²¹ to R ²⁴ are hydrogen atoms, linear alkyl groups, cyclic alkyl groups, or branched alkyl groups. Yes, at least one of R ¹ to R ⁸ ; and at least one of R ¹¹ to R ¹⁸ and R ²¹ to R ²⁴ are branched alkyl groups. R ¹ to R ⁸ , R ¹¹ to R ¹⁸ , and R ²¹ to R ²⁴ may be the same or different from each other. R ⁹ is a hydrocarbon group. A ¹ and A ² are linking groups. E is a trivalent heteroatom.

The number of carbon atoms of the linear alkyl group is preferably 1 to 12, more preferably 1 to 8, further preferably 1 to 5, and even more preferably 1 to 3. Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group. Examples thereof include an n-nonyl group, an n-decyl group and an n-dodecyl group. The linear alkyl group may further have a substituent such as a halogen atom.
Among the above, the linear alkyl group is preferably an unsubstituted linear alkyl group, more preferably a methyl group, an ethyl group, or an n-propyl group.
The cyclic alkyl group preferably has 5 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Specific examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. The cyclic alkyl group may further have a substituent such as an alkyl group having 1 to 3 carbon atoms and a halogen atom.
Among the above, the cyclic alkyl group is preferably an unsubstituted cyclic alkyl group, more preferably a cyclohexyl group.
The number of carbon atoms of the branched alkyl group is preferably 3 to 12, more preferably 3 to 8, further preferably 4 to 8, and even more preferably 4 to 6. Specific examples of the branched alkyl group include an isopropyl group, a 2-butyl group, a tert-butyl group, a tert-pentyl group, a 2-hexyl group, a 2-heptyl group, a 2-octyl group, a 2-dodecyl group and the like. Can be mentioned. The branched alkyl group may further have a substituent such as a halogen atom.
Among the above, the branched alkyl group is preferably an unsubstituted branched alkyl group, more preferably an isopropyl group, a 2-butyl group, a tert-butyl group, or a tert-pentyl group, and more preferably a tert-butyl group. Alternatively, it is more preferably a tert-pentyl group.

Examples of the hydrocarbon group represented by R ⁹ include an alkyl group, an alkenyl group, an alkynyl group and the like. Examples of the alkyl group include the linear alkyl group, the cyclic alkyl group, and the branched alkyl group exemplified above, and the preferred range is also the same. Further, as the alkenyl group and the alkynyl group, those having 2 to 8 carbon atoms are preferable, and examples thereof include a vinyl group and the like.

Examples of the linking group represented by A ¹ and A ² include a divalent hydrocarbon group having 1 to 6 carbon atoms, and a heteroatom having a divalent value or more (for example, an oxygen atom, a sulfur atom, etc.). But it may be. The hydrocarbon of the above hydrocarbon group may be a saturated hydrocarbon or an unsaturated hydrocarbon. Among them, the linking group is preferably a saturated hydrocarbon group, and the linking group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms. The linking group may further have a substituent such as a halogen atom, a methyl group or an ethyl group.

Examples of the trivalent heteroatom represented by E include a sulfur atom and a phosphorus atom, and among them, a phosphorus atom is preferable.

In the formula (1), it is preferable that at least one of R ¹ to R ⁴ and at least one of R ⁵ to R ⁸ are branched alkyl groups, respectively. Further, in the formula (2), from the group consisting of the group Ra selected from R ¹¹ to R ¹⁴ , the group Rb selected from R ¹⁵ to R ¹⁸ , and the group Rc selected from R ²¹ to R ²⁴ . It is preferred that at least two selected are branched alkyl groups.
Further, the phenyl group having a branched alkyl group (phenyl group with a branched alkyl group) preferably has a plurality of branched alkyl groups. Among them, ⁱⁿ the formulas ( ¹ ) and (2), at least two of ^R1 to ^R4 ; at ^least two of R5 to R8; at least two of R11 to ^R14 ; and ^R15 . It is preferable that at least two of the to ^R18 are branched alkyl groups.

For example, the compound having the structure represented by the formula (1) is preferably as follows:
R ¹ and R ⁸ are branched alkyl groups; R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms; R ³ and R ⁶ are branched or linear alkyl groups; R ⁹ are unsaturated hydrocarbon groups; A ¹ is a divalent saturated hydrocarbon group.

Further, the compound having the structure represented by the formula (1) is more preferably as follows:
R ¹ and R ⁸ are unsubstituted branched alkyl groups having 3 to 6 carbon atoms; R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms; R ³ and R ⁶ are unsubstituted branched alkyl groups having 4 to 5 carbon atoms. Alkyl group or unsubstituted linear alkyl group having 1 to 3 carbon atoms; R ⁹ is an unsubstituted vinyl group; A ¹ is an alkyl group substituted or unsubstituted methylene group.

Further, as the compound having the structure represented by the formula (1), it is more preferable that the compound has the structure represented by the following formula (3) or the formula (4).

The structure represented by the formula (2) is preferably as follows:
R ¹¹ , R ¹³ , R ¹⁶ , R ¹⁸ and R ²¹ are branched alkyl groups; R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ²² and R ²³ are hydrogen atoms; R ²⁴ is a linear alkyl group; A ² Is a divalent saturated hydrocarbon group containing an oxygen atom; E is a sulfur atom or a phosphorus atom.

Further, the structure represented by the formula (2) is more preferably as follows:
R ¹¹ , R ¹³ , R ¹⁶ , R ¹⁸ and R ²¹ are unsubstituted branched alkyl groups having 3 to 5 carbon atoms; R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁷ , R ²² and R ²³ are hydrogen atoms; R ²⁴ is an unsubstituted linear alkyl group having 1 to 3 carbon atoms; A ² is an unsubstituted alkyleneoxy group having 2 to 5 carbon atoms (in -OR-, R is an unsubstituted alkylene group having 2 to 5 carbon atoms). E is a phosphorus atom.

Furthermore, as the compound having the structure represented by the formula (2), it is more preferable that the compound has the structure represented by the following formula (5).

The compound having two or more phenyl groups having a branched alkyl group is particularly preferably a compound having a structure represented by the above formula (4) or the above formula (5).

The content of the antioxidant is preferably 0.1 part by mass or more and 10 parts by mass or less with respect to the total amount (100 parts by mass) of the epoxy resin and the copolymer (and the thermoplastic resin). When the content of the antiaging agent is 0.1 part by mass or more, the effect of improving the dispersibility of the copolymer and suppressing gelation can be sufficiently obtained, and when the content is 10 parts by mass or less, the effect is obtained. It is fully demonstrated.

Furthermore, it is preferable that the resin composition of the present invention further contains a styrene-based elastomer as a compatibilizer. This is to achieve both the strength and elongation of the resin composition at a higher level.

The styrene-based elastomer may be any as long as it has an effect as a compatibilizer, and is not particularly limited. For example, styrene / butadiene copolymer (SBS), styrene / ethylenebutylene / styrene block copolymer (SEBS), styrene / ethylenepropylene / styrene block copolymer (SEPS), styrene / ethylene / ethylenepropylene / styrene block. Examples include copolymers (SEEPS) and the like.
Among these, the styrene-based elastomer preferably contains at least one of a styrene-butadiene copolymer (SBS) and a styrene-ethylenebutylene-styrene block copolymer (SEBS).

The content of the styrene-based elastomer is preferably 1 to 20 parts by mass when the total content of the epoxy resin and the copolymer (and the thermoplastic resin) is 100 parts by mass. It is more preferably 5 to 15 parts by mass. When the content of the styrene-based elastomer is 1 part by mass or more with respect to 100 parts by mass of the total content of the epoxy resin and the copolymer, the effect as a compatibilizer can be surely exhibited. On the other hand, when the content of the styrene-based elastomer is 20 parts by mass or less, the epoxy resin as a resin can sufficiently function as a matrix.

In addition to the above-mentioned thermoplastic resin, antiaging agent and styrene elastomer, the resin composition of the present invention contains polymer components other than the copolymer, fillers such as carbon black and silica, and softening of oil and the like. It is possible to include an agent, a cross-linking agent such as sulfur or an organic peroxide, and various vulcanization accelerators.

However, in the present invention, it is preferable that the above-mentioned components do not contain fillers, oils, or sulfur in order to fully exert the functions of the resin composition.

Further, in the present invention, it is preferable to include a vulcanization accelerator because it contributes to the miniaturization of the domain size in the resin composition. Further, among the vulcanization accelerators, it is more preferable to use a dithiocarbamate-based accelerator.

<Sheet molded body>
Next, the sheet molded body of the present invention will be described. The sheet molded product of the present invention is characterized in that the above-mentioned resin composition of the present invention is used.
The sheet molded product of the present invention formed by using the above-mentioned resin composition has excellent strength and flexibility.

Here, the sheet molded body is a resin composition formed into a sheet and cured. The shape and size of the sheet molded product are not particularly limited, and can be appropriately selected depending on the applicable article and the required performance.

The method for manufacturing the sheet molded product of the present invention is not particularly limited. For example, a sheet-shaped molded product can be obtained by molding the resin composition of the present invention into a sheet shape (creating a pre-molded product), heating it as necessary, and allowing it to stand for a certain period of time.

The sheet molded product of the present invention can be used for various purposes. For example, tire parts, automobile parts (automobile seats, automobile batteries (lithium ion batteries, etc.), weather strips, hose tubes, anti-vibration rubbers, cables, sealing materials, etc.), conveyor belts, crawlers, etc. , Anti-vibration rubber, hose, resin piping, sound absorbing material, bedding, precision parts for office equipment (OA roller), bicycle frame, golf ball, tennis racket, golf shaft, resin additive, filter, adhesive, adhesive, Ink, medical equipment (medical tubes, bags, microneedles, rubber sleeves, artificial organs, caps, packings, injector gaskets, drug stoppers, artificial legs, artificial limbs), cosmetics (UV powder, puffs, containers, waxes, shampoos, conditioners) , Detergent, building materials (floor materials, anti-vibration rubber, seismic isolation rubber, building films, sound absorbing materials, waterproof sheets, heat insulating materials, joint materials, sealing materials), packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, Electronic materials, electronic devices, communication equipment, aircraft parts, mechanical parts, electronic parts, agricultural materials, electric wires, cables, fibers (wearable bases), daily necessities (toothbrushes, shoe soles, eyeglasses, artificial bait, binoculars, toys, dustproof masks) , Garden hose), robot parts, optical parts, road materials (asphalt, guard rails, poles, signs), protective equipment (shoes, bulletproof vests), electrical equipment exterior parts, OA exterior parts, soles, sealing materials, etc. Is.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

(Analysis of copolymer)
Number average molecular weight (Mn), weight average molecular weight (Mw), butadiene unit, ethylene unit and styrene unit content, melting point, heat absorption peak energy, glass transition temperature, crystallinity of the copolymer synthesized as described later. Was measured, and the main chain structure was confirmed.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: HLC-8121 GPC / HT manufactured by Toso Co., Ltd., column: GMH _HR -H (S) HT x 2 manufactured by Toso Co., Ltd., detector: differential refractometer (RI)] to obtain monodisperse polystyrene. As a reference, the polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the copolymer were determined. The measured temperature is 40 ° C.

(2) Content of butadiene unit, ethylene unit, styrene unit The content (mol%) of butadiene unit, ethylene unit, and styrene unit in the copolymer can be determined by ^{1 1} H-NMR spectrum (100 ° C, d-tetrachloroethane standard). : 6 ppm) was calculated from the integral ratio of each peak.

(3) Melting point (T _m )
The melting point of the copolymer was measured according to JIS K 7121-1987 using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000").

(4) Endothermic peak energy Using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000"), the temperature rise rate at 10 ° C / min in accordance with JIS K 7121-1987. The temperature was raised from −150 ° C. to 150 ° C., and the endothermic peak energy at 0 to 120 ° C. at that time (1st run) was measured.

(5) Glass transition temperature (Tg)
The glass transition temperature (Tg) of the copolymer was measured according to JIS K 7121-1987 using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000").

(6) Crystallinity The crystallinity was calculated from the crystal melting energy of polyethylene, which is a 100% crystal component, and the melting peak energy of the obtained copolymer, and the energy ratio between polyethylene and the copolymer. The melting peak energy was measured with a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000").

(7) Confirmation of main chain structure ¹³ C-NMR spectrum was measured for the synthesized copolymer.

(Synthesis of copolymer A)
52 g of styrene and 762 g of toluene were added to a sufficiently dried 2000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, a mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex: 1,3-[(t-Bu) in a glass container. ) Me ₂ Si] ₂ C ₉ H ₅ Gd [N (SiHMe ₂ ) ₂ ] 0.031 mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate: [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 0.031 mmol It was charged and 21 g of toluene was added to prepare a catalytic solution. The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 60 ° C. In addition, "t-Bu" means a tert-butyl group, "Me" means a methyl group, and "Ph" means a phenyl group (the same applies hereinafter).
Next, ethylene was charged into the pressure-resistant stainless steel reactor at a pressure of 1.0 MPa, and copolymerization was carried out at 75 ° C. for a total of 9 hours. 1,3-butadiene was continuously added to 0.6 mL / min. 108 g of a toluene solution containing 27 g of 1,3-butadiene was added at the rate of.
Then, 1 ml of an isopropanol solution of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in an amount of 5% by mass was added to the pressure-resistant stainless steel reactor to terminate the reaction.
Then, the copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain a copolymer.
The obtained copolymer has a number average molecular weight (Mn), a weight average molecular weight (Mw), a molecular weight distribution (Mw / Mn), a butadiene unit, an ethylene unit, a styrene unit content, a melting point ( _Tm ), and a heat absorption peak. Energy, glass transition temperature (Tg) and crystallinity were measured by the above methods. The results are shown in Table 1.
Further, when the main chain structure of the obtained copolymer was confirmed by the above method, no peak was observed at 10 to 24 ppm in the ¹³ C-NMR spectrum chart. It was confirmed that the main chain consisted only of an acyclic structure.

(Synthesis of copolymer B)
91 g of styrene and 379 g of toluene were added to a fully dried 2000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, a mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadrinium complex: 1,3-[(t-Bu) is placed in a glass container. ) Me ₂ Si] ₂ C ₉ H ₅ Gd [N (SiHMe ₂ ) ₂ ] 0.1 mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate: [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 0.1 mmol and 0.3 mmol of triisobutylaluminum was charged, and 63 mL of toluene was added to prepare a catalytic solution. The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 60 ° C.
Then, ethylene was charged into the pressure resistant stainless steel reactor at a pressure of 1 to 1.5 MPa, and copolymerization was carried out at 85 ° C. for a total of 4 hours. 1,3-Butadiene was continuously added at 1.1 to 1.2 mL / min. 280 g of a toluene solution containing 70 g of 1,3-butadiene was added at the rate of.
Then, 1 mL of a 5% by mass isopropanol solution of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) was added to the pressure resistant stainless steel reactor to terminate the reaction.
Then, the copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain the copolymer B.

<Preparation of samples of resin composition and sheet molded product>
A sample of the resin composition was prepared according to the formulation shown in Table 2. Specifically, a mixture of a thermoplastic resin (phenoxy resin) and an epoxy resin is prepared, and a copolymer, a styrene-based elastomer, a vulcanization accelerator, and an antiaging agent are added to the mixture, and then 10 at 130 ° C. Kneading was performed with a plastic mill under the condition of 1 minute. Then, after lowering the temperature to 100 ° C., a curing agent was added, and kneading was performed with a plast mill for 30 seconds.
A sample of the obtained resin composition was pressed at 100 ° C. for 3 minutes to prepare a presheet molded product. Then, the pre-sheet molded product was pressed at 190 ° C. for 10 minutes to cure it, and a sample of the sheet-molded product was obtained.
The blending amount of each component in Table 2 is indicated by the mass part with respect to 100 parts by mass of the thermoplastic.

<Evaluation>
(1) Strength (breaking point strength)
The breaking point strength (MPa) was measured for each sample sheet molded product in accordance with JIS K 6251: 2017.
Regarding the evaluation, the larger the value, the larger the breaking point strength and the better the strength. The evaluation results are shown in Table 2. The sheet molded body of Sample 5 (Comparative Example) had a high hardness and could not be punched, so that the breaking point strength could not be measured.

(2) Elongation (elongation at break point)
The break point elongation (%) was measured for the sheet molded product of each sample in accordance with JIS K 6251: 2017.
As for the evaluation, the larger the value, the larger the elongation at the breaking point and the better the extensibility. The evaluation results are shown in Table 2. The sheet molded body of Sample 5 (Comparative Example) had a high hardness and could not be punched, so that the elongation at the breaking point could not be measured.

(3) Domain size For the resin compositions of Samples 1 to 4, the domain size at the time of preparing the presheet molded body (before curing) and the domain size at the time of producing the sheet molded body (after curing) are determined by an atomic force microscope (AFM). Was measured by. The measurement results are shown in Table 2.
The domain in this example is the copolymer A or B.

* 1 Phenoxy resin: "YP-70" manufactured by Nittetsu Chemical & Materials Co., Ltd.
* 2 Bisphenol A type epoxy resin: Mitsubishi Chemical Corporation "JER1001"
* 3 Glycerin Bis Anhydrotrimeritate Monoacetate: NEW JAPAN CHEMICAL CO., LTD. "Ricashid TMTA-C"
* 4 Copolymers A and B synthesized by the above method
* 5 Hydrogenated styrene-based thermoplastic elastomer (SEBS): Asahi Kasei Corporation "Tough Tech (registered trademark) M1913"
* 6 Zinc dimethyldithiocarbamate, "2-PZ"
* 7 6-tert-Butyl-4- [3-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepine-6-yl) ) Oxy] Propyl] -2-Methylphenol: Sumitomo Chemical Co., Ltd. "Smilizer (registered trademark) GP"

From the results of the examples shown in Table 2, it can be seen that the sample of the sheet molded product of the example according to the present invention has both strength and elongation at a high level. On the other hand, since the sample of the sheet molded product of the comparative example had high hardness and was not flexible, neither the breaking point strength nor the breaking point elongation could be measured.
Regarding the domain size, there is a tendency for the domain size to become finer due to the presence of the vulcanization accelerator.

Claims

Epoxy resin and
A crystalline copolymer having a conjugated diene unit and a non-conjugated olefin unit and a proportion of butylene units of 0 mol%.
A resin composition comprising, and a curing agent.
The resin composition according to claim 1, wherein the content of the epoxy resin is 35 to 65% by mass with respect to the total content of the epoxy resin and the copolymer.
The resin composition according to claim 1 or 2, further comprising a thermoplastic resin.
The content of the epoxy resin is 15 to 50% by mass, and the content of the copolymer is 15 to 50% by mass with respect to the total content of the epoxy resin, the copolymer, and the thermoplastic resin. The resin composition according to claim 3, wherein the content of the thermoplastic resin is 30 to 60% by mass.
In addition, it contains an anti-aging agent
The resin composition according to any one of claims 1 to 4, wherein the antiaging agent has two or more phenyl groups containing a branched alkyl group.
The resin composition according to any one of claims 1 to 5, further comprising a styrene-based elastomer.
The resin composition according to any one of claims 1 to 6, further comprising a dithiocarbamate-based vulcanization accelerator.
The resin composition according to any one of claims 1 to 7, wherein the main chain of the copolymer has only an acyclic structure.
The resin composition according to any one of claims 1 to 8, wherein the copolymer further has an aromatic vinyl unit.
The copolymer has a conjugated diene unit content of 5 to 70 mol%, a non-conjugated olefin unit content of 25 to 94 mol%, and an aromatic vinyl unit content of 1 to 30 mol%. The resin composition according to any one of claims 1 to 9, wherein the resin composition is%.
The resin composition according to any one of claims 1 to 10, wherein the copolymer has a melting point of 30 to 130 ° C. as measured by a differential scanning calorimeter (DSC).
The resin composition according to any one of claims 1 to 11, wherein the copolymer has a weight average molecular weight (Mw) of 50,000 to 2,000,000.
The resin composition according to any one of claims 1 to 12, wherein the copolymer has a crystallinity of 0.5 to 50%.
The resin composition according to any one of claims 1 to 13, wherein the copolymer comprises only ethylene units as the non-conjugated olefin unit.
The resin composition according to any one of claims 9 to 14, wherein the copolymer contains a styrene unit as the aromatic vinyl unit.
The resin composition according to any one of claims 1 to 15, wherein the copolymer contains 1,3-butadiene units and / or isoprene units in the conjugated diene unit.
A sheet molded product, characterized in that the resin composition according to any one of claims 1 to 16 is used.